A kind of squaramide ionic organic catalyst and its synthesis method and application

Abstract

The present invention belongs to the technical field of catalysts and their applications, and relates to a squaramide ionic organic catalyst and a synthesis method and application thereof. The squaramide ionic organic catalyst has a structural formula as shown below: The catalyst disclosed in the present invention has a simple structure, an easy-to-operate synthesis route, and low cost. It has good catalytic activity in ring-opening polymerization reactions and alternating copolymerization reactions, can improve polymer purity and yield, and has strong industrial application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts and their applications, and relates to a squaramide ionic organic catalyst and a synthesis method and application thereof. Background Art

[0002] Compared with organometallic catalysts, organic / metal-free catalysts have the advantages of low biological toxicity, stable structure, good solubility, easy purification, good water and oxygen tolerance, easy availability of raw materials, simple synthesis and green environmental protection. As a result, organic / metal-free catalytic systems have achieved remarkable achievements in regulating the microscopic chain structure, stereostructure, sequence structure and even topological structure of polymers. In polymerization reactions, the catalytic activity and selectivity of organic / metal-free catalysts are comparable to or even exceed those of organometallic catalysts. At present, organic / metal-free catalytic polymerization has become an important part of green and sustainable development chemistry and materials research, especially in the fields of microelectronics and biomedicine that have strict requirements on metal residues in polymer materials. Organic / metal-free catalytic polymerization plays an irreplaceable role.

[0003] Organic / metal-free catalysts mainly include organic bases, organic (proton or Lewis) acids, and hydrogen bond donor-acceptor bifunctional catalysts. Among them, organic base catalysts are the most widely used, mainly including neutral (uncharged) organic bases such as N-heterocyclic carbenes, amidines, guanidines, phosphazene bases, and organophosphorus compounds, which can activate substrates (such as initiators), monomers, etc. by exerting their alkalinity or nucleophilicity. In the polymerization reaction system, the catalytic activity of organic base catalysts often depends on the strength of their alkalinity, but for neutral organic bases, the stronger the alkalinity, the more complex the conjugated structure is. The complex conjugated structure will lead to limited range and flexibility of catalyst activity regulation, cumbersome catalyst synthesis process, increased cost, and reduced practicality. These limitations of neutral organic bases greatly limit their industrial application.

[0004] Literature Zhuolun Jiang, et al., Ionic Organocatalyst with a Urea Anion and Tetra-n-utyl Ammonium Cation for Rapid, Selective, and Versatile Ring-Opening Polymerization of Lactide. ACS Macro Lett. 2019, 8 (7), 759-765, through a simple dehydration reaction between tetra-n-butylammonium hydroxide and N, N-disubstituted thiourea / urea, a series of hydrogen bond donor-acceptor bifunctional ionic organic catalysts were obtained, which have significant efficiency and controllability in catalyzing the ring-opening polymerization of lactide. After ionization of thiourea / urea and quaternary ammonium base through dehydration reaction, the anion part activates the initiator and the hydroxyl group at the end of the growing chain by hydrogen bonding, which is the main source of catalytic activity; and the remaining NH group can activate the monomer through hydrogen bonding, thereby achieving dual and synergistic activation of the monomer and initiator, thereby improving the catalytic efficiency and selectivity at the same time. Compared with neutral organic bases, the structure and preparation method of ionic organic catalysts are simpler, and their catalytic activity can be widely and flexibly adjusted through the rich substituent structures on the two N atoms. However, the full play of the bifunctional synergistic catalysis requires that the remaining NH group after ionization still has a strong hydrogen bond donor effect, which requires the catalyst precursor to have sufficient acidity. However, the intrinsic acidity of urea is low, so it often requires a benzene ring with multiple strong electron-withdrawing groups (such as F atoms and trifluoromethyl groups) as the N-substituent; although the intrinsic acidity of thiourea is higher than that of urea, it still requires a benzene ring with a certain amount of electron-withdrawing groups (such as Cl, F atoms and trifluoromethyl groups) as the N-substituent to have sufficient hydrogen bond donor effect, and the biological toxicity of the catalyst caused by the sulfur atom cannot be ignored. Studies have shown that although benzene ring substituents with electron-withdrawing conjugation effects (such as nitro, cyano, carbonyl, etc.) can increase the acidity of thiourea and urea, they are also strong hydrogen bond acceptors, which can damage or even completely lose the catalytic activity, thereby reducing the yield and purity of the product in the polymerization reaction. Summary of the invention

[0005] In view of the technical problems of low activity, complex structure and high cost of existing ionic organic catalysts, the present invention discloses a squaramide ionic organic catalyst and a synthesis method and application thereof. The catalyst has a simple structure, an easy-to-operate synthesis route, low cost, good catalytic activity in ring-opening polymerization and alternating copolymerization, and can improve the purity and yield of copolymers.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A square amide ionic organic catalyst, the structural formula of which is shown below:

[0008]

[0009] Where;

[0010] Y means N or P;

[0011] R 3 , R 4 , R 5 , R 6 Respectively represent four independent hydrocarbon groups with 1 to 12 carbon atoms;

[0012] R 1 and R 2 Each independently selected from C1-C10 straight chain alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl, R 7 -phenyl or R 7 -naphthyl; said R 7 -F, -Cl, -Br, -CF 3 、-OCH 3 At least one substituent selected from the group consisting of alkyl, N,N-disubstituted alkyl and N,N-disubstituted alkyl.

[0013] A method for synthesizing a squaramide ionic organic catalyst comprises the following steps:

[0014] Compound A, compound B and organic solvent tetrahydrofuran are mixed, reacted under vacuum conditions of 0.01 mbar to 1 mbar for 2 h to 4 h, and then dehydrated at 70° C. to 80° C. to obtain a solid product, which is a square amide ionic organic catalyst;

[0015] The structural formula of the compound A is shown in formula (1):

[0016]

[0017] In the above formula, R 1 and R 2 Each independently selected from C1-C10 straight chain alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl, R 7 -phenyl or R 7 -naphthyl; said R 7 -F, -Cl, -Br, -CF 3 、-OCH 3 , alkyl and N,N-disubstituted alkyl;

[0018] The structural formula of the compound B is shown in formula (2):

[0019]

[0020] In the above formula, Y represents N or P; R 3 , R 4 , R 5 , R 6 They represent four independent hydrocarbon groups having 1 to 12 carbon atoms.

[0021] Furthermore, the molar ratio of compound A to compound B is (1-10):1, the dosage ratio of compound B to organic solvent is 0.5mmol:15ml; the organic solvent is tetrahydrofuran, 2-methyltetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, toluene or acetonitrile.

[0022] The invention discloses an application of a squaramide ionic organic catalyst in the ring-opening polymerization reaction of a cyclic ester monomer or a cyclic carbonate monomer.

[0023] The invention discloses an application of a squaramide ion-type organic catalyst in the alternating copolymerization reaction of an epoxy compound and an isothiocyanate compound.

[0024] The invention discloses an application of a squaramide ionic organic catalyst in the alternating copolymerization reaction of epoxy compounds and phthalic anhydride.

[0025] Furthermore, the reaction conditions during the application are: temperature of 20°C to 60°C, and time of 5min to 68h.

