Polyether-containing carbon dioxide-based polycarbonate polyols

Abstract

The invention provides a carbon dioxide based polycarbonate-polyester-polyether block copolymerized diol, a star-shaped carbon dioxide based polycarbonate-polyester-polyether copolymerized polyol, and a star-shaped carbon dioxide based polycarbonate-polyester-polyether copolymerized polyol with a low molecular weight. By adjusting the specific polyether content, chain segment distribution and molecular weight, the three polyols can be used for preparing polyurethane elastomers, soft foam and hard foam respectively. The low-temperature brittleness of the polyurethane material is improved while the elasticity of the polyurethane material is improved.

Description

Technical Field

[0001] This invention relates to carbon dioxide-based polycarbonate polyols containing polyethers and their preparation methods, belonging to the field of polyurethane materials. Background Technology

[0002] Polyurethane is an important class of polymer materials, prepared by reacting polyether polyols with isocyanates (or polyester polyols). Polyether polyols are a commonly used polyol raw material in polyurethane preparation. Polyether polyols are a class of polyol compounds with multiple oxygen atoms. Common polyether polyols include polyether alcohols and polyether polyol copolymers. They possess good flexibility, abrasion resistance, and chemical resistance, providing the elasticity and durability required for polyurethane materials. Polyether polyols play two important roles in polyurethane preparation: providing long-chain flexibility and elasticity, and acting as reactants for isocyanates to form polyurethane. The choice of polyether polyol affects the properties of polyurethane materials, such as hardness, tensile strength, and abrasion resistance. Common polyether polyols include polyether alcohols (such as polyethylene glycol) and polyether polyol copolymers (such as polyether alcohol / polyester alcohol copolymers). These polyether polyols have different molecular weights, structures, and properties, and can be selected according to specific application requirements.

[0003] Chinese patent CN116003759A discloses a carbon dioxide-based polyester polycarbonate diol, which is obtained by one-pot, one-step polymerization of epoxy monomers, phthalic anhydride, and carbon dioxide in the presence of a bifunctional organoboron catalyst and a chain transfer agent containing two active hydrogen atoms. This carbon dioxide-based polyester polycarbonate diol can be used as a raw material to prepare biodegradable polyurethane materials. However, the polyurethane materials prepared from this diol still have shortcomings in terms of strength, hardness, and durability.

[0004] When polycarbonate polyols are used to prepare polyurethane, the formation of multiple interconnected molecular chains results in a better spatial structure, significantly improving the strength of the resulting polyurethane. However, this can lead to excessive rigidity and insufficient toughness in the final polyurethane material. For example, Chinese patent CN103827207A discloses an aliphatic polycarbonate for polyurethane, which involves the application of polycarbonate polyols. Although this invention can introduce polyether segments into its molecular structure through pre-polyethers, these segments can only be introduced at the center of the structure using chain transfer agents. This has very limited effect on adjusting the overall toughness of the resulting polyurethane. As can be seen from its examples, this method does not solve the problems of material toughness and specific molding of polycarbonate polyol-based polyurethanes.

[0005] CN105899572A discloses branched polyether carbonate polyols and their preparation methods; CN105473638A discloses higher-functionality polyether carbonate polyols obtained using branching agent molecules; CN117024728A discloses hyperbranched carbon dioxide-based polycarbonate ether polyols; CN110023374A discloses new high-molecular-weight polymers from waste materials; CN101535364A discloses a method for producing flexible polyurethane foam; CN101611074A discloses a method for preparing polyether carbonate polyols; and CN114230781A discloses a method for preparing low-molecular-weight polycarbonate polyether polyols with autocatalytic effects. All these patent documents use bimetallic catalysts (DMCs). In the preparation of carbon dioxide-based polycarbonate polyols, if epoxide (e.g., ethylene oxide) monomers and metal catalysts are used, the metal catalyst cannot or does not easily cause ethylene oxide to undergo ring-opening, making it difficult for the epoxide monomer (e.g., ethylene oxide) to self-polymerize and form polyether segments. Furthermore, metal catalysts cannot be separated from polymers and therefore remain in the polymer, which can have adverse effects on the performance and environmental aspects of polyurethane products in subsequent applications such as the preparation of polyurethane products.

[0006] CN105829379A discloses the use of urethane alcohols in the preparation of polyether carbonate polyols, CN107849232A discloses the use of alcohols containing at least two urethane groups in the preparation of polyether carbonate polyols, and CN115651159A discloses hyperbranched polyurethane adhesives.

[0007] CN111378101A discloses a method for preparing a biodegradable carbon dioxide-based polyester-polycarbonate terpolymer with a polyether content of less than 10%; CN115044024A discloses a biodegradable copolymer for plasticizing and toughening polyvinyl chloride with a polyether content of less than 10%; CN116217904A discloses a high-toughness carbon dioxide-based polyester-polycarbonate with a polyether mass fraction of less than 5%; and CN116355195A discloses a method for preparing an aliphatic polycarbonate polyol with a PPO mol% (molar percentage of polyether units self-polymerized from epoxy monomers) of less than 3.7.

[0008] Existing CO2-based polycarbonate polyols increase the glass transition temperature of polyurethanes prepared from them by introducing hard monomer units (such as polyester units), but such polyurethanes are brittle at lower temperatures (e.g., below 5°C), i.e., low-temperature brittleness. Summary of the Invention

[0009] The object of this invention is to provide (liquid) carbon dioxide-based polycarbonate diols or polyols containing polyether segments or blocks, which are free of metal catalyst residues (e.g., bimetallic catalysts such as DMC). On the one hand, it exhibits low-temperature flexibility, i.e., flexibility at lower temperatures (e.g., below 5°C), and on the other hand, it possesses high strength properties (glass transition temperature above 40°C, even above 42, 45, 47, or 50°C, i.e., a certain degree of toughness or stiffness).

[0010] In this application, optional means either present or absent.

[0011] According to a first embodiment of the present invention, a carbon dioxide-based polycarbonate-polyester-polyether block copolydiol having general formula (I) is provided:

[0012]

[0013] R is a divalent residue formed from any of the following diols used as chain transfer agents: 1) C2-C15 organic diols (e.g., C2-C15 or C3-C14 aliphatic diols, or C6-C15 aromatic diols, such as diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, bisphenol A, bisphenol F, or bisphenol S), 2) number-average molecular weight of 500-2000 (preferably). Polybutadiene glycol with a number average molecular weight of 600-1800 (e.g., 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700), and 3) polybutadiene glycol with a number average molecular weight of 800-2000 (preferably 900-1800, e.g., 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700). 00) polytetrahydrofuran diol, 4) aromatic or semi-aromatic polyester diols (preferably aromatic or semi-aromatic polyester diols, such as polyethylene terephthalate diol) with a number average molecular weight of 500-2000 (preferably 600-1800, e.g. 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700), 5) number Aromatic or semi-aromatic polycarbonate diols (such as bisphenol-type aromatic polycarbonate diols) with an average molecular weight of 400-2000 (preferably 500-1800, for example 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700); and two branched chains (formed by polymerization) are attached to R;

[0014] Each branch of the block copolymer diol (I) includes three types of blocks: (flexible) polyether blocks or segments formed by the self-polymerization of (first) epoxide monomers; polycarbonate blocks or segments formed by the copolymerization of (second) epoxide monomers with CO2; and optionally (rigid) polyester blocks or segments formed by the copolymerization of (second) epoxide monomers with phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride.

[0015] In the polymer diol of the above general formula (I), two branched chains are attached to R.

[0016] The carbon dioxide-based polycarbonate-polyester-polyether block copolymer diol (I) is liquid at room temperature. It is used to prepare polyurethane elastomers, such as those used in leather, coatings, TPU, PU adhesives, and plastic running tracks.

[0017] Preferably, the polyether (repeating unit) content of the carbon dioxide-based polycarbonate-polyester-polyether block copolydiol of general formula (I) is 2-18 mol%, preferably 3-17 mol%, preferably 3.5-16.5 mol%, preferably 4-16 mol%, preferably 5-15 mol%, preferably 6-14 mol%, preferably 7-13 mol%, preferably 8-12 mol%, and the polyester (PE) (repeating unit) content is 10-20 mol%, preferably 11-19 mol%, preferably 11.5-18.5 mol%. The content of polycarbonate (repeating unit) is 62-88 mol%, preferably 63-87 mol%, preferably 63.5-86.5 mol%, preferably 64-86 mol%, preferably 65-85 mol%, preferably 66-84 mol%, preferably 67-83 mol%, preferably 68-82 mol%, preferably 70-80 mol%, based on the total mol content of polyether, polyester and polycarbonate (repeating unit).

[0018] Preferably, the (flexible) polyether block is formed from the self-polymerization (or homopolymerization) of one or more (e.g., two, three, or four) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, and 1,2-epoxybutane, wherein the polyether block has one or more (e.g., two, three, or four) of the following structural units:

[0019]

[0020]

[0021] n is an integer from 2 to 50, preferably 3 to 49, and more preferably 4 to 48, 5 to 47, 6 to 46, 7 to 45, 8 to 44, for example 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 31, 32, 35, 38, 40 or 43.

[0022] The polycarbonate block is formed by reacting one or more (two, three, four or five) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide with carbon dioxide, and the polycarbonate block has one or more (two, three, four or five) of the following structural units:

[0023]

[0024] In the formula, m is an integer from 2 to 30, preferably 3-28, 4-26, 5-25, 6-24, 7-23, 8-22, 9-21, 10-20, 11-19, 12-18, 13-17, or 14-16;

[0025] (Rigid) polyester blocks are formed by reacting one or more (e.g., two, three, four, or five) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane, and cyclohexane oxide with phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride, wherein the polyester block has one or more (e.g., two, three, four, five, six, seven, eight, nine, or ten) structural units:

[0026]

[0027]

[0028] In the formula, p is an integer from 2 to 20, preferably 3 to 19, 4 to 18, 5 to 17, 6 to 16, 7 to 15, 8 to 14, 9 to 13, or 10 to 12. Alternatively, the average value of p is 2 to 20, preferably 3 to 19, 4 to 18, 5 to 17, 6 to 16, 7 to 15, 8 to 14, 9 to 13, or 10 to 12.

[0029] More preferably, the (flexible) polyether block is formed from the self-polymerization (or homopolymerization) of ethylene oxide monomer, and the polyether block has the following structural units:

[0030]

[0031] More preferably, the polycarbonate block is formed from the reaction of one or two epoxide monomers selected from ethylene oxide and propylene oxide with carbon dioxide, and the polycarbonate block has one or two of the following structural units:

[0032]

[0033] More preferably, the (rigid) polyester block is formed from the reaction of propylene oxide monomer and phthalic anhydride, and the polyester block has the following structural unit:

[0034]

[0035] Preferably, in the carbon dioxide-based polycarbonate-polyester-polyether block copolydiol of general formula (I), the molar ratio of the epoxide monomer unit used to form the polyether block to the divalent R group (formed from the chain transfer agent) is (6-30):1, preferably (6.5-28):1, preferably (7-26):1, (7.5-24):1, preferably (8-23):1, preferably (8.5-22):1, preferably (9-21):1, preferably (10-20):1. The molar ratio of the epoxide monomer unit used to form the polycarbonate block to the divalent R group (formed from the chain transfer agent) is (14-40):1, preferably (16-38):1, preferably (18-36):1, preferably (20-34):1, preferably (22-32):1, preferably (24-30):1, preferably (25-35):1. The molar ratio of the epoxide monomer unit used to form the polyester block to the divalent R group (formed from the chain transfer agent) is (4-12):1, preferably (4.5-10):1, preferably (5-8):1, preferably (5-7.5):1, and preferably (5-7):1.

[0036] Generally, carbon dioxide-based polycarbonate-polyester-polyether block copolydiols of general formula (I) have a molecular weight of 1000-20000 Da. The preferred molecular weight is 1050-19500 Da, more preferably 1100-19000 Da, for example 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 4 000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 11000, 11500, 12000, 12500, 13000, 13500, 14000, 14500, 15000, 15500, 16000, 16500, 17000, 17500 or 18000 Da.

[0037] The kinematic or kinetic viscosity (40°C) of the carbon dioxide-based polycarbonate-polyester-polyether block copolydiol of general formula (I) is 300-2200 centipoise, preferably 350-2000 centipoise, preferably 400-1900 centipoise, preferably 500-1800 centipoise, preferably 600-1700 centipoise, preferably 700-1600 centipoise, preferably 800-1500 centipoise, and preferably 900-1400 centipoise.