[0026] Furthermore, the cyclic ester monomer is ε-caprolactone, δ-valerolactone, racemic lactide, levorotatory lactide, dextral lactide or C1-C12 δ-alkyl valerolactone; and the cyclic carbonate monomer is trimethylene carbonate.

[0027] Furthermore, the epoxy compound is ethylene oxide, C1-C20 straight-chain alkyl ethylene oxide, C1-C16 straight-chain alkyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, glycidyl methacrylate, cyclohexene oxide, 4-vinyl cyclohexene oxide or limonene oxide.

[0028] Furthermore, the isothiocyanate compound is at least one of methyl isothiocyanate, linear alkyl isothiocyanate, alicyclic isothiocyanate, isopropyl isothiocyanate, sec-butyl isothiocyanate, isobutyl isothiocyanate, benzyl isothiocyanate, phenyl isothiocyanate, o- / m- / p-toluene isothiocyanate, benzoyl isothiocyanate, chloroethyl isothiocyanate, cyclohexyl methyl isothiocyanate and allyl isothiocyanate; the linear alkyl has 2 to 20 carbon atoms, and the alicyclic ring in the alicyclic isothiocyanate has 3 to 12 carbon atoms.

[0029] The beneficial effects of the present invention are:

[0030] 1. The catalyst of the present invention uses squaramide derivatives as raw materials. Compared with commonly used classical hydrogen bond donor organic small molecules, squaramide has higher acidity when containing the same N-substituent, which can avoid the introduction of S and halogen (mainly Cl and F) atoms into the catalyst molecular structure. The catalyst is constructed only by the C, H, O, and N atoms of squaramide itself, so as to obtain sufficient hydrogen bond strength and synergistic catalytic effect, thereby simplifying the catalyst structure and synthesis path, reducing costs, and further improving the biosafety and environmental friendliness of the organic catalyst.

[0031] 2. In the present invention, the squaramide derivatives are subjected to a dehydration reaction with tetraalkyl-substituted ammonium hydroxide / phosphorus. Due to the structure of the squaramide itself, a squaramide-based ionic organic catalyst system with rich structure and stable properties can be easily synthesized.

[0032] 3. In the present invention, the ionic organic catalyst of the quaternary amide type can flexibly change the structure of the two N-substituents and the tetraalkylammonium / phosphonium counterion, as well as the ratio of the catalyst ion part and the neutral part to adjust the catalytic activity to meet the needs of different polymerization reactions. In addition, the ionic organic catalyst of the quaternary amide type can achieve dual activation of the monomer and the initiator under the action of the anion and the retained NH group, which greatly ensures that the polymerization reaction is carried out in a controllable and efficient manner, thereby solving the problem of limited range and flexibility of activity adjustment of existing single-component organic strong base catalysts.

[0033] 4. In the present invention, the squaramide ionic organic catalyst is used in combination with different initiators (such as functionalized initiators, multifunctional initiators, macromolecular initiators) and monomers to efficiently and controllably carry out the ring-opening polymerization of cyclic ester monomers and cyclic carbonate monomers to prepare polymers with controllable molecular weight and clear and rich structures (having structural characteristics such as end group functionalization, side group functionalization, block, multi-block, star-shaped and grafted), especially polyester / polycarbonate and copolymers with polyester / polycarbonate as the main components, which are flexible and convenient to use.

[0034] 5. In the present invention, the squaramide ionic organic catalyst can effectively inhibit or even eliminate the side reactions such as isothiocyanate trimerization, epoxy and isothiocyanate dimerization in the alternating copolymerization of epoxy compounds and isothiocyanates, improve the purity and yield of the copolymer, make the epoxy and isothiocyanate compounds undergo strict alternating copolymerization, and completely avoid the homopolymerization of epoxy and the formation of polyether segments.

[0035] 6. In the present invention, the squaramide ionic organic catalyst can realize the alternating copolymerization of epoxy compounds and phthalic anhydride at a relatively low temperature (such as room temperature), freeing the reaction from the need for high temperature and high pressure conditions, greatly improving the simplicity, flexibility and safety of the operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the SEC curve of the crude product obtained by the ring-opening polymerization of lactide catalyzed by Sq1A3;

[0037] Figure 2 The crude product obtained by the ring-opening polymerization of lactide catalyzed by Sq1A3 1 HNMR spectrum;

[0038] Figure 3 This is the SEC curve of the crude product obtained by the ring-opening polymerization of δ-valerolactone catalyzed by Sq5A3;

[0039] Figure 4 The crude product obtained by the ring-opening polymerization of δ-valerolactone catalyzed by Sq5A3 1 HNMR spectrum;

[0040] Figure 5 This is the SEC curve of the crude product obtained by the ring-opening polymerization of ε-caprolactone catalyzed by Sq5A2;

[0041] Figure 6 The crude product obtained by ring-opening polymerization of ε-caprolactone catalyzed by Sq5A2 1 H NMR spectrum;

[0042] Figure 7 This is the SEC curve of the purified product obtained by the ring-opening polymerization of lactide catalyzed by Sq1A3;

[0043] Figure 8 The purified product obtained by the ring-opening polymerization of lactide catalyzed by Sq1A3 1 HNMR spectrum;

[0044] Fig. 9 This is the MALDI-TOF spectrum of the purified product obtained by the ring-opening polymerization of lactide catalyzed by Sq1A3;

[0045] Fig.10 This is the SEC curve of the purified product obtained by alternating copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by Sq5A3;

[0046] Fig.11 The purified product was obtained by alternating copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by Sq5A3 1 HNMR spectrum;

[0047] Fig.12 This is the SEC curve of the crude product obtained by the alternating copolymerization of propylene oxide and isopropyl isocyanate catalyzed by Sq5A3;

[0048] Fig.13 The crude product obtained by the alternating copolymerization of propylene oxide and isopropyl cyanide sulfate catalyzed by Sq5A31 HNMR spectrum;

[0049] Fig.14 This is the SEC curve of the crude product obtained by the alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq5A3;

[0050] Fig.15 The crude product obtained by alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq5A3 1 HNMR spectrum;

[0051] Fig.16 This is the SEC curve of the crude product obtained by the alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq10A3;

[0052] Fig.17 The crude product obtained by alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq10A3 1 HNMR spectrum

[0053] Fig.18 This is the SEC curve of the crude product obtained by the alternating copolymerization of styrene oxide and phthalic anhydride catalyzed by Sq5A3;

[0054] Fig.19 The crude product obtained by alternating copolymerization of styrene oxide and phthalic anhydride catalyzed by Sq5A3 1 HNMR spectrum. DETAILED DESCRIPTION

[0055] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0056] The present invention prepares ionic organic catalysts by dehydration reaction of squaramide and quaternary ammonium / phosphorus base, and then applies them to ring-opening polymerization of cyclic ester or cyclic carbonate monomers, alternating copolymerization of epoxy compounds and phthalic anhydride, and alternating copolymerization of epoxy compounds and isothiocyanate.

[0057] The quaternary amide ionic organic catalyst provided by the present invention has a structural formula as shown below:

[0058]

[0059] Where;

[0060] Y means N or P;

[0061] R 3 , R 4 , R 5 , R 6 Respectively represent four independent hydrocarbon groups with 1 to 12 carbon atoms;

[0062] R 1 and R 2Each independently selected from C1-C10 straight chain alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl, R 7 -phenyl or R 7 -Naphthyl; R 7 -F, -Cl, -Br, -CF 3 、-OCH 3 At least one substituent selected from the group consisting of alkyl, N,N-disubstituted alkyl and N,N-disubstituted alkyl.

[0063] The method for synthesizing the quaternary amide ionic organic catalyst of the present invention comprises the following steps:

[0064] Compound A, compound B and organic solvent tetrahydrofuran are mixed, reacted under vacuum conditions of 0.01 mbar to 1 mbar for 2 h to 4 h, and then dehydrated at 70° C. to 80° C. to obtain a solid product, which is a square amide ionic organic catalyst;

[0065] The structural formula of compound A is shown in formula (1).

[0066]

[0067] In the above formula, R 1 and R 2 Each independently selected from a C1-C10 straight chain alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl or a group containing -F, -Cl, -Br, -CF 3 、-OCH 3 phenyl and naphthyl having at least one substituent selected from the group consisting of alkyl, N,N-disubstituted alkyl.

[0068] The structural formula of compound B is shown in formula (2).

[0069]

[0070] In the above formula, Y represents N or P; R 3 , R 4 , R 5 , R 6 They represent four independent hydrocarbon groups having 1 to 12 carbon atoms.

[0071] The organic solvent of the present invention is tetrahydrofuran, 2-methyltetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, toluene or acetonitrile. Preferably, the organic solvent is tetrahydrofuran.

[0072] In the present invention, the molar ratio of compound A to compound B is (1-10):1, and the usage ratio of compound B to the organic solvent is 0.05mmol:15ml.

[0073] The reaction formula of the synthesis method is shown below.

[0074]

[0075] The square amide ionic organic catalyst prepared by the present invention has good catalytic activity, a simple synthesis route, a simple catalyst structure, low cost, and good catalytic activity, and can be well used for monomer ring-opening polymerization reaction and alternating copolymerization reaction.

[0076] Preferably, the squaramide ionic organic catalyst of the present invention is used for the ring-opening polymerization of cyclic ester monomers or cyclic carbonate monomers.

[0077] More preferably, the cyclic ester monomer is ε-caprolactone (ε-CL), δ-valerolactone (δ-VL), racemic lactide (LA), levorotatory lactide (LLA), dextrorotatory lactide (DLA), δ-alkyl valerolactone (5-alkyl-VL) with alkyl carbon number of 1 to 12. The cyclic carbonate monomer is trimethylene carbonate (TMC). The specific structural formula is as follows.

[0078]

[0079] Preferably, the squaramide ionic organic catalyst of the present invention is used for the alternating copolymerization of epoxy compounds and isothiocyanate compounds, and for the alternating copolymerization of epoxy compounds and phthalic anhydride.

[0080] Preferably, the epoxy compound is at least one of (1) ethylene oxide, (2) C1 to C20 linear alkyl ethylene oxide, (3) styrene oxide, (4) cyclohexene oxide, (5) 4-vinyl cyclohexene oxide, (6) limonene oxide, (7) C1 to C16 linear alkyl glycidyl ether, (8) isopropyl glycidyl ether, (9) tert-butyl glycidyl ether, (10) 2-ethylhexyl glycidyl ether, (11) phenyl glycidyl ether, (12) benzyl glycidyl ether, (13) allyl glycidyl ether, (14) propargyl glycidyl ether and (15) glycidyl methacrylate. The structure is shown in the figure below.

[0081]

[0082] Preferably, the isothiocyanate compound is at least one of (1) methyl isothiocyanate, (2) linear alkyl isothiocyanate, wherein the linear alkyl group contains 2 to 20 carbon atoms, (3) alicyclic isothiocyanate, wherein the alicyclic group contains 3 to 12 carbon atoms, (4) isopropyl isothiocyanate, (5) sec-butyl isothiocyanate, (6) isobutyl isothiocyanate, (7) benzyl isothiocyanate, (8) phenyl isothiocyanate, (9) o- / m- / p-toluene isothiocyanate, (10) benzoyl isothiocyanate, (11) chloroethyl isothiocyanate, (12) cyclohexyl methyl isothiocyanate and (13) allyl isothiocyanate. The specific structural formula is as follows.

[0083]

[0084] Furthermore, the polymerization reaction adopts solution polymerization or bulk polymerization, that is, the catalyst directly participates in the polymerization reaction, or the catalyst is prepared into a solution to participate in the reaction.

[0085] In solution polymerization, the solvent used is one or a mixture of two or more of toluene, acetone, tetrahydrofuran, 1,4-dioxane, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, propylene carbonate and acetonitrile. The catalyst concentration in the solution is 0.04 mol / L to 0.2 mol / L.

[0086] Furthermore, in the polymerization reaction, an alcohol initiator may be added according to the reaction requirements, and the molar ratio of the ionic organic catalyst to the alcohol initiator is (0.01-10):1.

[0087] Preferably, the alcohol initiator is: (1) methanol or a straight-chain alkyl alcohol having 2 to 18 carbon atoms, (2) isopropanol, (3) 2-butanol, (4) tert-butanol, (5) a 1-phenyl straight-chain alkyl alcohol having 1 to 10 alkyl carbon atoms, (6) allyl alcohol or a straight-chain terminal olefin 1-ol having 2 to 10 saturated carbon atoms, (7) 1-naphthalene methanol, (8) butene glycol, (9) ethylene glycol, (10) 1,4-butanediol, (11) terephthalimethanol, (12) 1,1,1-trimethylolpropane, (13) glycerol, (14) pentaerythritol, (15) dipentaerythritol, (16) sorbitol, (17) tripentaerythritol, (18) polyethylene glycol or polyethylene glycol monomethyl ether having a number average molecular weight of 400 to 20,000 g / mol. The specific structural formula is as follows.

[0088]

[0089] Furthermore, the reaction conditions of the catalyst are a temperature of 20 to 60° C. and a reaction time of 5 min to 68 h.

[0090] The catalyst, synthesis method and application in ring-opening polymerization and alternating copolymerization provided by the present invention are described below with several groups of specific embodiments.

[0091] It should be noted that the conversion rate of the cyclic ester monomer or cyclic carbonate monomer and the polymer structure characteristics in the following examples were tested by Bruker AV600 NMR spectrometer, CDCl 3 DMSO-d 6 as solvent and tetramethylsilane as internal standard.

[0092] The molecular weight and molecular weight dispersion of polyester or polycarbonate were measured by size exclusion chromatography (SEC) using an Agilent 1260 Infinity size exclusion chromatograph with tetrahydrofuran as the mobile phase, a column temperature of 35°C, and a flow rate of 1 mL / min. A series of polystyrene standard samples were used to make a calibration curve.

[0093] The mass spectrum peak of polyester was tested using a Bruker AutoflexШ Smartbeam MALDL-TOF mass spectrometer. The sample was dissolved in THF to form a 10 mg / mL solution, which was then mixed with a 10 mg / mL THF solution of sodium trifluoroacetate at a volume ratio of 5 / 1. The mixed solution was then mixed with a THF solution of 2,5-dihydroxybenzoic acid (20 mg / mL) at a volume ratio of 1 / 10, and 0.4 μL of the mixed solution was dropped onto the test plate for testing, and the mass spectrum peak of the sample was obtained by the cation reflection mode.