[0038] According to a second embodiment of the present invention, a method for preparing a carbon dioxide-based polycarbonate-polyester-polyether block copolydiol having general formula (I) is provided, the method comprising:

[0039] 1) Add the first epoxide monomer, organoborane, organic quaternary ammonium salt and chain transfer agent (e.g., C2-C15 or C3-C14 organic diol HO-R-OH as chain transfer agent) together into a high-pressure reactor, heat (e.g., heat to 45℃-50℃), and maintain the pressure inside the reactor to carry out the reaction (e.g., 3-15 hours, e.g., 6-10 hours);

[0040] The chain transfer agent is any of the following diols: 1) C2-C15 organic diols (e.g., C2-C15 or C3-C14 aliphatic diols, or C6-C15 aromatic diols, such as diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, bisphenol F, or bisphenol S); 2) polybutadiene glycol with a number average molecular weight of 500-2000 (preferably 600-1800, e.g., 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, or 1700); 3) polybutadiene glycol with a number average molecular weight of 800-2000 (preferably 900-1800, e.g., 1000, 1100, 1200, 1300, 1400, or 1700). 4) Polytetrahydrofuran diols with a number average molecular weight of 500-2000 (preferably 600-1800, such as 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700) (preferably aromatic or semi-aromatic polyester diols). 5) Aromatic or semi-aromatic polycarbonate diols (such as bisphenol A aromatic polycarbonate diols) with a number average molecular weight of 400-2000 (preferably 500-1800, such as 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700).

[0041] The molar ratio of the first epoxide monomer to the chain transfer agent is (6-24):1, preferably (7-23):1, preferably (8-22):1, preferably (9-21):1, preferably (10-20):1, preferably (11-19):1, preferably (12-18):1, preferably (13-17):1, preferably (14-16):1;

[0042] The molar ratio of borane to chain transfer agent is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100;

[0043] The molar ratio of quaternary ammonium salt to chain transfer agent is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100 or 0.12:100;

[0044] The first epoxide monomer is selected from one or more (such as two, three or four) of ethylene oxide, propylene oxide, epichlorohydrin and 1,2-epoxybutane.

[0045] Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron;

[0046] Preferably, the organic quaternary ammonium salt is a tetra(C1-C6 alkyl)ammonium halide, more preferably a tetra(C2-C4 alkyl)ammonium halide, such as tetra-n-butylammonium halide; more preferably a tetra(C1-C6 alkyl)ammonium chloride, even more preferably a tetra(C2-C4 alkyl)ammonium chloride, such as tetra-n-butylammonium chloride;

[0047] Preferably, the C2-C15 organic diol is a C2-C15 or C3-C14 aliphatic diol, or a C6-C15 aromatic diol, such as diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, bisphenol F, or bisphenol S;

[0048] 2) Add the second epoxide monomer and optionally phthalic anhydride and / or 1,8-naphthalic anhydride to the reaction system; and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 3.0 or 3.5 MPa), and heat (e.g., to 50-60 °C) to continue the reaction (e.g., 6-20 hours, such as 12 hours);

[0049] The molar ratio of carbon dioxide consumption (mol) to the chain transfer agent in step 1) is (14-40):1, preferably (16-38):1, preferably (18-36):1, preferably (20-36):1, preferably (22-36.5):1, preferably (24-36):1, preferably (25-35):1, preferably (30-34):1;

[0050] The molar ratio of the second epoxide monomer to the chain transfer agent in step 1) is (14-56):1, preferably (15-55):1, preferably (16-54):1, preferably (17-53):1, preferably (18-52):1, preferably (19-51):1, preferably (20-50):1, preferably (21-49):1. Preferred (22-48): 1, preferred (23-47): 1, preferred (24-46): 1, preferred (25-45): 1, preferred (26-44): 1, preferred (27-43): 1, preferred (28-42): 1, preferred (29-41): 1, preferred (30-40): 1, preferred (32-38): 1;

[0051] The molar ratio of phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the chain transfer agent in step 1) is (3-9):1, preferably (3.2-8.8):1, preferably (3.5-8.5):1, preferably (4-8):1, preferably (4.5-7.5):1, preferably (5-7):1;

[0052] The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide.

[0053] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the block copolymer diol product.

[0054] According to a second embodiment of the present invention, a method for preparing a carbon dioxide-based polycarbonate-polyester-polyether block copolydiol having general formula (I) is also provided, the method comprising:

[0055] 1) Add the second epoxide monomer, organoborane, organic quaternary ammonium salt and chain transfer agent (e.g., C2-C15 or C3-C14 organic diol HO-R-OH) together into a high-pressure reactor, and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 2.7, 3.0 or 3.5 MPa), raise the temperature (e.g., raise to 45-50°C), and maintain the pressure inside the reactor to carry out the reaction (e.g., 3-8 hours, e.g., 5-6 hours);

[0056] The chain transfer agent is any of the following diols: 1) C2-C15 organic diols (e.g., C2-C15 or C3-C14 aliphatic diols, or C6-C15 aromatic diols, such as diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, bisphenol F, or bisphenol S); 2) polybutadiene glycol with a number average molecular weight of 500-2000 (preferably 600-1800, e.g., 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, or 1700); 3) polybutadiene glycol with a number average molecular weight of 800-2000 (preferably 900-1800, e.g., 1000, 1100, 1200, 1300, 1400, or 1700). 4) Polytetrahydrofuran diols with a number average molecular weight of 500-2000 (preferably 600-1800, such as 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700) (preferably aromatic or semi-aromatic polyester diols). 5) Aromatic or semi-aromatic polycarbonate diols (such as bisphenol A aromatic polycarbonate diols) with a number average molecular weight of 400-2000 (preferably 500-1800, such as 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700).

[0057] The molar ratio of the second epoxide monomer to the chain transfer agent is (6-14):1, preferably (6.5-13.5):1, preferably (7-13):1, preferably (7.5-12.5):1, preferably (8-12):1, preferably (9-11):1;

[0058] The molar ratio of borane to chain transfer agent is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100;

[0059] The molar ratio of quaternary ammonium salt to chain transfer agent is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100;

[0060] The molar ratio of carbon dioxide consumption (mol) to chain transfer agent is (6-14):1, preferably (6.5-13.5):1, preferably (6.8-13):1, preferably (7-12.5):1, preferably (7.7-12):1, preferably (8-11.5):1, preferably (8.5-11):1, preferably (9-10.5):1, preferably (9.5-10):1;

[0061] The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide.

[0062] Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron;

[0063] The organic quaternary ammonium salt is a tetra(C1-C6 alkyl)ammonium halide, more preferably a tetra(C2-C4 alkyl)ammonium halide, such as tetra-n-butylammonium halide; more preferably a tetra(C1-C6 alkyl)ammonium chloride, more preferably a tetra(C2-C4 alkyl)ammonium chloride, such as tetra-n-butylammonium chloride;

[0064] Preferably, the C2-C15 organic diol (i.e., HO-R-OH) is a C2-C15 or C3-C14 aliphatic diol, or a C6-C15 aromatic diol, more preferably 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, bisphenol F or bisphenol S.

[0065] 2) Release the carbon dioxide from the reactor, open the bottom valve, and use high-purity nitrogen to press the material in the reactor from the bottom into another high-pressure reactor, while trying to avoid the entry of carbon dioxide gas. Continue to add the first epoxide monomer into the reactor, raise the reaction temperature (for example, raise it to 45-55℃), and continue the reaction (for example, 3-8 hours, such as 5-6 hours).

[0066] The molar ratio of the first epoxide monomer feed amount (mol) to the chain transfer agent in step 1) is (10-20):1, preferably (10.5-19.5):1, preferably (11-19):1, preferably (11.5-18.5):1, preferably (12-18):1, preferably (12.5-17.5):1, preferably (13-17):1, preferably (13.5-16.5):1, preferably (14-16):1, preferably (15-16):1;

[0067] The first epoxide monomer is selected from one or more (e.g., two, three or four) of ethylene oxide, propylene oxide, epichlorohydrin and 1,2-epoxybutane.

[0068] 3) Add the second epoxide monomer and optional phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the reaction system, and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 2.7, 3.0 or 3.5 MPa), and heat (e.g., to 45-50 °C) to continue the reaction (e.g., for 5-15 hours, such as 8-10 hours);

[0069] The molar ratio of the second epoxide monomer to the chain transfer agent in step 1) is (14-46):1, preferably (15-45):1, preferably (16-44):1, preferably (17-43):1, preferably (18-42):1, preferably (19-41):1, preferably (20-40):1, preferably (21-39):1, preferably (22-38):1, preferably (23-37):1, preferably (24-36):1, preferably (26-34):1, preferably (28-32):1, for example 30:1;

[0070] The molar ratio of phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the chain transfer agent in step 1) is (3-7):1, preferably (3.2-6.8):1, preferably (3.5-6.5):1, preferably (4-6):1, preferably (4.5-5.5):1, for example 5:1;

[0071] The molar ratio of carbon dioxide consumption (mol) to the chain transfer agent in step 1) is (18-32):1, preferably (19-31):1, preferably (20-30):1, preferably (20.5-29.5):1, preferably (21-29):1, preferably (21.5-28.5):1, preferably (22-28):1, preferably (22.5-27.5):1, preferably (23-27):1, for example 25:1;

[0072] The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide.

[0073] 4) After terminating the reaction, remove excess monomer and discharge the material to obtain the final product.

[0074] According to a third embodiment of the invention, a star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolymer or random copolymer polyol having the general formula (II) (containing polyether) is provided:

[0075]

[0076] In the formula, t represents the number of branch chains and is an integer of 3-8, preferably 3-7, preferably 3-6, preferably 3-5, preferably 3-4.

[0077] R 1 It is a polyvalent residue formed from a C3-C12 organic polyol with a hydroxyl (OH) functionality of 3-8, preferably 3-7, preferably 3-6, preferably 3-5, preferably 3-4, as a chain transfer agent; in R 1 It connects to 3-8, preferably 3-7, preferably 3-6, preferably 3-5, and preferably 3-4 branch chains.

[0078] C3-C12 organic polyols are selected from one or more of the following: glycerol, trimethylolpropane (TMP), 1,2,3-butanetriol, triethylene glycol, pentaerythritol, sorbitol, 2,5-dehydro-D-glucanol, glucol, and sucrose.

[0079] Each branch of the (polyether-containing) star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolyol or random copolyol (II) comprises the following structures: 0-2 (preferably 0-1) (flexible) polyether segments or blocks formed by polymerization of (first) epoxide monomers; 3-9 (preferably 4-8, preferably 4-7, preferably 5-6) polycarbonate segments or blocks formed by copolymerization of (second) epoxide monomers with CO2; and 0-3 (preferably 1-2) (rigid) polyester segments or blocks formed by polymerization or copolymerization of (second) epoxide monomers with optional phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride.

[0080] In addition, all the branched chains of the (polyether-containing) star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolyol or random copolyol (II) include the following structures: 1-3 (preferably 1-2) (flexible) polyether segments or blocks formed by the polymerization of (first) epoxide monomers; 4-12 (preferably 5-11, preferably 5-10, preferably 6-8) polycarbonate segments or blocks formed by the copolymerization of (second) epoxide monomers with CO2; and 2-5 (preferably 3-4) (rigid) polyester segments or blocks formed by the copolymerization of (second) epoxide monomers with phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride.

[0081] The aforementioned copolyol (II) has a star-shaped random copolymer or block copolymer structure with a molecular weight of 3000–5000 Da and a polyether content (based on the total number of repeating units, in mol) of epoxide monomer repeating units, of 5–12 mol%, preferably 6–10 mol%. It is suitable for preparing polyurethane flexible foams, such as PU foam (EO), slow rebound (PO), self-skinning PU, and automotive steering wheels.

[0082] Preferably, the polyether (repeating unit) content of the above-mentioned copolyol (II) is 4-12 mol%, preferably 4.5-11 mol%, preferably 5-10 mol%, preferably 6-9 mol%, the polyester (PE) (repeating unit) content is 16-32 mol%, preferably 17-31 mol%, preferably 18-30 mol%, preferably 19-29 mol%, preferably 20-28 mol%, and the polycarbonate (repeating unit) content is 62-76 mol%, preferably 64-74 mol%, preferably 66-72 mol%, preferably 68-70 mol%, based on the total mol content of polyether, polyester and polycarbonate (repeating unit).