[0094] The parts described in the following examples are all molar parts.

[0095] Other operations not specifically described are routine operations in this field.

[0096] Example 1

[0097] This example is the synthesis of 1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq1A3).

[0098] The synthesis method of catalyst Sq1A3 is as follows:

[0099] 1,4-Diphenylsquaramide (0.648mmol), tetrabutylammonium hydroxide (0.54mmol) and 15mL tetrahydrofuran (THF) were added to a 50mL Schlenk bottle and stirred at 40°C for 4h. Then, the tetrahydrofuran (THF) was slowly removed under a vacuum of 0.1-0.01mbar, and the remaining solid was heated to 80°C under vacuum conditions for 2h. The generated solid was dissolved in 2.7mL dimethyl sulfoxide (DMSO) to prepare a 0.2mol / L catalyst solution.

[0100] Example 2

[0101] This example is the synthesis of 1,4-bis(4-p-methoxyphenyl)squaramide tetrabutylammonium catalyst (Sq2A3).

[0102] The synthesis method of catalyst Sq2A3 is as follows:

[0103] 1,4-bis(4-p-methoxyphenyl)squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed uniformly. Other operations were the same as those in Example 1.

[0104] Example 3

[0105] This example is the synthesis of 1,4-dicyclohexyl tetrabutylammonium squaramide catalyst (Sq5A3).

[0106] The synthesis method of catalyst Sq5A3 is as follows:

[0107] 1,4-dicyclohexyl squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed uniformly. Other operations were the same as those in Example 1.

[0108] Example 4

[0109] This example is the synthesis of 1,4-dicyclohexyl squaramide tetrabutylphosphonium catalyst (Sq5P1).

[0110] The synthesis method of catalyst Sq5P1 is as follows:

[0111] 1,4-Dicyclohexyl squaramide (0.648 mmol), tetrabutylphosphonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed evenly, and other operations were the same as those in Example 1.

[0112] Example 5

[0113] This example is the synthesis of 1,4-dicyclohexylsquarylamide tetramethylamine catalyst (Sq5A1).

[0114] The synthesis method of catalyst Sq5A1 is as follows:

[0115] 1,4-Dicyclohexyl squaramide (0.648 mmol), tetramethylammonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed uniformly, and other operations were the same as in Example 1.

[0116] Example 6

[0117] This example is the synthesis of 1,4-dicyclohexylsquarylamide benzyltrimethylamine catalyst (Sq5A2).

[0118] The synthesis method of catalyst Sq5A2 is as follows:

[0119] 1,4-dicyclohexyl squaramide (0.648 mmol), benzyltrimethylammonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed uniformly, and other operations were the same as those in Example 1.

[0120] Example 7

[0121] This example is the synthesis of 1,4-(2,5-di-p-methoxyphenyl)squaramide tetrabutylamine catalyst (Sq3A3).

[0122] The synthesis method of catalyst Sq3A3 is as follows:

[0123] 1,4-(2,5-di-p-methoxyphenyl)squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed uniformly, and other operations were the same as those in Example 1.

[0124] Example 8

[0125] This example is the synthesis of 1,4-(3,4,5-tri-p-methoxyphenyl)squaramide tetrabutylamine catalyst (Sq4A3).

[0126] The synthesis method of catalyst Sq4A3 is as follows:

[0127] 1,4-(3,4,5-tri-p-methoxyphenyl)squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed uniformly, and other operations were the same as those in Example 1.

[0128] Example 9

[0129] This example is the synthesis of 1,4-di-tert-butyl squaramide tetrabutylammonium catalyst (Sq10A3).

[0130] The synthesis method of catalyst Sq10A3 is as follows:

[0131] 1,4-tert-butyl squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed uniformly, and other operations were the same as those in Example 1.

[0132] Example 10

[0133] This example is the synthesis of 1,4-tricyclo[3,3,1,1(3,7)]decyl tetrabutylammonium squaramide catalyst (Sq11A3).

[0134] The synthesis method of catalyst Sq11A3 is as follows:

[0135] 1,4-tricyclo[3,3,1,1(3,7)]decyl squaramide (0.648 mmol), tetrabutylammonium hydroxide (0.54 mmol) and 15 mL of tetrahydrofuran (THF) were mixed evenly, and other operations were the same as those in Example 1.

[0136] The above-mentioned Examples 1 to 10 list 10 groups of square amide ionic organic catalysts with different structures, but the structure of the square amide ionic organic catalyst provided by the present invention is not limited thereto; in addition, during the synthesis process, the dosage ratio of the compounds and the synthesis parameters are arbitrarily selected within the aforementioned range of the present invention, and square amide ionic organic catalysts can be obtained.

[0137] The catalytic activity of the catalyst is further illustrated below by using the application of the catalysts of Examples 1 to 10.

[0138] Embodiment 11

[0139] This example is a ring-opening polymerization of lactide (LA) catalyzed by 1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq1A3).

[0140] In this embodiment, the reaction formula of the ring-opening polymerization is as follows.

[0141]

[0142] The method for preparing polylactide (PLA) by ring-opening polymerization of lactide (LA) catalyzed by catalyst (Sq1A3) is as follows.

[0143] (1) 2.88 g of LA was dissolved in 26.5 mL of dichloromethane (DCM) to prepare a 0.75 mol / L LA solution, and 0.3160 ​​g of 1-naphthalenemethanol (NtA) was dissolved in 40 mL of DCM to prepare a 0.05 mol / L NtA solution.

[0144] (2) Under an inert gas atmosphere, 75 parts of LA (1.0 mL, 0.75 mmol), 1 part of NtA (200 μL, 0.01 mmol), and 1 part of catalyst Sq1A3 (50 μL, 0.01 mmol) were added to a dried container and reacted at room temperature for 5 min. Then, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1According to HNMR test, the remaining crude product was poured into 20 mL of methanol to precipitate the polymer, and the final product was collected and dried in a vacuum oven at 40° C. overnight.

[0145] In this example, the SEC curve of the crude product prepared by the ring-opening polymerization of lactide catalyzed by catalyst Sq1A3 and 1 HNMR spectra, such as Figure 1 and Figure 2 shown.

[0146] See also Figure 1 and Figure 2 SEC and 1 The results of H NMR showed that the conversion rate of lactide LA was 90%, and the theoretical number average molecular weight (M n,th ) is 9.7 kg / mol, and the number average molecular weight (M n,SEC ) is 15.3 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 9.9 kg / mol, and the molecular weight distribution is 1.10.

[0147] Example 12

[0148] This example is a ring-opening polymerization of γ-butyrolactone (BL) catalyzed by 1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq1A3).

[0149] The catalyst Sq1A3 was dissolved in 2.7 mL of γ-butyrolactone (BL), and the other steps were the same as those in Example 11. After reacting at room temperature for 5 min, 0.5 mL of acetic acid was added to terminate the reaction, and a small amount of the crude product was taken for SEC and 1 H NMR test.

[0150] The conversion rate of BL was 81%, and the theoretical number average molecular weight (M n,th ) is 8.7 kg / mol, and the number average molecular weight (M n,SEC ) is 12.3 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 8.7 kg / mol and the molecular weight distribution is 1.07.