[0083] The (kinematic) viscosity (40°C) of the above-mentioned copolyol (II) is 300-2500 centipoise, preferably 350-2400 centipoise, preferably 400-2300 centipoise, preferably 500-2200 centipoise, preferably 600-2100 centipoise, preferably 700-2000 centipoise, preferably 800-1900 centipoise, preferably 900-1800 centipoise, preferably 1000-1700 centipoise, and preferably 1100-1600 centipoise.

[0084] Preferably, the (flexible) polyether segments or blocks are formed by the polymerization (self-polymerization, homopolymerization, or copolymerization) of one or more (e.g., two, three, or four) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, and 1,2-epoxybutane, wherein the (flexible) polyether segments or blocks have one or more (e.g., two, three, or four) of the following structural units:

[0085]

[0086] In the formula, n1 is the number of repeating units of the epoxide monomer and is 0, 1 or 2.

[0087] The polycarbonate segment or block is formed by reacting one or more (e.g., two, three, four, or five) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane, and cyclohexane oxide with carbon dioxide, and the polycarbonate segment or block has one or more (e.g., two, three, four, or five) of the following structural units:

[0088]

[0089] In the formula, m1 is the number of polycarbonate repeating units and is an integer of 3-8, preferably 4-7 or 5-6;

[0090] (Rigid) polyester segments or blocks are formed from the reaction of one or more (e.g., two, three, four, or five) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane, and cyclohexane oxide with phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride, wherein the polyester segment or block has one or more (e.g., two, three, four, five, six, seven, eight, nine, or ten) structural units:

[0091]

[0092]

[0093]

[0094] In the formula, p1 is the number of repeating polyester units and is an integer from 1 to 3, preferably 1 to 2.

[0095] According to a fourth embodiment of the present invention, a method for preparing a star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolymer or random copolymer having general formula (II) (containing polyether) is provided, the method comprising:

[0096] 1) Add the first epoxide monomer, organoborane, organoammonium salt and chain transfer agent together into a high-pressure reactor, heat (e.g., heat to 40℃-50℃), and maintain the pressure inside the reactor to carry out the reaction (e.g., 3-15 hours, e.g., 4-10 hours);

[0097] The chain transfer agent is a C3-C12 organic polyol with a hydroxyl (OH) functionality of 3-8, preferably 3-7, preferably 3-6, preferably 3-5, preferably 3-4.

[0098] The molar ratio of the first epoxide monomer to the chain transfer agent is (1-3):1, preferably (1.2-2.8):1, preferably (1.5-2.5):1, preferably (1.7-2.3):1, and preferably (2-2.2):1.

[0099] The molar ratio of borane to chain transfer agent is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100;

[0100] The molar ratio of the organic ammonium salt to the chain transfer agent is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100;

[0101] The first epoxide monomer is selected from one or more (such as two, three or four) of ethylene oxide, propylene oxide, epichlorohydrin and 1,2-epoxybutane.

[0102] Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron;

[0103] Preferably, the organic ammonium salt is a C1-C5 fatty acid ammonium (e.g., ammonium acetate), a tetra(C1-C6 alkyl) ammonium chloride, more preferably a tetra(C2-C4 alkyl) ammonium chloride, such as tetra-n-butylammonium chloride;

[0104] Preferably, the chain transfer agent C3-C12 organic polyol is selected from one or more of glycerol, trimethylolpropane (TMP), 1,2,3-butanetriol, triethylene glycol, pentaerythritol, sorbitol, 2,5-dehydro-D-glucanol, glucol and sucrose.

[0105] 2) Add the second epoxide monomer and optionally phthalic anhydride and / or 1,8-naphthalic anhydride to the reaction system; and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 3.0 or 3.5 MPa), and heat (e.g., to 50-60 °C) to continue the reaction (e.g., 6-20 hours, such as 12-14 hours);

[0106] The molar ratio of carbon dioxide consumption (mol) to the chain transfer agent in step 1) is (18-38):1, preferably (20-36):1, preferably (21-35):1, preferably (22-34):1, preferably (23-33):1, preferably (24-32):1, preferably (25-31):1, preferably (26-30):1, preferably (27-29):1, for example 28:1;

[0107] The molar ratio of the second epoxide monomer to the chain transfer agent in step 1) is (25-55):1, preferably (26-54):1, preferably (27-53):1, preferably (28-52):1, preferably (29-51):1, preferably (30-50):1, preferably (31-49):1, preferably (32-48):1, preferably (33-47):1, preferably (34-46):1, preferably (35-45):1, preferably (36-44):1, preferably (37-43):1, preferably (38-42):1, preferably (39-41):1;

[0108] The molar ratio of phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the chain transfer agent in step 1) is (5-15):1, preferably (5.5-14.5):1, preferably (6-14):1, preferably (6.5-13.5):1, preferably (7-13):1, preferably (7.5-12.5):1, preferably (8-12):1, preferably (8.5-11.5):1, preferably (9-11):1, preferably 10:1;

[0109] The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide.

[0110] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the product.

[0111] According to a fourth embodiment of the present invention, a method for preparing a star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolymer or random copolymer having general formula (II) (containing polyether) is also provided, the method comprising:

[0112] 1) Add the second epoxide monomer, organoborane, organoquaternary ammonium salt and chain transfer agent together into a high-pressure reactor, and purge with carbon dioxide to 2-4 MPa (e.g. 2.5, 2.7, 3.0 or 3.5 MPa), raise the temperature (e.g. to 45-55°C) and maintain the pressure inside the reactor to carry out the reaction (e.g. 3-8 hours, e.g. 5-6 hours);

[0113] The chain transfer agent is a C3-C12 organic polyol with a hydroxyl (OH) functionality of 3-8, preferably 3-7, preferably 3-6, preferably 3-5, preferably 3-4.

[0114] The molar ratio of the second epoxide monomer to the chain transfer agent is (4.5-11.5):1, preferably (5-11):1, preferably (5.5-10.5):1, preferably (6-10):1, preferably (6.5-9.5):1, preferably (7-9):1;

[0115] The molar ratio of borane to chain transfer agent is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100;

[0116] The molar ratio of the organic quaternary ammonium salt to the chain transfer agent is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100;

[0117] The molar ratio of carbon dioxide consumption (mol) to chain transfer agent is (4.5-11.5):1, preferably (5-11):1, preferably (5.5-10.5):1, preferably (6-10):1, preferably (6.5-9.5):1, preferably (7-9):1;

[0118] The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide.

[0119] Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron;

[0120] The organic quaternary ammonium salt is a tetra(C1-C6 alkyl)ammonium halide, more preferably a tetra(C2-C4 alkyl)ammonium halide, such as tetra-n-butylammonium halide; more preferably a tetra(C1-C6 alkyl)ammonium chloride, more preferably a tetra(C2-C4 alkyl)ammonium chloride, such as tetra-n-butylammonium chloride;

[0121] Preferably, the chain transfer agent C3-C12 organic polyol is selected from one or more of glycerol, trimethylolpropane (TMP), 1,2,3-butanetriol, triethylene glycol, pentaerythritol, sorbitol, 2,5-dehydro-D-glucanol, glucol and sucrose.

[0122] 2) Release the carbon dioxide from the reactor, open the bottom valve, and use high-purity nitrogen to press the material in the reactor from the bottom into another high-pressure reactor, while trying to avoid the entry of carbon dioxide gas. Continue to add the first epoxide monomer into the reactor, raise the reaction temperature (for example, raise it to 45-60℃, such as 55℃), and continue the reaction (for example, 3-8 hours, such as 4-6 hours).

[0123] The molar ratio of the first epoxide monomer feed amount (mol) to the chain transfer agent in step 1) is (2-6):1, preferably (2.5-5.5):1, preferably (2.8-5.2):1, preferably (3-5):1, preferably (3.2-4.7):1, preferably (3.5-4.5):1, preferably (3.8-4.2):1, preferably 4:1;

[0124] The first epoxide monomer is selected from one or more (such as two, three or four) of ethylene oxide, propylene oxide, epichlorohydrin and 1,2-epoxybutane.

[0125] 3) Add the second epoxide monomer and phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the reaction system, and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 2.7, 3.0, 3.2 or 3.5 MPa), raise the temperature (e.g., raise to 45-65℃, such as 50-60℃) and continue the reaction (e.g., 5-15 hours, such as 8-10 hours);

[0126] The molar ratio of the second epoxide monomer to the chain transfer agent in step 1) is (13-47):1, preferably (14-46):1, preferably (15-45):1, preferably (16-44):1, preferably (17-43):1, preferably (18-42):1, preferably (19-41):1, preferably (20-40):1, preferably (21-39):1, preferably (22-38):1;

[0127] The molar ratio of phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the chain transfer agent in step 1) is (3.5-12.5):1, preferably (4-12):1, preferably (4.5-11.5):1, preferably (5-11):1, preferably (5.5-10.5):1, preferably (6-10):1;

[0128] The molar ratio of carbon dioxide consumption (mol) to the chain transfer agent in step 1) is (12-32):1, preferably (12.5-31.5):1, preferably (13-31):1, preferably (13.5-30.5):1, preferably (14-30):1, preferably (14.5-29.5):1, preferably (15-29):1, preferably (15.5-28.5):1, preferably (16-28):1;

[0129] The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide.

[0130] 4) After terminating the reaction, remove excess monomer and discharge the material to obtain the product.

[0131] According to a fifth embodiment of the invention, a star-shaped carbon dioxide-based polycarbonate-polyether random copolymer polyol having the general formula (III) is provided:

[0132]

[0133] In the formula, s represents the number of branch chains and is an integer between 3 and 4.

[0134] R 2 It is derived from C3-C12 organic polyols with a functionality of 3-4 (i.e., C3-C12 organic polyol R) that act as chain transfer agents. 2 (OH)s) forming multivalent residues; in R 2 It connects to 3-4 branch chains.

[0135] C3-C12 organic polyols are selected from one, two, or more of glycerol, trimethylolpropane (TMP), 1,2,3-butanetriol, and pentaerythritol.

[0136] Each branch of the (polyether-containing) star-shaped carbon dioxide-based polycarbonate-polyether random copolymer polyol (III) comprises the following structure: 1-3 (preferably 2-3) (rigid) polyether segments formed by the polymerization of epoxide monomers; and 1-2 polycarbonate segments formed by the copolymerization of epoxide monomers with CO2.

[0137] In addition, all the branched chains of the (polyether-containing) star-shaped carbon dioxide-based polycarbonate-polyether random copolymer polyol (III) include the following structural repeating units: 2-4 (preferably 2-3) (rigid) polyether segments formed by the polymerization of epoxide monomers; and 2-3 polycarbonate segments formed by the copolymerization of (second) epoxide monomers with CO2.

[0138] The aforementioned copolyol (III) has a random copolymer structure and a molecular weight of 1000–2000 Da. Its polyether content (based on the total number of mol of repeating units in epoxide monomers) is preferably 12–55 mol%, preferably 16–52 mol%, preferably 20–50 mol%, preferably 28–48 mol%, preferably 30–46 mol%. Its polycarbonate content (based on the total number of mol of repeating units in polycarbonate) is 45–88 mol%, preferably 48–84 mol%, preferably 50–80 mol%, preferably 52–72 mol%, preferably 54–70 mol%. It is suitable for use in the preparation of rigid polyurethane foams, such as for the preparation of PU insulation materials and wood-look products.

[0139] The kinematic or kinetic viscosity (40°C) of the above-mentioned random copolymer polyol (III) is 300-2500 centipoise, preferably 350-2400 centipoise, preferably 400-2300 centipoise, preferably 500-2200 centipoise, preferably 600-2100 centipoise, preferably 700-2000 centipoise, preferably 800-1900 centipoise, preferably 900-1800 centipoise, preferably 1000-1700 centipoise, and preferably 1100-1600 centipoise.

[0140] Preferably, the (rigid) polyether segment is formed from the polymerization (self-polymerization, homopolymerization, or copolymerization) of one or more (e.g., two, three, or four) epoxide monomers selected from propylene oxide, epichlorohydrin, 1,2-epoxybutane, and epicyclohexane, wherein the (rigid) polyether segment has one or more (e.g., two, three, or four) of the following structural units:

[0141]

[0142] In the formula, n2 is the number of repeating units of the epoxide monomer and is 1-3, preferably 1-2.