[0151] Example 13

[0152] This example is a ring-opening polymerization of LA catalyzed by 1,4-bis(4-p-methoxyphenyl)squaramide tetrabutylammonium catalyst (Sq2A3).

[0153] The method for preparing poly-PLA by ring-opening polymerization of LA catalyzed by catalyst (Sq2A3) is the same as that in Example 11.

[0154] According to the SEC and 1 The results of H NMR showed that the conversion rate of LA was 100%, and the theoretical number average molecular weight (M n,th ) is 10.8 kg / mol, and the number average molecular weight (M n,SEC ) is 14.3 kg / mol, 1 The number average molecular weight (M) calculated by HNMR n,NMR ) is 10.1 kg / mol, and the molecular weight distribution is 1.15.

[0155] Embodiment 14

[0156] This example is a ring-opening polymerization of LA catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0157] The method for preparing PLA by ring-opening polymerization of LA catalyzed by catalyst (Sq5A3) is the same as that in Example 11.

[0158] According to the SEC and 1 The results of H NMR showed that the conversion rate of LA was 100%, and the theoretical number average molecular weight (M n,th ) is 10.8 kg / mol, and the number average molecular weight (M n,SEC ) is 10.8 kg / mol, 1 The number average molecular weight calculated by HNMR is (M n,NMR )11.5kg / mol, molecular weight distribution is 1.75.

[0159] Embodiment 15

[0160] This example is a ring-opening polymerization of δ-valerolactone (δ-VL) catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0161] In this embodiment, the reaction formula for the ring-opening polymerization of δ-valerolactone (δ-VL) is shown below.

[0162]

[0163] In an inert gas atmosphere, 100 parts of δ-VL (0.9 mL, 9 mmol), 1 part of benzyl alcohol (90 μL, 0.09 mmol) and 1 part of catalyst Sq5A3 (0.45 mL, 0.09 mmol) were added to a dried container. After reacting at room temperature for 5 min, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate the polymer. The final product was collected and dried in a vacuum oven at 40°C overnight.

[0164] SEC curve of crude product prepared by ring-opening polymerization of δ-valerolactone catalyzed by catalyst Sq5A3 and 1 H NMR spectrum Figure 3 and Figure 4 shown.

[0165] See also Figure 3 and Figure 4 , according to the SEC and 1 The results of H NMR showed that the conversion rate of δ-VL was 100%, and the theoretical number average molecular weight (M n,th ) is 10.0 kg / mol, and the number average molecular weight (M n,SEC ) is 12.4 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 10.1 kg / mol, and the molecular weight distribution is 1.36.

[0166] Example 16

[0167] This example is the ring-opening polymerization of ε-caprolactone (ε-CL) catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0168] In this embodiment, the ring-opening polymerization reaction formula of ε-caprolactone (ε-CL) is as follows.

[0169]

[0170] In an inert gas atmosphere, 100 parts of ε-CL (1.0 mL, 9 mmol), 1 part of benzyl alcohol (90 μL, 0.09 mmol) and 1 part of catalyst Sq5A3 (0.45 mL, 0.09 mmol) were added to a dried container. After reacting at room temperature for 2 h, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate the polymer, and the final product was collected and dried in a vacuum oven at 40°C overnight.

[0171] In this embodiment, according to SEC and 1 The results of H NMR showed that the conversion of ε-CL was 100%, and the theoretical number average molecular weight (M n,th ) is 11.4 kg / mol, and the number average molecular weight (M n,SEC ) is 14.6 kg / mol, 1The number average molecular weight (M) calculated by H NMR n,NMR ) is 11.9 kg / mol, and the molecular weight distribution It is 1.29.

[0172] Embodiment 17

[0173] This example is an ε-CL ring-opening polymerization catalyzed by 1,4-dicyclohexylsquaramide tetrabutylphosphine catalyst (Sq5P1).

[0174] The method for preparing polycaprolactone (PCL) by ring-opening polymerization of ε-caprolactone (ε-CL) catalyzed by catalyst (Sq5P1) is the same as that in Example 16. After reacting at room temperature for 2 h, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of crude product was taken for SEC and 1 H NMR test.

[0175] According to the SEC and 1 The results of H NMR showed that the conversion of ε-CL was 100%, and the theoretical number average molecular weight (M n,th ) is 11.4 kg / mol, and the number average molecular weight (M n,SEC ) is 13.4 kg / mol, 1 The number average molecular weight (M) calculated by HNMR n,NMR ) is 11.9 kg / mol, and the molecular weight distribution is 1.21.

[0176] Embodiment 18

[0177] This example is an ε-CL ring-opening polymerization catalyzed by 1,4-dicyclohexylsquaramide tetramethylamine catalyst (Sq5A1).

[0178] The method for preparing PCL by ring-opening polymerization of ε-CL catalyzed by catalyst (Sq5A1) was the same as that in Example 16. After reacting at room temperature for 2 h, 0.5 mL of acetic acid was added to terminate the reaction, and a small amount of crude product was taken for SEC and 1 H NMR test.

[0179] According to the SEC and 1 The results of H NMR were based on SEC and 1 The results of H NMR showed that the conversion of ε-CL was 76%, and the theoretical number average molecular weight (M n,th ) is 8.7 kg / mol, and the number average molecular weight (M n,SEC ) is 11.2 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 8.9 kg / mol, and the molecular weight distribution is 1.07.

[0180] Embodiment 19

[0181] This example is an ε-CL ring-opening polymerization catalyzed by 1,4-dicyclohexylsquarylamide benzyltrimethylamine catalyst (Sq5A2).

[0182] The method for preparing PCL by ring-opening polymerization of ε-CL catalyzed by catalyst (Sq5A2) was the same as that in Example 16. After reacting at room temperature for 2 h, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of crude product was taken for SEC and 1 H NMR test.

[0183] SEC curve of crude product prepared by ring-opening polymerization of ε-caprolactone catalyzed by catalyst Sq5A2 and 1 The H NMR spectra are shown in Figure 5 and Figure 6 shown.

[0184] See also Figure 5 and Figure 6 , according to the SEC and 1 The results of HNMR showed that the conversion of ε-CL was 45%, and the theoretical number average molecular weight (M n,th ) is 5.2 kg / mol, and the number average molecular weight (M n,SEC ) is 6.7 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 5.4 kg / mol, and the molecular weight distribution is 1.15.

[0185] Embodiment 20

[0186] This example is a ring-opening polymerization of δ-delta-DL catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0187] The reaction formula for the ring-opening polymerization of δ-delta-DL in this embodiment is as follows.

[0188]

[0189] In an inert gas atmosphere, 100 parts of δ-DL (1.6 mL, 9 mmol), 1 part of benzyl alcohol (90 μL, 0.09 mmol) and 1 part of catalyst Sq5A3 (0.45 mL, 0.09 mmol) were added to a dried container and reacted at room temperature for 15 min. 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1 HNMR test. The remaining crude product was poured into 20 mL of methanol to precipitate the polymer, and the final product was collected and dried in a vacuum oven at 40° C. overnight.

[0190] According to the SEC and 1 The results of HNMR showed that the conversion of δ-DL was 89%, and the theoretical number average molecular weight (M n,th ) is 15.2 kg / mol, and the number average molecular weight (M n,SEC ) is 19.7 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 15.6 kg / mol, and the molecular weight distribution is 1.17.