[0143] The polycarbonate segment is formed by reacting one, two, or three epoxide monomers selected from propylene oxide, epichlorohydrin, 1,2-epoxybutane, and epicyclohexane with carbon dioxide, and the polycarbonate segment has one or more (e.g., two, three, or four) of the following structural units:

[0144]

[0145]

[0146] In the formula, m2 is the number of polycarbonate repeating units and is an integer from 1 to 3, preferably 1 to 2.

[0147] According to a sixth embodiment of the present invention, a method for preparing a star-shaped carbon dioxide-based polycarbonate-polyether random copolymer polyol having general formula (III) (containing polyether) is provided, the method comprising:

[0148] 1) An epoxide monomer, an organoborane, an organoammonium salt, and a C3-C12 organic polyol with a functionality of 3-4 (i.e., C3-C12 organic polyol R) as a chain transfer agent are used. 2 (OH)s)) are added together into a high-pressure reactor, and the temperature is raised (e.g., to 50℃-65℃). The pressure inside the reactor is maintained to carry out the reaction (e.g., 3-15 hours, e.g., 6-12 hours).

[0149] The molar ratio of epoxide monomers to chain transfer agent C3-C12 organic polyols is (4.5-14):1, preferably (5-13):1, preferably (5.5-12.5):1, preferably (6-12):1, preferably (6.5-11):1, preferably (7-10):1;

[0150] The molar ratio of borane to chain transfer agent C3-C12 organic polyol is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100;

[0151] The molar ratio of the organic ammonium salt to the chain transfer agent C3-C12 organic polyol is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100;

[0152] The epoxide monomer is selected from one or more (such as two, three or four) of propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane.

[0153] Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron;

[0154] Preferably, the organic ammonium salt is a C1-C5 fatty acid ammonium (e.g., ammonium acetate), a tetra(C1-C6 alkyl) ammonium chloride, more preferably a tetra(C2-C4 alkyl) ammonium chloride, such as tetra-n-butylammonium chloride;

[0155] Preferably, the chain transfer agent, C3-C12 organic polyol, is selected from one or more of glycerol, trimethylolpropane (TMP), 1,2,3-butanetriol, and pentaerythritol.

[0156] The molar ratio of carbon dioxide consumption (mol) to chain transfer agent C3-C12 organic polyol is (3-12):1, preferably (3-11):1, preferably 3.5-10:1, preferably 4-9, and preferably 5-8:1.

[0157] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the product.

[0158] The present invention also provides the use of the above-described block copolymer diols, or the above-described copolymer polyols, wherein they are used in the preparation of rigid polyurethane foams, coatings, adhesives, sealants, leather, and elastomers (including synthetic leather, shoe soles, and plastic running tracks).

[0159] Compared with the prior art, the technical solution of this application has the following beneficial technical effects:

[0160] This invention, through precise design of the length and distribution of various chain segments in carbon dioxide-based polycarbonate polyols, obtains a variety of carbon dioxide-based polycarbonate polyols (polymer polyols) capable of meeting various requirements in different types of polyurethane products. This improves the strength properties of polyurethane products and mitigates their low-temperature brittleness.

[0161] In addition, selecting appropriate chain transfer agents under different conditions can help improve the performance of the prepared polymer products.

[0162] This application demonstrates a significant improvement in the flexibility and elasticity of polymer products by using long-chain chain transfer agents, such as polybutadiene glycol, polytetrahydrofuran glycol, polyester glycol, or polycarbonate diol. Furthermore, dehydration from these long-chain chain transfer agents is remarkably easy.

[0163] The inventors of this application have discovered that two-branched linear carbon dioxide-based polycarbonate diols with two branches are softer than linear carbon dioxide-based polycarbonate monools with one chain. However, star-shaped carbon dioxide-based polycarbonate polyols with three or more branches (even with a high content of polyether repeating units) are harder, reaching the hardness of plastics. The star-shaped carbon dioxide-based polycarbonate polyols of this invention can be used to prepare polyurethane products with excellent properties.

[0164] The inventors of this application have discovered that random copolymers have good compatibility with commonly used foaming agents, and therefore are suitable for use in the preparation of rigid PU foam.

[0165] Compared to ordinary polyether-type rigid PU foam (120°C), the polycarbonate-type rigid PU foam of this invention has a temperature resistance of up to 150°C, and after introducing acid anhydride, the high temperature resistance of the PU of this invention exceeds 170-180°C. Furthermore, the temperature resistance contribution of cyclohexane oxide is even higher than that of acid anhydride. Detailed Implementation

[0166] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.

[0167] I. Block copolymer diols

[0168] It is used to prepare polyurethane elastomer plastics, which can be used in the polyurethane field for leather, coatings, TPU, PU adhesives (sealants), plastic running tracks, etc.

[0169] Experimental results show that block copolymer diols with a number average molecular weight of 2300-5000 (preferably 2500-4800, more preferably 2600-4500) are suitable for preparing polyurethane coatings. More preferably, the content of polyether repeating units in the block copolymer diol used to prepare polyurethane coatings is 2-18 mol%, preferably 3-17 mol%, preferably 3.5-15 mol%, preferably 4-13 mol%, for example 4.5, 5, 6, 7, 8, 9, 10, or 12 mol%. When the content of polyether repeating units is higher than 22 mol%, the block copolymer diol has poor storage stability (less than 3 months), and the coating formed using the block copolymer diol has the disadvantage of low-temperature brittleness.

[0170] Block copolymer diols with a number average molecular weight of 1000-2000 (preferably 1200-1800) are suitable for preparing polyurethane elastomers.

[0171] Block copolymer diols with a number average molecular weight of 5100-15000 (preferably 5500-14000, more preferably 5800-12000, such as 7000, 8000, 9000, 10000), and especially with a polyether repeating unit content in the range of 2-20 mol% (e.g. 3-18 mol%), are suitable for use in the preparation of polyurethane adhesives or sealants.

[0172] Example A1 (for preparing coatings)

[0173] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and 1,4-butanediol were added together into a high-pressure reactor. The molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and 1,4-butanediol was 800:0.5:0.1:100. The temperature was raised to 45°C, and the reactor pressure was maintained for 6 hours.

[0174] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and 1,4-butanediol in step 1) is 3700:700:100; and purge carbon dioxide to 1.5 MPa, raise the temperature to 50°C, and continue the reaction for 16 h. The molar ratio of carbon dioxide consumption to 1,4-butanediol in step 1) is 2993:100.

[0175] 3) After terminating the reaction, excess monomer is removed and the material is discharged to obtain the polymeric diol. The number-average molecular weight (Mn) of the polymeric diol is 4300, the content of polyether repeating units is 17.9 mol%, the content of polyester (PE) repeating units is 15.6 mol%, and the content of polycarbonate repeating units is 66.5 mol%. The viscosity of the polymeric diol (40℃) is 890 centipoise.

[0176] In this embodiment, the CO2 pressure is high, the reaction is slow, and there is a large amount of carbonate.

[0177] Example A2 (for preparing coatings)

[0178] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and bisphenol A type polycarbonate diol with a number average molecular weight of 400 as a chain transfer agent were added together into a high-pressure reactor. The molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and bisphenol A type polycarbonate diol was 400:0.05:0.01:100. The temperature was raised to 45°C, and the reactor pressure was maintained for 6 hours.

[0179] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and bisphenol A type polycarbonate diol in step 1) is 2800:530:100; and purge carbon dioxide to 1.5 MPa, raise the temperature to 50°C, and continue the reaction for 12 h, wherein the molar ratio of carbon dioxide consumption to bisphenol A type polycarbonate diol in step 1) is 2269:100;

[0180] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymeric polyol. With Mn 3950, excluding bisphenol A type polycarbonate diol itself, the content of polyether repeating units is 12.5 mol%, PE repeating units is 16.6 mol%, and polycarbonate repeating units is 70.9 mol%. The viscosity of the polymeric diol (40℃) is 1030 centipoise.

[0181] Example A3 (for preparing coatings)

[0182] 1) Ethylene oxide, phthalic anhydride, triethylboron, tetra-n-butylammonium chloride, and bisphenol A type polycarbonate diol with a number average molecular weight of 920 as a chain transfer agent were added together into a high-pressure reactor. The molar ratio of ethylene oxide, phthalic anhydride, triethylboron, tetra-n-butylammonium bromide, and polycarbonate diol was 1800:200:0.5:0.1:100. Carbon dioxide was introduced to 2.0 MPa, the temperature was raised to 45°C, and the reactor pressure was maintained for 26 hours. The molar ratio of carbon dioxide consumption to polycarbonate diol was 1399.3:100.

[0183] 2) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymeric polyol. With Mn 2600, excluding bisphenol A type polycarbonate diol itself, the content of polyether repeating units is 11 mol%, PE repeating units is 11 mol%, and polycarbonate repeating units is 78 mol%. The viscosity of the polymeric diol (40℃) is 573 centipoise.

[0184] Coating Application Examples

[0185] Under a nitrogen atmosphere, according to the notes in the examples, 80 parts by weight of the polymer diols obtained from Examples A1, A2 and A3 suitable for preparing coatings were added to a reaction vessel. The temperature was raised to 80°C and 50 parts by weight of butanone were added as a solvent. 30 parts by weight of dimethyl phthalate was added dropwise, followed by 0.5 parts by weight of dibutyltin dilaurate. The reaction was carried out for 5 hours, and then 15 parts by weight of diethylene glycol crosslinking agent were added. The reaction was continued at a constant temperature for 2 hours. After the reaction was completed, the temperature was lowered to room temperature, water was added, and the organic solvent was removed under vacuum. The amount of water added was controlled to obtain a polyurethane emulsion with a solid content of 40 wt% as a coating.

[0186] Table 1 - Performance of Coatings

[0187]

[0188] The data in Table 1 show that by controlling the mol% of flexible polyether repeating units of polyether blocks, polycarbonate repeating units of polycarbonate blocks, and rigid polyester repeating units of polyester blocks, as well as the arrangement order of the three blocks in the carbon dioxide-based polycarbonate diol product, the block polymer molecular chain can have suitable flexibility, thereby reducing the viscosity of the coating and improving the storage stability of the coating.

[0189] Furthermore, in Example A1, 1,4-butanediol was used as a chain transfer agent. On the one hand, dehydration from 1,4-butanediol is significantly easier compared to glycerol or ethylene glycol (from which dehydration is difficult, and the presence of water can damage the catalyst). On the other hand, the medium-length chain of 1,4-butanediol, as a chain transfer agent, is located at the center of the final polymer molecular chain, which increases the flexibility of the final polymer molecular chain and the coating containing it. In Examples A2 and A3, higher molecular weight polycarbonate diols were used as chain transfer agents. On the one hand, using a higher molecular weight chain transfer agent facilitates easier dehydration from the agent. On the other hand, the polycarbonate diol, as a chain transfer agent, is located at the center of the final polymer molecular chain, which increases the flexibility of the final polymer molecular chain and the coating containing it.

[0190] Example B1 (for the preparation of elastomers)

[0191] 1) Ethylene oxide, triethylboron, tetrapropylammonium bromide, and 1,4-butanediol were added together into a high-pressure reactor. The molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and 1,4-butanediol was 200:0.5:0.1:100. The temperature was raised to 45°C, and the reactor pressure was maintained for 3 hours.

[0192] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and 1,4-butanediol in step 1) is 1250:250:100; and purge carbon dioxide to 1.7 MPa, raise the temperature to 50°C, and continue the reaction for 12 h, wherein the molar ratio of carbon dioxide consumption to 1,4-butanediol in step 1) is 999:100.

[0193] 3) After terminating the reaction, excess monomer was removed and the material was discharged to obtain the polymeric diol. Mn 1700, polyether repeating unit content was 13.8 mol%, polyester (PE) repeating unit content was 17.2 mol%, and polycarbonate repeating unit content was 69.0 mol%. The viscosity (40℃) of the obtained polymeric diol was 485 centipoise.