[0191] Embodiment 21

[0192] This example is a ring-opening polymerization of L-lactide (LLA) catalyzed by 1,4-(2,5-di-p-methoxyphenyl)squaramide tetrabutylamine catalyst (Sq3A3).

[0193] In this embodiment, the ring-opening polymerization reaction formula of L-lactide (LLA) is as follows.

[0194]

[0195] The method for preparing poly (L-lactide) (PLLA) by ring-opening polymerization of L-lactide (LLA) catalyzed by catalyst (Sq3A3) is as follows.

[0196] Under an inert gas atmosphere, 200 parts of LLA (2.7 mL, 2.0 mmol), 1 part of NtA (200 μL, 0.01 mmol) and 1 part of catalyst Sq3A3 (50 μL, 0.01 mmol) were added to a dried container and reacted at room temperature for 15 min. 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate the polymer. The final product was collected and dried in a vacuum oven at 40°C overnight.

[0197] According to the SEC and 1 The results of HNMR showed that the conversion rate of LLA was 100%, and the theoretical number average molecular weight (M n,th ) is 28.8 kg / mol, and the number average molecular weight (M n,SEC ) is 37.4 kg / mol, 1 The number average molecular weight (M) calculated by HNMR n,NMR ) is 30.8kg / mol, and the molecular weight distribution is 1.09.

[0198] Embodiment 22

[0199] This example is a LLA ring-opening polymerization catalyzed by 1,4-(3,4,5-tri-p-methoxyphenyl)squaramide tetrabutylamine catalyst (Sq4A3).

[0200] In this embodiment, the reaction formula of LLA ring-opening polymerization is as follows.

[0201]

[0202] In this embodiment, the method for preparing PLLA by ring-opening polymerization of LLA catalyzed by catalyst (Sq4A3) is as follows.

[0203] The operation of this example is the same as that of Example 11, except that lactide is replaced with L-lactide, and the initiator is replaced with 1,1,1-trihydroxypropane. After reacting at room temperature for 2 minutes, 0.5 mL of acetic acid is added to terminate the reaction. A small amount of crude product is taken for SEC and 1 HNMR test. The remaining crude product was poured into 20 mL of methanol to precipitate the polymer. The final product was collected and dried in a vacuum oven at 40°C overnight.

[0204] According to the SEC and 1 The results of H NMR showed that the conversion rate of LLA was 88%, and the theoretical number average molecular weight (M n,th ) is 9.5 kg / mol, and the number average molecular weight (M n,SEC ) is 12.3 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 11.0 kg / mol, and the molecular weight distribution is 1.04.

[0205] Embodiment 23

[0206] This example is a ring-opening copolymerization of ε-CL and L-lactide (LLA) catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0207] In this embodiment, the ring-opening copolymerization reaction formula of L-lactide (LLA) is as follows.

[0208]

[0209] In this embodiment, the ring-opening copolymerization method of ε-CL and L-lactide (LLA) catalyzed by catalyst (Sq5A3) is as follows.

[0210] Under an inert gas atmosphere, 100 parts of ε-CL (1.0 mL, 9 mmol), 1 part of NtA (90 μL, 0.09 mmol) and 1 part of catalyst Sq5A3 (0.45 mL, 0.09 mmol) were added to a dried container and reacted at room temperature for 1 h. A small amount of the crude product was taken for SEC and 1 H NMR test.

[0211] According to the SEC and 1 The results of H NMR showed that the conversion of ε-CL was 86%, and the number average molecular weight (M n,SEC ) is 12.8 kg / mol, 1 The number average molecular weight calculated by H NMR is 10.3 kg / mol, and the molecular weight distribution is 1.07.

[0212] Then, 75 parts of LLA (1.0 mL, 0.75 mmol) was added and reacted at room temperature for 1 min. Then, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate the polymer. The final product was collected and dried in a vacuum oven at 40°C overnight.

[0213] According to the SEC and 1 The results of H NMR showed that the conversion rate of LA was 100%, and the number average molecular weight (M n,SEC ) is 28.4 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 21.8 kg / mol, and the molecular weight distribution is 1.14.

[0214] Embodiment 24

[0215] This example is a ring-opening polymerization of LA catalyzed by 1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq1A3).

[0216] Under an inert gas atmosphere, 35 parts of LA (0.47 mL, 0.35 mmol), 1 part of NtA (200 μL, 0.01 mmol) and 1 part of catalyst Sq1A3 (50 μL, 0.01 mmol) were added to a dried container. After reacting at room temperature for 5 min, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0217] In this example, the SEC curve of the purified product prepared by the ring-opening polymerization of lactide catalyzed by catalyst Sq1A3, 1 HNMR spectra and MALDI-TOF spectra, see Figure 7 , Figure 8 and Fig. 9 As shown, where: Fig. 9 (a) is the MALDI-TOF spectrum of the purified product. Fig. 9 (b) Fig. 9 Enlarged view of the dashed part in (a).

[0218] See also Figure 7 to Figure 9 , according to the SEC and 1 The results of H NMR showed that the conversion rate of LA was 100%, and the theoretical number average molecular weight (M n,th ) is 4.9 kg / mol, and the number average molecular weight (M n,SEC ) is 7.2 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 5.1 kg / mol, and the molecular weight distribution is 1.05.

[0219] Embodiment 25

[0220] This example is an alternating copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0221] In this embodiment, the reaction formula for the alternating copolymerization of propylene oxide and phenyl isothiocyanate is as follows.

[0222]

[0223] In this embodiment, the method of catalyzing the alternating copolymerization of propylene oxide and phenyl isothiocyanate using catalyst Sq5A3 is as follows.

[0224] The catalyst Sq5A3 is insoluble in any solvent. 100 parts of phenyl isothiocyanate (1.6 mL, 13.4 mmol), 150 parts of propylene oxide (1.4 mL, 20 mmol), and 1 part of cis-butene glycol (268 μL, 0.134 mmol) were directly added to a Schlenk bottle under an inert atmosphere. After reacting at room temperature for 26 h, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1 HNMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0225] SEC curves and 1 HNMR spectra, respectively. Fig.10 and Fig.11 shown.

[0226] See also Fig.10 and Fig.11 , according to the SEC and 1 The results of H NMR showed that the conversion rate of phenyl isothiocyanate was 75%, and the theoretical number average molecular weight (M n,th ) is 14.5 kg / mol, and the number average molecular weight (M n,SEC ) is 11.8 kg / mol, 1 The number average molecular weight (M) calculated by HNMR n,NMR ) is 11.8 kg / mol, and the molecular weight distribution is 1.07.

[0227] Embodiment 26

[0228] This example is an alternating copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by 1,4-bis(4-p-methoxyphenyl)squaramide tetrabutylammonium catalyst (Sq2A3).

[0229] In this embodiment, the ionic catalyst Sq2A3 was dissolved in DMSO to prepare a 0.2 mol / L catalyst solution. Then, 30 parts of phenyl isothiocyanate (0.8 mL, 6.7 mmol), 45 parts of propylene oxide (0.7 mL, 10 mmol), 1 part of cis-butene glycol (450 μL, 0.225 mmol) and 0.1 part of Sq5A3 (0.0225 mmol) were added to a dried container under an inert atmosphere, and reacted at room temperature for 36 h. Then, 0.5 mL of acetic acid was added to terminate the reaction, and a small amount of crude product was taken for SEC and 1 HNMR test.