[0194] Preparation of elastomers

[0195] According to the notes in the examples, 20 parts by weight of the polymer diol suitable for preparing elastomers obtained in Example B1 and 70 parts by weight of toluene-2,4-diisocyanate were mixed and reacted at 70°C for 3 hours. Then, the material was placed in a mold at 110°C, and 0.1 parts by weight of 1,4-butanediol and 0.05 parts by weight of stannous octoate catalyst were added. The mixture was stirred and mixed, and then heat-cured at 120°C for 1 hour. The mixture was then placed in a blower dryer and vulcanized at 100°C for 12 hours. Finally, it was left at room temperature for 5 days to obtain polyurethane elastomer.

[0196] Table 2 - Properties of Elastomers

[0197]

[0198] Example C1 (for preparing adhesives)

[0199] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and 1,3-propanediol were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and 1,3-propanediol was 2000:0.5:0.1:100; carbon dioxide was introduced to 2.7 MPa, the temperature was raised to 45°C, and the reactor pressure was maintained for 5 hours, wherein the molar ratio of carbon dioxide consumption to 1,3-propanediol was 1999:100.

[0200] 2) Release the carbon dioxide from the reactor, open the bottom valve, and use high-purity nitrogen to press the material in the reactor from the bottom into another high-pressure reactor, while trying to avoid the entry of carbon dioxide gas. Continue to add ethylene oxide into the reactor. The molar ratio of the added ethylene oxide to 1,3-propanediol in step 1) is 100:100. Maintain the reaction temperature at 45°C and continue the reaction for 5 hours.

[0201] 3) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and 1,3-propylene glycol in step 1) is 3000:500:100; and purge carbon dioxide to 1.2 MPa, raise the temperature to 50°C, and continue the reaction for 15 h, wherein the molar ratio of carbon dioxide consumption to 1,3-propylene glycol in step 1) is 2498:100;

[0202] 4) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymeric diol. Mn 4900, polyether content 2.0 mol%, PE 10.0 mol%, polycarbonate 88.0 mol%. The viscosity of the polymeric polyol (40℃) is 1127 centipoise.

[0203] Example C2 (for preparing adhesives)

[0204] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polybutadiene glycol with a number average molecular weight of 500 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polybutadiene glycol was 600:0.5:0.1:100; the temperature was raised to 45°C, and the reactor pressure was maintained for 6 hours.

[0205] 2) Add ethylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of ethylene oxide, phthalic anhydride and polybutadiene glycol in step 1) is 3800:660:100, and purge carbon dioxide to 1.0 MPa, raise the temperature to 50°C, and continue the reaction for 18 h, wherein the molar ratio of carbon dioxide consumption to polybutadiene glycol in step 1) is 3140:100.

[0206] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. With Mn4800, excluding polybutadiene glycol itself, the content of polyether repeating units is 13.6 mol%, PE 15.0 mol%, and polycarbonate 71.4 mol%. The viscosity of the polymer diol (40℃) is 981 centipoise.

[0207] Example C3 (for preparing adhesives)

[0208] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polybutadiene glycol with a number average molecular weight of 900 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polybutadiene glycol was 400:0.5:0.1:100; the temperature was raised to 45°C, and the reactor pressure was maintained for 6 hours.

[0209] 2) Add ethylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of ethylene oxide, phthalic anhydride and polybutadiene glycol in step 1) is 2000:450:100, and purge carbon dioxide to 1.0 MPa, raise the temperature to 50°C, and continue the reaction for 18 h, wherein the molar ratio of carbon dioxide consumption to polybutadiene glycol in step 1) is 1546:100;

[0210] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. With Mn 3300, excluding polybutadiene glycol itself, the content of polyether repeating units is 16.7 mol%, PE repeating units is 18.7 mol%, and polycarbonate repeating units is 64.6 mol%. The viscosity of the polymer diol (40℃) is 765 centipoise.

[0211] Example C4 (for preparing adhesives)

[0212] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polytetrahydrofuran glycol with a number average molecular weight of 800 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polytetrahydrofuran glycol was 800:0.05:0.1:100; the temperature was raised to 45°C, and the reaction was carried out under pressure in the reactor for 6 hours.

[0213] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and chain transfer agent in step 1) is 3900:800:100; and purge carbon dioxide to 2.0 MPa, raise the temperature to 50°C, and continue the reaction for 12 h, wherein the molar ratio of carbon dioxide consumption to polytetrahydrofuran glycol in step 1) is 3099:100;

[0214] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. With Mn 5950, excluding polytetrahydrofuran diol itself, the content of polyether repeating units is 17.1 mol%, PE repeating units is 17.0 mol%, and polycarbonate repeating units is 65.9 mol%. The viscosity of the polymer polyol (40℃) is 1292 centipoise.

[0215] Adhesive application

[0216] According to the notes in the examples, 20 parts by weight of the polymer diol, 20 parts by weight of isoflurone diisocyanate, and 8 parts by weight of toluene diisocyanate obtained from Examples C1-C4 suitable for preparing adhesives were added to a reaction vessel and stirred and heated. After heating to 75°C, 0.4 parts by weight of silane coupling agent, 10 parts by weight of polytetrahydrofuran, and 1 part by weight of 1,4-butanediol were slowly added to carry out the reaction. 4 parts by weight of dimethylolpropionic acid and 3 parts by weight of 3,5-dimethylpyrazole were added to the mixture after the reaction, and the temperature was controlled to be constant at 55°C for the reaction. After the reaction was completed, the temperature was maintained at 55°C, and 2 parts by weight of triethylamine and 80 parts by weight of deionized water were added and stirred to carry out the salt formation reaction. Then, 1.2 parts by weight of ethylenediamine was added to carry out the chain extension reaction and dispersed fully to obtain the polyurethane adhesive.

[0217] Table 3 - Properties of Adhesives

[0218]

[0219] Example D1 (for preparing sealant)

[0220] 1) Ethylene oxide, triethylboron, tetrapropylammonium bromide, and 1,6-hexanediol were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and 1,6-hexanediol was 1500:0.5:0.1:100; the temperature was raised to 45°C, and the reactor pressure was maintained for 4 hours.

[0221] 2) Add epichlorohydrin and phthalic anhydride to the reaction system, wherein the molar ratio of epichlorohydrin, phthalic anhydride and 1,6-hexanediol in step 1) is 8000:1200:100; and purge with carbon dioxide to 1.7 MPa, raise the temperature to 50°C, and continue the reaction for 24 h, wherein the molar ratio of carbon dioxide consumption to 1,6-hexanediol in step 1) is 6791:100;

[0222] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn 12900, the content of polyether repeating units in the polymer is 15.8 mol%, the content of PE repeating units is 12.6 mol%, and the content of polycarbonate repeating units is 71.6 mol%. The viscosity of the polymer polyol (40℃) is 1637 centipoise.

[0223] Example D2 (for preparing sealant)

[0224] 1) Ethylene oxide, triethylboron, tetrapropylammonium bromide, and 1,4-butanediol were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and 1,4-butanediol was 900:0.5:0.1:100; the temperature was raised to 40°C, and the reactor pressure was maintained for 4 hours.

[0225] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and 1,4-butanediol in step 1) is 4100:1000:100; and purge carbon dioxide to 2.0 MPa, raise the temperature to 45°C, and continue the reaction for 18 h, wherein the molar ratio of carbon dioxide consumption to 1,4-butanediol in step 1) is 3098:100;

[0226] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn 5700, polyether content 18.0 mol%, PE 20.0 mol%, polycarbonate 62.0 mol%. The viscosity of the polymer polyol (40℃) is 1109 centipoise.

[0227] Example D3 (for preparing sealant)

[0228] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polybutadiene glycol with a number average molecular weight of 2000 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polybutadiene glycol was 1000:0.5:0.1:100; the temperature was raised to 45°C, and the reactor pressure was maintained for 6 hours.

[0229] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and polybutadiene glycol in step 1) is 11500:1500:100, and purge carbon dioxide to 1.0 MPa, raise the temperature to 50°C, and continue the reaction for 18 h, wherein the molar ratio of carbon dioxide consumption to polybutadiene glycol in step 1) is 9992:100.

[0230] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. With Mn 15000, excluding polybutadiene glycol itself, the content of polyether repeating units is 8.0 mol%, PE repeating units is 12.1 mol%, and polycarbonate repeating units is 79.9 mol%. The viscosity of the polymer polyol (40℃) is 1755 centipoise.

[0231] Example D4 (for preparing sealant)

[0232] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polyethylene terephthalate diol with a number average molecular weight of 500 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polyethylene terephthalate diol was 600:0.05:0.01:100; the temperature was raised to 45°C, and the reaction was carried out under pressure in the reactor for 6 hours.

[0233] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and polyethylene terephthalate diol in step 1) is 6400:1340:100; and purge carbon dioxide to 1.0 MPa, raise the temperature to 50°C, and continue the reaction for 12 h. The molar ratio of carbon dioxide consumption to polyethylene terephthalate diol in step 1) is 5057:100.

[0234] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn8650, excluding polyethylene terephthalate diol itself, contains 8.6 mol% polyether repeating units, 19.1 mol% PE repeating units, and 72.3 mol% polycarbonate repeating units. The viscosity of the polymer polyol (40℃) is 1873 centipoise.

[0235] Example D5 (for preparing sealant)

[0236] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polyethylene terephthalate diol with a number-average molecular weight of 890 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polyethylene terephthalate diol was 600:0.05:0.01:100; the temperature was raised to 45°C, and the reaction was carried out under pressure in the reactor for 6 hours.

[0237] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and polyethylene terephthalate diol in step 1) is 4000:800:100; and purge with carbon dioxide to 1.0 MPa, raise the temperature to 50°C, and continue the reaction for 12 h, wherein the molar ratio of carbon dioxide consumption to polyethylene terephthalate diol in step 1) is 3193:100;

[0238] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn6000, excluding polyethylene terephthalate (diol) itself, contains 13.0 mol% polyether, 17.4 mol% PE, and 69.6 mol% polycarbonate. The viscosity of the polymer polyol (40℃) is 1237 centipoise.

[0239] Example D6 (for preparing sealant)

[0240] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polyethylene terephthalate diol with a number average molecular weight of 2000 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polyethylene terephthalate diol was 700:0.05:0.01:100; the temperature was raised to 45°C, and the reaction was carried out under pressure in the reactor for 6 hours.

[0241] 2) Add ethylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of ethylene oxide, phthalic anhydride and polyethylene terephthalate diol in step 1) is 3500:800:100; and purge with carbon dioxide to 1.5 MPa, raise the temperature to 50°C, and continue the reaction for 12 h, wherein the molar ratio of carbon dioxide consumption to polyethylene terephthalate in step 1) is 2697:100;

[0242] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. With Mn6200, excluding polyethylene terephthalate diol itself, the content of polyether repeating units is 16.7 mol%, the content of PE repeating units is 19.0 mol%, and the content of polycarbonate repeating units is 64.3 mol%. The viscosity of the polymer polyol (40℃) is 1253 centipoise.

[0243] Example D7 (for preparing sealant)

[0244] 1) Ethylene oxide, phthalic anhydride, triethylboron, tetra-n-butylammonium chloride, and bisphenol A type polycarbonate diol with a number average molecular weight of 2000 as a chain transfer agent were added together into a high-pressure reactor. The molar ratio of ethylene oxide, phthalic anhydride, triethylboron, tetra-n-butylammonium bromide, and polycarbonate diol was 4500:640:0.5:0.1:100. Carbon dioxide was introduced to 2.0 MPa, the temperature was raised to 45°C, and the reactor pressure was maintained for 26 hours. The molar ratio of carbon dioxide consumption to polycarbonate (diol) was 3147:100.

[0245] 2) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. With Mn2600, excluding bisphenol A type polycarbonate diol itself, the content of polyether repeating units is 15.8 mol%, the content of PE repeating units is 14.2 mol%, and the content of polycarbonate repeating units is 70.0 mol%. The viscosity of the polymer polyol (40℃) is 596 centipoise.

[0246] Example D8 (for preparing sealant)

[0247] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polytetrahydrofuran glycol with a number average molecular weight of 1300 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polytetrahydrofuran glycol was 500:0.05:0.05:100; the temperature was raised to 45°C, and the reactor pressure was maintained for 6 hours.

[0248] 2) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and chain transfer agent in step 1) is 5800:800:100; and purge carbon dioxide to 2.0 MPa, raise the temperature to 50°C, and continue the reaction for 12 h, wherein the molar ratio of carbon dioxide consumption to polytetrahydrofuran glycol in step 1) is 4997:100;

[0249] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. With Mn 8200, excluding polytetrahydrofuran diol itself, the content of polyether repeating units is 7.9 mol%, PE repeating units is 12.7 mol%, and polycarbonate repeating units is 79.4 mol%. The viscosity of the polymer polyol (40℃) is 1452 centipoise.

[0250] Example D9 (for preparing sealant)

[0251] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium chloride, and polytetrahydrofuran glycol with a number average molecular weight of 2000 as a chain transfer agent were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and polytetrahydrofuran glycol was 400:0.05:0.05:100; the temperature was raised to 45°C, and the reactor pressure was maintained for 6 hours.

[0252] 2) Add ethylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of ethylene oxide, phthalic anhydride and chain transfer agent in step 1) is 3800:500:100; and purge carbon dioxide to 1.5 MPa, raise the temperature to 50°C, and continue the reaction for 12 h, wherein the molar ratio of carbon dioxide consumption to polytetrahydrofuran glycol in step 1) is 3292:100;

[0253] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. With Mn6000, excluding polytetrahydrofuran diol itself, the content of polyether repeating units is 9.5 mol%, the content of PE repeating units is 11.9 mol%, and the content of polycarbonate repeating units is 78.6 mol%. The viscosity of the polymer polyol (40℃) is 1292 centipoise.

[0254] Sealant Application Examples

[0255] According to the notes in the examples, 50 parts by weight of the polyether diol and 20 parts by weight of hexamethylene diisocyanate obtained in the examples suitable for making sealant were added to a reaction vessel and stirred and heated. After heating to 75°C, 0.4 parts by weight of silane coupling agent, 10 parts by weight of polytetrahydrofuran diol and 1 part by weight of 1,4-butanediol were slowly added to carry out the reaction. 4 parts by weight of dimethylolpropionic acid and 3 parts by weight of 3,5-dimethylpyrazole were added to the mixture after the reaction, and the temperature was controlled to be constant at 55°C for the reaction to proceed. After the reaction was completed, the temperature was maintained at 55°C, and 2 parts by weight of triethylamine and 80 parts by weight of deionized water were added and stirred to carry out the salt formation reaction. Then, 1.2 parts by weight of ethylenediamine was added to carry out the chain extension reaction and after being fully dispersed, the polyurethane sealant was obtained.

[0256] Table 4 - Product Performance

[0257]

[0258] In Examples D1-D9, higher molecular weight polymeric diols were used as chain transfer agents, resulting in polycarbonate diols with a narrow molecular weight distribution. The polyurethane materials prepared from these diols exhibited high elasticity and stiffness. Conversely, existing technologies use low molecular weight polyols such as glycerol or propylene glycol as chain transfer agents. However, because the trapped water is difficult to remove, the water present in these low molecular weight polyols consumes the catalyst, leading to a wider molecular weight distribution and affecting the polymer's structure and properties.

[0259] II. Star-shaped copolymer polyols

[0260] It has a random or block structure with a number-average molecular weight of 2k to 1W and a polyether repeating unit content greater than 2 mol%. It can be used to prepare polyurethane flexible foam, such as PU foam (EO), slow rebound (PO) (molecular weight around 6K), self-skinning (silicone oil-modified reactive heat car steering wheel), semi-rigid foam, etc.

[0261] Example E1

[0262] 1) Add ethylene oxide, triphenylborone, ammonium acetate and glucosyl alcohol together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triphenylborone, ammonium acetate and glucosyl alcohol is 600:0.5:0.1:100; raise the temperature to 40°C and maintain the pressure inside the reactor for 4 hours.

[0263] 2) Add ethylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of ethylene oxide, phthalic anhydride and chain transfer agent in step 1) is 1200:1200:100; raise the temperature to 45℃ and continue the reaction for 8 hours;

[0264] 3) Add ethylene oxide to the reaction system, wherein the molar ratio of ethylene oxide to the chain transfer agent in step 1) is 4800:100; introduce carbon dioxide to 1.5 MPa, raise the temperature to 55°C, and continue the reaction for 14 h, wherein the molar ratio of carbon dioxide consumption to glucosol in step 1) is 4776:100.

[0265] 4) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn 6900, polyether repeating unit content 9.1 mol%, PE repeating unit content 18.2 mol%, and polycarbonate repeating unit content 72.7 mol%.

[0266] Example E2

[0267] 1) Ethylene oxide, triphenylboron, tetra-n-butylammonium bromide and glucosyl alcohol are added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triphenylboron, tetra-n-butylammonium bromide and glucosyl alcohol is 100:0.5:0.1:100; the temperature is raised to 40°C and the reaction is carried out under pressure for 4 hours.

[0268] 2) Add ethylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of ethylene oxide, phthalic anhydride and chain transfer agent in step 1) is 1500:1500:100; raise the temperature to 50℃ and continue the reaction for 8 hours;

[0269] 3) Add ethylene oxide to the reaction system, wherein the molar ratio of ethylene oxide to the chain transfer agent in step 1) is 3500:100; introduce carbon dioxide to 1.5 MPa, maintain the reaction temperature at 50℃, and continue the reaction for 10 h, wherein the molar ratio of carbon dioxide consumption to glucosol in step 1) is 3498:100.

[0270] 4) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn 6000, polyether repeating unit content 2.0 mol%, PE repeating unit content 29.4 mol%, and polycarbonate repeating unit content 68.6 mol%.

[0271] Example E3

[0272] 1) Propylene oxide, triethylboron, tetra-n-butylphosphine bromide, and 2,5-dehydro-D-glucanol were added together into a high-pressure reactor, wherein the molar ratio of propylene oxide, triethylboron, tetra-n-butylammonium bromide, and 2,5-dehydro-D-glucanol was 800:0.5:0.1:100; carbon dioxide was introduced to 1.0 MPa, the temperature was raised to 50°C, and the reactor pressure was maintained for 4 hours, wherein the molar ratio of carbon dioxide consumption to 2,5-dehydro-D-glucanol was 800:100.

[0273] 2) Release the carbon dioxide from the reactor, open the bottom valve, and use high-purity nitrogen to force the material in the reactor from the bottom into another high-pressure reactor, while trying to avoid the entry of carbon dioxide gas. Continue to add propylene oxide into the reactor, wherein the molar ratio of the added propylene oxide to the chain transfer agent in step 1) is 400:100. Maintain the reaction temperature at 55°C and continue the reaction for 4 hours.

[0274] 3) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and chain transfer agent in step 1) is 1000:1000:100; maintain the reaction temperature at 55℃ and continue the reaction for 8 hours.

[0275] 4) Add ethylene oxide to the reaction system, wherein the molar ratio of ethylene oxide to the chain transfer agent in step 1) is 2800:100; and purge carbon dioxide to 1.2 MPa, raise the temperature to 60°C, and continue the reaction for 10 h, wherein the molar ratio of carbon dioxide consumption to 2,5-dehydr-D-glucol in step 1) is 2800:100;

[0276] 5) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn 7200, polyether repeating unit content 8.0 mol%, PE repeating unit content 20.0 mol%, and polycarbonate repeating unit content 72.0 mol%.

[0277] Example E4

[0278] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and trimethylolpropane were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and trimethylolpropane was 480:0.5:0.1:100; carbon dioxide was introduced to 2.5 MPa, the temperature was raised to 45°C, and the reactor pressure was maintained for 4 hours, wherein the molar ratio of carbon dioxide consumption to trimethylolpropane was 480:100.

[0279] 2) Empty the gas in the reactor and continue to add ethylene oxide into the reactor. The molar ratio of the added ethylene oxide to the chain transfer agent in step 1) is 300:100. Maintain the reaction temperature at 45°C and continue the reaction for 4 hours.

[0280] 3) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride and chain transfer agent in step 1) is 600:600:100, maintain the reaction temperature at 45℃, and continue the reaction for 4 hours.

[0281] 4) Add propylene oxide to the reaction system, wherein the molar ratio of propylene oxide to the chain transfer agent in step 1) is 1620:100; and purge carbon dioxide to 1.5 MPa, raise the temperature to 60°C, and continue the reaction for 10 h, wherein the molar ratio of carbon dioxide consumption to trimethylolpropane in step 1) is 1620:100.

[0282] 5) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. The polyol contains Mn3400, with a polyether repeating unit content of 10 mol%, a PE repeating unit content of 20 mol%, and a polycarbonate repeating unit content of 70 mol%.

[0283] Example E5

[0284] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and 1,2,3-butanetriol were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide, and 1,2,3-butanetriol was 400:0.5:0.1:100; the temperature was raised to 45°C, and the reactor pressure was maintained for 3 hours.

[0285] 2) Add propylene oxide to the reaction system, wherein the molar ratio of propylene oxide to the chain transfer agent in step 1) is 1700:100; and purge carbon dioxide to 1.5 MPa, raise the temperature to 50°C, and continue the reaction for 10 h, wherein the molar ratio of carbon dioxide consumption to 1,2,3-butanetriol in step 1) is 1698:100;

[0286] 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. The polyether repeating unit content is 19.1 mol%, and the polycarbonate repeating unit content is 80.9 mol%.

[0287] Example E6

[0288] 1) Add propylene oxide, triethylboron, tetra-n-butylammonium chloride and pentaerythritol together into a high-pressure reactor, wherein the molar ratio of propylene oxide, triethylboron, tetra-n-butylammonium bromide and pentaerythritol is 1085:0.05:0.1:100; raise the temperature to 50°C and maintain the pressure inside the reactor for 5 hours.

[0289] 2) Add propylene oxide to the reaction system, wherein the molar ratio of propylene oxide to the chain transfer agent in step 1) is 6760:100; introduce carbon dioxide to 1.5 MPa, raise the temperature to 50°C, and continue the reaction for 10 h, wherein the molar ratio of carbon dioxide consumption to pentaerythritol in step 1) is 6758:100.

[0290] 3) Add propylene oxide and phthalic anhydride to the reaction system, wherein the molar ratio of propylene oxide, phthalic anhydride, and the chain transfer agent in step 1) is 1200:1200:100; maintain the reaction temperature at 50℃ and continue the reaction for 10 hours.

[0291] 4) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn is 1W, the content of polyether repeating units is 12.0 mol%, the content of PE repeating units is 13.3 mol%, and the content of polycarbonate repeating units is 74.7 mol%.

[0292] Polyurethane flexible foam

[0293] The following components were added by weight: 80 parts of polyether polyol suitable for flexible foaming, 0.2 parts of triethylenediamine catalyst, 0.3 parts of stannous octoate, 5 parts of ethylene glycol chain extender, 3 parts of water, 0.5 parts of dichloromethane, and 81 parts of foam stabilizer AK15 (Xuzhou Yihuiyang New Material Co., Ltd.). The mixture was quickly stirred until homogeneous to form component A. 70 parts of toluene diisocyanate (TDI) were weighed and added to component A. The mixture was mechanically stirred until homogeneous and then quickly poured into a mold at 40°C for foaming reaction. After the reaction was completed, the mixture was allowed to stand at room temperature for 18 hours to obtain polyurethane flexible foam material.

[0294] Table 5 - Performance of Flexible Foam

[0295]

[0296] III. Low molecular weight random copolymer polyols

[0297] It has a random copolymer structure with a number average molecular weight of 400-2k and a polyether repeating unit content greater than 10 mol%. It can be used to prepare rigid polyurethane foam, such as PU insulation materials and wood-look products.

[0298] Example F1

[0299] 1) 1,2-epoxybutane, triethylboron, tetra-n-butylammonium bromide and glycerol were added together into a high-pressure reactor, wherein the molar ratio of 1,2-epoxybutane, triethylboron, tetra-n-butylammonium bromide and glycerol was 660:0.5:0.1:100; carbon dioxide was introduced to 1.5 MPa, the temperature was raised to 50°C, and the reactor pressure was maintained for 10 h, wherein the molar ratio of carbon dioxide consumption to glycerol was 537.2:100.

[0300] 2) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn800, with a polyether repeating unit content of 18.6 mol% and a polycarbonate repeating unit content of 81.4 mol%.

[0301] Example F2

[0302] 1) Add 1,2-epoxybutane, triethylboron, ammonium acetate and glycerol together into a high-pressure reactor, wherein the molar ratio of 1,2-epoxybutane, triethylboron, ammonium acetate and glycerol is 660:0.5:0.1:100; and purge with carbon dioxide to 1.5 MPa, raise the temperature to 50°C, and maintain the pressure inside the reactor for 10 hours, wherein the molar ratio of carbon dioxide consumption to glycerol is 526.5:100.