[0230] According to the SEC and 1 The results of HNMR showed that the conversion rate of phenyl isothiocyanate was 74%, and the theoretical number average molecular weight (M n,th ) is 4.3 kg / mol, and the number average molecular weight (M n,SEC ) is 3.3 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 2.9 kg / mol, and the molecular weight distribution is 1.08.

[0231] Embodiment 27

[0232] This example is an alternating copolymerization of propylene oxide and isopropyl isothiocyanate catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0233] In this embodiment, the alternating copolymerization reaction formula is as follows.

[0234]

[0235] In this example, the alternating copolymerization process of propylene oxide and isopropyl isothiocyanate catalyzed by catalyst (Sq5A3) was the same as that in Example 26, except that catalyst Sq2A3 was replaced by Sq5A3, phenyl isothiocyanate was replaced by isopropyl isothiocyanate, and the reaction was continued at room temperature for 48 h, and 0.5 mL of acetic acid was added to terminate the reaction. A small amount of crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0236] SEC curves of crude products prepared by alternating copolymerization of propylene oxide and isopropyl isocyanate catalyzed by Sq5A3 and 1 HNMR spectra, respectively. Fig.12 and Fig.13 shown.

[0237] See also Fig.12 and Fig.13 , according to the SEC and 1 The results of H NMR showed that the conversion rate of isopropyl isothiocyanate was 98%, and the theoretical number average molecular weight (M n,th ) is 4.7 kg / mol, and the number average molecular weight (M n,SEC ) is 3.2 kg / mol, 1 The number average molecular weight (M) calculated by HNMR n,NMR ) is 3.2kg / mol, and the molecular weight distribution is 1.08.

[0238] Embodiment 28

[0239] This example is an alternating copolymerization of propylene oxide and isoethyl isothiocyanate catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0240] In this embodiment, the reaction formula of alternating copolymerization is as follows.

[0241]

[0242] In this example, the alternating copolymerization reaction catalyzed by catalyst Sq5A3 was the same as that in Example 26, except that catalyst Sq2A3 was replaced by Sq5A3, phenyl isothiocyanate was replaced by isoethyl isothiocyanate, and the reaction was continued at room temperature for 96 h, and 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0243] According to the SEC and 1 The results of HNMR showed that the conversion rate of ethyl isothiocyanate was 98%, and the theoretical number average molecular weight (M n,th ) is 4.2 kg / mol, and the number average molecular weight (M n,SEC ) is 4.4 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 4.7kg / mol, and the molecular weight distribution is 1.14.

[0244] Embodiment 29

[0245] This example is an alternating copolymerization of propylene oxide and phenyl isothiocyanate catalyzed by 1,4-diphenylsquaramide tetrabutylammonium catalyst (Sq1A3).

[0246] In this example, the alternating copolymerization method of propylene oxide and phenyl isothiocyanate catalyzed by catalyst Sq1A3 was the same as that in Example 25, except that catalyst Sq5A3 was replaced by Sq1A3. After reacting at room temperature for 36 h, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0247] According to the SEC and 1 The results of HNMR showed that the conversion rate of phenyl isothiocyanate was 94%, and the theoretical number average molecular weight (M n,th ) is 18.2 kg / mol, and the number average molecular weight (M n,SEC ) is 10.1 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 19.4 kg / mol, and the molecular weight distribution is 1.17.

[0248] Embodiment 30

[0249] This example is an alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3) at 60°C.

[0250] In this embodiment, the reaction formula of the alternating copolymerization of catalyst Sq5A3 is as follows.

[0251]

[0252] In this embodiment, the method for alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by catalyst Sq5A3 is as follows.

[0253] Under inert conditions, 50 parts of phthalic anhydride (1 mL, 1 mmol), 150 parts of propylene oxide (210 μL, 3 mmol), 1 part of terephthalic acid (40 μL, 0.02 mmol) and 1 part of catalyst Sq5A3 (100 μL, 0.02 mmol) were added to a dried container, reacted at 60°C for 48 h, and then 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was taken for SEC and 1 HNMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0254] According to the SEC and 1 The results of H NMR showed that the conversion rate of phthalic anhydride was 52%, and the theoretical number average molecular weight (M n,th ) is 5.2 kg / mol, and the number average molecular weight (M n,SEC ) is 2.6 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 6.6 kg / mol, and the molecular weight distribution is 1.25.

[0255] Embodiment 31

[0256] This example is an alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3) at room temperature.

[0257] The operation of this example is the same as that of Example 30. After reacting at room temperature for 48 hours, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0258] In this example, the SEC curve of the crude product prepared by the alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by catalyst Sq5A3 and 1 H NMR spectra, respectively. Fig.14 and Fig.15 shown.

[0259] See also Fig.14 and Fig.15 , according to the SEC and 1 The results of H NMR showed that the conversion rate of phthalic anhydride was 41%, and the theoretical number average molecular weight (M n,th ) is 4.0 kg / mol, and the number average molecular weight (M n,SEC ) is 2.3 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 3.7kg / mol, and the molecular weight distribution is 1.26.

[0260] Embodiment 32

[0261] This example is an alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by 1,4-di-tert-butyl squaramide tetrabutylammonium catalyst (Sq10A3).

[0262] The method for the alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by the catalyst (Sq10A3) is as follows: The operation is the same as in Example 30. After reacting at 60°C for 48 hours, 0.5 mL of acetic acid is added to terminate the reaction. A small amount of crude product is taken for SEC and 1 HNMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0263] SEC curves of crude products prepared by alternating copolymerization of propylene oxide and phthalic anhydride catalyzed by Sq10A3 and 1 H NMR spectra, respectively. Fig.16 and Fig.17 shown.

[0264] See also Fig.16 and Fig.17 , according to the SEC and 1 The results of H NMR showed that the conversion rate of phthalic anhydride was 52%, and the theoretical number average molecular weight (M n,th ) is 5.2 kg / mol, and the number average molecular weight (M n,SEC ) is 3.3 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 7.8kg / mol, and the molecular weight distribution is 1.13.

[0265] Embodiment 33

[0266] This example is an alternating copolymerization of styrene oxide and phthalic anhydride catalyzed by 1,4-dicyclohexylsquaramide tetrabutylammonium catalyst (Sq5A3).

[0267] In this embodiment, the reaction formula of alternating copolymerization is as follows.

[0268]

[0269] The method for the alternating copolymerization of styrene oxide and phthalic anhydride catalyzed by catalyst Sq5A3 is as follows.

[0270] Under inert conditions, 20 parts of phthalic anhydride (0.4 mL, 0.04 mmol), 740 parts of styrene oxide (1.5 mL, 14.8 mmol), 1 part of p-phenylenediol (40 μL, 0.02 mmol) and 1 part of catalyst Sq5A3 (100 μL, 0.02 mmol) were added to a dried container, reacted at 60 ° C for 68 h, and then 0.5 mL of acetic acid was added to terminate the reaction. A small amount of crude product was taken for SEC and 1 H NMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0271] SEC curves of crude products prepared by alternating copolymerization of styrene oxide and phthalic anhydride catalyzed by Sq5A3 1 H NMR spectra, respectively. Fig.18 and Fig.19 shown.