[0303] 2) After terminating the reaction, remove excess monomer and discharge the material to obtain the final product. Mn 800, polyether repeating unit content is 20.2 mol%, and polycarbonate repeating unit content is 79.8 mol%.

[0304] Example F3

[0305] 1) Propylene oxide, cyclohexane oxide, tributylboron, tetrabutylammonium bromide, and trimethylolpropane were added together into a high-pressure reactor, wherein the molar ratio of propylene oxide, cyclohexane oxide, tributylboron, tetrabutylammonium bromide, and trimethylolpropane was 1600:400:0.5:0.1:100; carbon dioxide was introduced to 2.0 MPa, the temperature was raised to 65°C, and the reactor pressure was maintained for 12 hours, wherein the molar ratio of carbon dioxide consumption to trimethylolpropane was 1240:100.

[0306] 2) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. The polyether repeating unit content is 37.8 mol%, and the polycarbonate repeating unit content is 62.2 mol%.

[0307] Example F4

[0308] 1) Ethylene oxide, triethylboron, tetra-n-butylammonium bromide and glycerol were added together into a high-pressure reactor, wherein the molar ratio of ethylene oxide, triethylboron, tetra-n-butylammonium bromide and glycerol was 370:0.5:0.1:100; carbon dioxide was introduced to 1.5 MPa, the temperature was raised to 50°C, and the reactor pressure was maintained for 6 hours, wherein the molar ratio of carbon dioxide consumption to pentaerythritol was 326:100.

[0309] 2) After terminating the reaction, remove excess monomer and discharge the material to obtain the polymer polyol. Mn400, polyether repeating unit content is 11.9 mol%, and polycarbonate repeating unit content is 88.1 mol%.

[0310] To facilitate performance comparison between embodiments, only one formulation and process are given for each type of application embodiment. Those skilled in the art can adjust it as needed in actual application.

[0311] rigid polyurethane foam

[0312] Component A was prepared by rapidly mixing 80 parts by weight of the polyether polyol (suitable for rigid foam production), 11 parts by weight of the blowing agent cyclopentane, 0.2 parts by weight of the catalyst triethylenediamine, 0.3 parts by weight of the catalyst stannous octoate, 5 parts by weight of the chain extender ethylene glycol, 0.5 parts by weight of the chain extender dichloromethane, and 81 parts by weight of the foam stabilizer AK15 (Xuzhou Yihuiyang New Material Co., Ltd.) at 21°C. Component A was then reacted with 110 parts by weight of PM-200 (purchased from Wanhua Chemical) at 20°C and 120 bar (gauge pressure) to obtain rigid polyurethane foam. The mold temperature was 35°C, and the feed density was 48 kg / m³. 3 .

[0313] Table 6 - Performance of Rigid Foam

[0314]

[0315] This invention, through precise design of the length and distribution of various chain segments in carbon dioxide-based polycarbonate polyols, obtains a variety of carbon dioxide-based polycarbonate polyols (polymer polyols) capable of meeting various requirements in different types of polyurethane products. This improves the strength properties of polyurethane products and mitigates their low-temperature brittleness.

Claims

1. Carbon dioxide-based polycarbonate-polyester-polyether block copolymer diol having general formula (I): R is a divalent residue formed from any of the following diols that act as chain transfer agents: 1) C2-C15 organic diols (e.g., C2-C15 or C3-C14 aliphatic diols, or C6-C15 aromatic diols, such as diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, bisphenol A, bisphenol F, or bisphenol S), 2) Polybutadiene glycol with a number average molecular weight of 500-2000 (preferably 600-1800, such as 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700). 3) Polytetrahydrofuran diol with a number average molecular weight of 800-2000 (preferably 900-1800, such as 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700), 4) Aromatic or semi-aromatic polyester glycols (preferably aromatic or semi-aromatic polyester glycols, such as polyethylene terephthalate glycol) with a number average molecular weight of 500-2000 (preferably 600-1800, for example 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700), with a number average molecular weight of 500-2000 (preferably 600-1800, such as 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700). 5) Aromatic or semi-aromatic polycarbonate diols (such as bisphenol-type aromatic polycarbonate diols) with a number average molecular weight of 400-2000 (preferably 500-1800, such as 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700); Furthermore, two branched chains (formed through polymerization) are connected to R; Each branch of the block copolymer diol (I) includes the following three types of blocks: polyether blocks or segments formed by the self-polymerization of the first epoxide monomer; polycarbonate blocks or segments formed by the copolymerization of the second epoxide monomer with CO2; and optionally polyester blocks or segments formed by the copolymerization of the second epoxide monomer with phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride. Preferably, the polyether block or segment is formed from the self-polymerization (or homopolymerization) of one or more (e.g., two, three, or four) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, and 1,2-epoxybutane, wherein the polyether block has one or more (e.g., two, three, or four) of the following structural units: In the formula, n is an integer from 2 to 50, preferably 3 to 49, preferably 4 to 48, 5 to 47, 6 to 46, 7 to 45, 8 to 44, for example 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 31, 32, 35, 38, 40 or 43; Preferably, the polycarbonate block is formed by reacting one or more (e.g., two, three, four, or five) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane, and cyclohexane with carbon dioxide, and the polycarbonate block has one or more (two, three, four, or five) of the following structural units: In the formula, m is an integer from 2 to 30, preferably 3-28, 4-26, 5-25, 6-24, 7-23, 8-22, 9-21, 10-20, 11-19, 12-18, 13-17, or 14-16; Preferably, the polyester block is formed by reacting one or more (e.g., two, three, four, or five) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane, and cyclohexane oxide with phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride, and the polyester block has one or more (e.g., two, three, four, five, six, seven, eight, nine, or ten) structural units: In the formula, p is an integer from 2 to 20, preferably 3 to 19, 4 to 18, 5 to 17, 6 to 16, 7 to 15, 8 to 14, 9 to 13, or 10 to 12; Preferably, the polyether repeating unit content in the carbon dioxide-polycarbonate-polyester-polyether block copolydiol of general formula (I) containing polyether blocks is 2-18 mol%, preferably 3-17 mol%, preferably 4-16 mol%, preferably 5-15 mol%, preferably 6-14 mol%, preferably 7-13 mol%, preferably 8-12 mol%, the polyester (PE) repeating unit content is 10-20 mol%, preferably 11-19 mol%, preferably 12-18 mol%, preferably 13-17 mol%, preferably 14-16 mol%, and the polycarbonate repeating unit content is 62-88 mol%, preferably 63-87 mol%, preferably 64-86 mol%, preferably 65-85 mol%, preferably 66-84 mol%, preferably 67-83 mol%, preferably 68-82 mol%, preferably 70-80 mol%, based on the total mol content of polyether, polyester and polycarbonate repeating units.

2. The block copolymer diol according to claim 1, wherein... The polyether block is formed from the self-polymerization or homopolymerization of ethylene oxide monomers, and the polyether block has the following structural units: and / or The polycarbonate block is formed by reacting one or two epoxide monomers selected from ethylene oxide and propylene oxide with carbon dioxide, and the polycarbonate block has one or two of the following structural units: and / or The polyester block is formed from the reaction of propylene oxide monomer and phthalic anhydride, and the polyester block has the following structural units:

3. The block copolymer diol according to claim 1 or 2, wherein... In the carbon dioxide-based polycarbonate-polyester-polyether block copolydiol of general formula (I), the molar ratio of the epoxide monomer unit used to form the polyether block to the divalent R group formed from the chain transfer agent is (6-30):1, preferably (6.5-28):1, preferably (7-26):1, (7.5-24):1, preferably (8-23):1, preferably (8.5-22):1, preferably (9-21):1, preferably (10-20):1; The molar ratio of the epoxide monomer unit used to form the polycarbonate block to the divalent R group formed from the chain transfer agent is (14-40):1, preferably (16-38):1, preferably (18-36):1, preferably (20-34):1, preferably (22-32):1, preferably (24-30):1, preferably (25-35):1; The molar ratio of the epoxide monomer unit used to form the polyester block to the divalent R group formed from the chain transfer agent is (4-12):1, preferably (4.5-10):1, preferably (5-8):1, preferably (5-7.5):1, and preferably (5-7):

1. Preferably, the carbon dioxide-based polycarbonate-polyester-polyether block copolydiol of general formula (I) has a molecular weight of 1000-20000 Da, more preferably 1050-19500 Da, and more preferably 1100-19000 Da, for example 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3 100, 3200, 3300, 3400, 3500, 3600, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 11000, 11500, 12000, 12500, 13000, 13500, 14000, 14500, 15000, 15500, 16000, 16500, 17000, 17500 or 18000 Da; Preferably, the viscosity (40°C) of the carbon dioxide-based polycarbonate-polyester-polyether block copolydiol of general formula (I) is 300-2200 centipoise, preferably 350-2000 centipoise, preferably 400-1900 centipoise, preferably 500-1800 centipoise, preferably 600-1700 centipoise, preferably 700-1600 centipoise, preferably 800-1500 centipoise, and preferably 900-1400 centipoise.

4. A method for preparing a carbon dioxide-based polycarbonate-polyester-polyether block copolydiol having general formula (I) according to any one of claims 1-3, the method comprising: 1) Add the first epoxide monomer, organoborane, organic quaternary ammonium salt and chain transfer agent (e.g., C2-C15 or C3-C14 organic diol HO-R-OH as chain transfer agent) together into a high-pressure reactor, heat (e.g., heat to 45℃-50℃), and maintain the pressure inside the reactor to carry out the reaction (e.g., 3-15 hours, e.g., 6-10 hours); The chain transfer agent is any of the following diols: 1) C2-C15 organic diols (e.g., C2-C15 or C3-C14 aliphatic diols, or C6-C15 aromatic diols, such as diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, bisphenol F, or bisphenol S); 2) polybutadiene glycol with a number average molecular weight of 500-2000 (preferably 600-1800, e.g., 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, or 1700); 3) polybutadiene glycol with a number average molecular weight of 800-2000 (preferably 900-1800, e.g., 1000, 1100, 1200, 1300, 1400, or 1700). 4) Polytetrahydrofuran diols with a number average molecular weight of 500-2000 (preferably 600-1800, such as 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700) (preferably aromatic or semi-aromatic polyester diols). 5) Aromatic or semi-aromatic polycarbonate diols (such as bisphenol A aromatic polycarbonate diols) with a number average molecular weight of 400-2000 (preferably 500-1800, such as 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700). The molar ratio of the first epoxide monomer to the chain transfer agent is (6-24):1, preferably (7-23):1, preferably (8-22):1, preferably (9-21):1, preferably (10-20):1, preferably (11-19):1, preferably (12-18):1, preferably (13-17):1, preferably (14-16):1; The molar ratio of borane to chain transfer agent is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100; The molar ratio of quaternary ammonium salt to chain transfer agent is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100 or 0.12:100; The first epoxide monomer is selected from one or more (such as two, three or four) of ethylene oxide, propylene oxide, epichlorohydrin and 1,2-epoxybutane. Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron; Preferably, the organic quaternary ammonium salt is a tetra(C1-C6 alkyl)ammonium halide, more preferably a tetra(C2-C4 alkyl)ammonium halide, such as tetra-n-butylammonium halide; more preferably a tetra(C1-C6 alkyl)ammonium chloride, even more preferably a tetra(C2-C4 alkyl)ammonium chloride, such as tetra-n-butylammonium chloride; Preferably, the C2-C15 organic diol is a C2-C15 or C3-C14 aliphatic diol, or a C6-C15 aromatic diol, such as diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, bisphenol F, or bisphenol S; 2) Add the second epoxide monomer and phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the reaction system; and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 3.0 or 3.5 MPa), and heat (e.g., to 50-60°C) to continue the reaction (e.g., 6-20 hours, such as 12 hours); The molar ratio of carbon dioxide consumption (mol) to the chain transfer agent (e.g., organic diol HO-R-OH) in step 1) is (14-40):1, preferably (16-38):1, preferably (18-36):1, preferably (20-36):1, preferably (22-36.5):1, preferably (24-36):1, preferably (25-35):1, preferably (30-34):1; The molar ratio of the second epoxide monomer to the chain transfer agent (organic diol HO-R-OH) in step 1) is (14-56):1, preferably (15-55):1, preferably (16-54):1, preferably (17-53):1, preferably (18-52):1, preferably (19-51):1, preferably (20-50):1, preferably (21):

1. -49):1, preferably (22-48):1, preferably (23-47):1, preferably (24-46):1, preferably (25-45):1, preferably (26-44):1, preferably (27-43):1, preferably (28-42):1, preferably (29-41):1, preferably (30-40):1, preferably (32-38):1; The molar ratio of phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the chain transfer agent (organic diol HO-R-OH) in step 1) is (3-9):1, preferably (3.2-8.8):1, preferably (3.5-8.5):1, preferably (4-8):1, preferably (4.5-7.5):1, preferably (5-7):1; The second epoxide monomer is selected from one, two, three, or four of ethylene oxide, propylene oxide, 1,2-epoxybutane, and cyclohexane oxide. 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the block copolymer diol product.