[0272] See also Fig.18 and Fig.19 , according to the SEC and 1 The results of H NMR showed that the conversion rate of phthalic anhydride was 100%, and the theoretical number average molecular weight (M n,th ) is 4.9 kg / mol, and the number average molecular weight (M n,SEC ) is 1.1 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 2.5kg / mol, molecular weight distribution is 1.53.

[0273] Embodiment 34

[0274] This embodiment is an alternating copolymerization of styrene oxide and phthalic anhydride catalyzed by 1,4-tricyclo[3,3,1,1(3,7)]decyl squarylamide tetrabutylammonium catalyst (Sq11A3).

[0275] The method for the alternating copolymerization of styrene oxide and phthalic anhydride catalyzed by the catalyst (Sq11A3) was the same as that in Example 33. After the reaction was carried out at 60°C for 68 hours, 0.5 mL of acetic acid was added to terminate the reaction. A small amount of the crude product was subjected to SEC and 1 HNMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0276] According to the SEC and 1 The results of HNMR showed that the conversion rate of phthalic anhydride was 100%, and the theoretical number average molecular weight (M n,th ) is 4.9 kg / mol, and the number average molecular weight (M n,SEC ) is 1.7 kg / mol, 1 The number average molecular weight (M) calculated by H NMRn,NMR ) is 4.8kg / mol, and the molecular weight distribution is 1.23.

[0277] Embodiment 35

[0278] This embodiment is an alternating copolymerization of isopropyl glycidyl ether and phthalic anhydride catalyzed by 1,4-tricyclo[3,3,1,1(3,7)]decyl squarylamide tetrabutylammonium catalyst (Sq11A3).

[0279] In this embodiment, the reaction formula of alternating copolymerization is as follows.

[0280]

[0281] The process of alternating copolymerization in this example is the same as that in Example 33, except that styrene oxide is replaced with isopropyl glycidyl ether. After reacting at 60°C for 68 hours, 0.5 mL of acetic acid is added to terminate the reaction. A small amount of the crude product is taken for SEC and 1 HNMR test. The remaining crude product was poured into 20 mL of methanol to precipitate a polymer.

[0282] According to the SEC and 1 The results of HNMR showed that the conversion rate of phthalic anhydride was 100%, and the theoretical number average molecular weight (M n,th ) is 5.3 kg / mol, and the number average molecular weight (M n,SEC ) is 2.7 kg / mol, 1 The number average molecular weight (M) calculated by H NMR n,NMR ) is 4.4 kg / mol, and the molecular weight distribution is 1.44.

[0283] It can be seen from the above embodiments that the catalyst of the present invention is simple to synthesize, has low cost, simple catalyst structure, good catalytic activity and good biosafety; the conversion rate of ring-opening polymerization at room temperature can quickly reach 100%; in the alternating copolymerization reaction at room temperature, the conversion rate of isothiocyanate compounds reaches 98%, and the conversion rate of phthalic anhydride is 100%. The catalyst has a wide range of industrial applications, a high yield of the product, good purity, and has good application prospects.

[0284] The above embodiments are only preferred implementation modes of the present invention and are only used to explain the present invention rather than to limit the present invention. Any changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit of the present invention should fall within the scope of protection of the present invention.

Claims

1. A quaternary amide ionic organic catalyst, It is characterized in that The structural formula of the square amide ionic organic catalyst is shown below: Where: Y means N or P; R 3 , R 4 , R 5 , R 6 Respectively represent four independent hydrocarbon groups with 1 to 12 carbon atoms; R 1 and R 2 Each independently selected from C1-C10 straight chain alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl, R 7 -phenyl or R 7 -naphthyl; said R 7 -F, -Cl, -Br, -CF 3 、-OCH 3 , alkyl and N, N-disubstituted alkyl, the quaternary amide ionic organic catalyst has good catalytic activity in ring-opening polymerization and alternating copolymerization, and can improve the purity and yield of the copolymer; The synthesis method of the square amide ionic organic catalyst comprises the following steps: After mixing compound A, compound B and an organic solvent, react under a vacuum condition of 0.01 mbar to 1 mbar for 2 h to 4 h, and then dehydrate at 70° C. to 80° C. to obtain a solid product, which is a square amide ionic organic catalyst; The molar ratio of the compound A to the compound B is (1-10):1, and the amount ratio of the compound B to the organic solvent is 0.5mmol:15ml; The structural formula of the compound A is shown in formula (1): In the above formula, R 1 and R 2 Each independently selected from C1-C10 straight chain alkyl, cyclohexyl, tert-butyl, isopropyl, allyl, phenyl, naphthyl, R 7 -phenyl or R 7 -naphthyl; said R 7 -F, -Cl, -Br, -CF 3 、-OCH 3 , alkyl and N,N-disubstituted alkyl; The structural formula of the compound B is shown in formula (2): In the above formula, Y represents N or P; R 3 , R 4 , R 5 , R 6 They represent four independent hydrocarbon groups having 1 to 12 carbon atoms.

2. The squaramide ionic organic catalyst according to claim 1, It is characterized in that The organic solvent is tetrahydrofuran, 2-methyltetrahydrofuran, methanol, ethanol, n-propanol, isopropanol, toluene or acetonitrile.

3. Use of the squaramide ionic organic catalyst as claimed in claim 1 in the ring-opening polymerization reaction of cyclic ester monomers or cyclic carbonate monomers.

4. Use of the squaramide ionic organic catalyst as claimed in claim 1 in the alternating copolymerization of epoxy compounds and isothiocyanate compounds.

5. Use of the squaramide ionic organic catalyst as claimed in claim 1 in the alternating copolymerization of epoxy compounds and phthalic anhydride.

6. In the application according to claim 3, 4 or 5, It is characterized in that The reaction conditions during the application are: temperature of 20°C to 60°C and time of 5min to 68h.

7. The use according to claim 3, It is characterized in that The cyclic ester monomer is ε-caprolactone, δ-valerolactone, racemic lactide, levorotatory lactide, dextrorotatory lactide or C1-C12 δ-alkyl valerolactone; the cyclic carbonate monomer is trimethylene carbonate.

8. The use according to claim 4 or 5, It is characterized in that The epoxy compound is ethylene oxide, C1-C20 straight-chain alkyl ethylene oxide, C1-C16 straight-chain alkyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, glycidyl methacrylate, cyclohexene oxide, 4-vinyl cyclohexene oxide or limonene oxide.

9. The use according to claim 4, It is characterized in that The isothiocyanate compound is at least one of methyl isothiocyanate, linear alkyl isothiocyanate, alicyclic isothiocyanate, isopropyl isothiocyanate, sec-butyl isothiocyanate, isobutyl isothiocyanate, benzyl isothiocyanate, phenyl isothiocyanate, o- / m- / p-toluene isothiocyanate, benzoyl isothiocyanate, chloroethyl isothiocyanate, cyclohexyl methyl isothiocyanate and allyl isothiocyanate; the linear alkyl has 2 to 20 carbon atoms, and the alicyclic ring in the alicyclic isothiocyanate has 3 to 12 carbon atoms.

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