5. A method for preparing a carbon dioxide-based polycarbonate-polyester-polyether block copolydiol having general formula (I) according to any one of claims 1-3, the method comprising: 1) Add the second epoxide monomer, organoborane, organic quaternary ammonium salt and chain transfer agent (such as C2-C15 organic diol HO-R-OH) together into a high-pressure reactor, and purge with carbon dioxide to 2-4 MPa (e.g. 2.5, 2.7, 3.0 or 3.5 MPa), raise the temperature (e.g. to 45-50°C) and maintain the pressure inside the reactor to carry out the reaction (e.g. 3-8 hours, e.g. 5-6 hours); The chain transfer agent is any of the following diols: 1) C2-C15 organic diols (e.g., C2-C15 or C3-C14 aliphatic diols, or C6-C15 aromatic diols, such as diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, bisphenol F, or bisphenol S); 2) polybutadiene glycol with a number average molecular weight of 500-2000 (preferably 600-1800, e.g., 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, or 1700); 3) polybutadiene glycol with a number average molecular weight of 800-2000 (preferably 900-1800, e.g., 1000, 1100, 1200, 1300, 1400, or 1700). 4) Polytetrahydrofuran diols with a number average molecular weight of 500-2000 (preferably 600-1800, such as 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700) and aromatic or semi-aromatic polyester diols (preferably aromatic or semi-aromatic polyester diols). 5) Aromatic or semi-aromatic polycarbonate diols (such as bisphenol A aromatic polycarbonate diols) with a number average molecular weight of 400-2000 (preferably 500-1800, such as 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600 or 1700). The molar ratio of the second epoxide monomer to the chain transfer agent is (6-14):1, preferably (6.5-13.5):1, preferably (7-13):1, preferably (7.5-12.5):1, preferably (8-12):1, preferably (9-11):1; The molar ratio of borane to chain transfer agent is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100; The molar ratio of quaternary ammonium salt to chain transfer agent is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100; The molar ratio of carbon dioxide consumption (mol) to chain transfer agent is (6-14):1, preferably (6.5-13.5):1, preferably (6.8-13):1, preferably (7-12.5):1, preferably (7.7-12):1, preferably (8-11.5):1, preferably (8.5-11):1, preferably (9-10.5):1, preferably (9.5-10):1; The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide. Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron; Preferably, the organic quaternary ammonium salt is tetra(C1-C6 alkyl)ammonium halide, more preferably tetra(C2-C4 alkyl)ammonium halide, such as tetra-n-butylammonium halide; more preferably, the organic quaternary ammonium salt is tetra(C1-C6 alkyl)ammonium chloride, more preferably tetra(C2-C4 alkyl)ammonium chloride, such as tetra-n-butylammonium chloride; Preferably, the C2-C15 organic diol is a C2-C15 or C3-C14 aliphatic diol, or a C6-C15 aromatic diol, such as diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, bisphenol F, or bisphenol S; 2) Release the carbon dioxide from the reactor, open the bottom valve, and use high-purity nitrogen to press the material in the reactor from the bottom into another high-pressure reactor, while trying to avoid the entry of carbon dioxide gas. Continue to add the first epoxide monomer into the reactor, raise the reaction temperature (for example, raise it to 45-55℃), and continue the reaction (for example, 3-8 hours, such as 5-6 hours). The molar ratio of the first epoxide monomer feed amount (mol) to the chain transfer agent in step 1) is (10-20):1, preferably (10.5-19.5):1, preferably (11-19):1, preferably (11.5-18.5):1, preferably (12-18):1, preferably (12.5-17.5):1, preferably (13-17):1, preferably (13.5-16.5):1, preferably (14-16):1, preferably (15-16):1; The first epoxide monomer is selected from one or more (e.g., two, three or four) of ethylene oxide, propylene oxide, epichlorohydrin and 1,2-epoxybutane. 3) Add the second epoxide monomer and optional phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the reaction system, and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 2.7, 3.0 or 3.5 MPa), and heat (e.g., to 45-50 °C) to continue the reaction (e.g., for 5-15 hours, such as 8-10 hours); The molar ratio of the second epoxide monomer to the chain transfer agent in step 1) is (14-46):1, preferably (15-45):1, preferably (16-44):1, preferably (17-43):1, preferably (18-42):1, preferably (19-41):1, preferably (20-40):1, preferably (21-39):1, preferably (22-38):1, preferably (23-37):1, preferably (24-36):1, preferably (26-34):1, preferably (28-32):1, for example 30:1; The molar ratio of phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the chain transfer agent in step 1) is (3-7):1, preferably (3.2-6.8):1, preferably (3.5-6.5):1, preferably (4-6):1, preferably (4.5-5.5):1, for example 5:1; The molar ratio of carbon dioxide consumption (mol) to the chain transfer agent in step 1) is (18-32):1, preferably (19-31):1, preferably (20-30):1, preferably (20.5-29.5):1, preferably (21-29):1, preferably (21.5-28.5):1, preferably (22-28):1, preferably (22.5-27.5):1, preferably (23-27):1, for example 25:1; The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide. 4) After terminating the reaction, remove excess monomer and discharge the material to obtain the final product.

6. Star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolymer polyols or random copolymer polyols having general formula (II): In the formula, t represents the number of branch chains and is an integer of 3-8, preferably 3-7, preferably 3-6, preferably 3-5, preferably 3-4; R 1 It is a polyvalent residue formed from C3-C12 organic polyols with a hydroxyl functionality of 3-8, preferably 3-7, preferably 3-6, preferably 3-5, preferably 3-4, acting as a chain transfer agent, in R 1 It connects to 3-8, preferably 3-7, preferably 3-6, preferably 3-5, and preferably 3-4 branch chains; C3-C12 organic polyols are selected from one or more of glycerol, trimethylolpropane (TMP), 1,2,3-butanetriol, triethylene glycol, pentaerythritol, sorbitol, 2,5-dehydro-D-glucanol, glucol and sucrose; Each branch chain of the star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolymer polyol or random copolymer polyol (II) comprises the following structures: 0-2 (preferably 0-1) polyether segments or blocks formed by the polymerization of (first) epoxide monomers; 3-9 (preferably 4-8, preferably 4-7, preferably 5-6) polycarbonate segments or blocks formed by the copolymerization of (second) epoxide monomers with CO2; and 0-3 (preferably 1-2) polyester segments or blocks formed by the polymerization or copolymerization of (second) epoxide monomers with phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride. Preferably, the polyether segment or block is formed by the polymerization reaction of one or more (e.g., two, three, or four) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, and 1,2-epoxybutane, wherein the polyether segment or block has one or more (e.g., two, three, or four) of the following structural units: In the formula, n1 is the number of repeating units of the epoxide monomer and is 0, 1 or 2; The polycarbonate segment or block is formed by reacting one or more (e.g., two, three, four, or five) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane, and cyclohexane oxide with carbon dioxide, and the polycarbonate segment or block has one or more (e.g., two, three, four, or five) of the following structural units: In the formula, m1 is the number of polycarbonate repeating units and is an integer of 3-8, preferably 4-7 or 5-6; The polyester segment or block is formed by reacting one or more (e.g., two, three, four, or five) epoxide monomers selected from ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane, and cyclohexane oxide with phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride, wherein the polyester segment or block has one or more (e.g., two, three, four, five, six, seven, eight, nine, or ten) structural units: In the formula, p1 is the number of repeating polyester units and is an integer from 1 to 3, preferably 1 to 2.

7. The star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolymer or random copolymer polyol having general formula (II) according to claim 6, wherein... The aforementioned copolyol (II) has a star-shaped random copolymer or block copolymer structure with a molecular weight of 3000–5000 Da; and / or The polyether (repeating unit) content of the above-mentioned copolyol (II) is 4-12 mol%, preferably 4.5-11 mol%, preferably 5-10 mol%, preferably 6-9 mol%, the polyester (PE) (repeating unit) content is 16-32 mol%, preferably 17-31 mol%, preferably 18-30 mol%, preferably 19-29 mol%, preferably 20-28 mol%, and the polycarbonate (repeating unit) content is 62-76 mol%, preferably 64-74 mol%, preferably 66-72 mol%, preferably 68-70 mol%, based on the total mol content of polyether, polyester, and polycarbonate (repeating unit); and / or The (kinematic) viscosity (40°C) of the above-mentioned copolyol (II) is 300-2500 centipoise, preferably 350-2400 centipoise, preferably 400-2300 centipoise, preferably 500-2200 centipoise, preferably 600-2100 centipoise, preferably 700-2000 centipoise, preferably 800-1900 centipoise, preferably 900-1800 centipoise, preferably 1000-1700 centipoise, and preferably 1100-1600 centipoise.

8. A method for preparing the star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolymer or random copolymer polyol having general formula (II) as described in claim 6 or 7, the method comprising: 1) Add the first epoxide monomer, organoborane, organoammonium salt and chain transfer agent together into a high-pressure reactor, heat (e.g., to 40℃-50℃), and maintain the pressure inside the reactor to carry out the reaction (e.g., 3-15 hours, e.g., 4-10 hours). The chain transfer agent is a C3-C12 organic polyol with a hydroxyl functionality of 3-8, preferably 3-7, preferably 3-6, preferably 3-5, preferably 3-4. The molar ratio of the first epoxide monomer to the chain transfer agent is (1-3):1, preferably (1.2-2.8):1, preferably (1.5-2.5):1, preferably (1.7-2.3):1, and preferably (2-2.2):

1. The molar ratio of borane to chain transfer agent is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100; The molar ratio of the organic ammonium salt to the chain transfer agent is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100; The first epoxide monomer is selected from one or more (such as two, three or four) of ethylene oxide, propylene oxide, epichlorohydrin and 1,2-epoxybutane. Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron; Preferably, the organic ammonium salt is a C1-C5 fatty acid ammonium (e.g., ammonium acetate), a tetra(C1-C6 alkyl) ammonium chloride, more preferably a tetra(C2-C4 alkyl) ammonium chloride, such as tetra-n-butylammonium chloride; Preferably, the chain transfer agent is selected from one or more of glycerol, trimethylolpropane (TMP), 1,2,3-butanetriol, triethylene glycol, pentaerythritol, sorbitol, 2,5-dehydro-D-glucanol, glucol and sucrose. 2) Add the second epoxide monomer and optionally phthalic anhydride and / or 1,8-naphthalic anhydride to the reaction system; and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 3.0 or 3.5 MPa), and heat (e.g., to 50-60 °C) to continue the reaction (e.g., 6-20 hours, such as 12-14 hours); The molar ratio of carbon dioxide consumption (mol) to the chain transfer agent in step 1) is (18-38):1, preferably (20-36):1, preferably (21-35):1, preferably (22-34):1, preferably (23-33):1, preferably (24-32):1, preferably (25-31):1, preferably (26-30):1, preferably (27-29):1, for example 28:1; The molar ratio of the second epoxide monomer to the chain transfer agent in step 1) is (25-55):1, preferably (26-54):1, preferably (27-53):1, preferably (28-52):1, preferably (29-51):1, preferably (30-50):1, preferably (31-49):1, preferably (32-48):1, preferably (33-47):1, preferably (34-46):1, preferably (35-45):1, preferably (36-44):1, preferably (37-43):1, preferably (38-42):1, preferably (39-41):1; The molar ratio of phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the chain transfer agent in step 1) is (5-15):1, preferably (5.5-14.5):1, preferably (6-14):1, preferably (6.5-13.5):1, preferably (7-13):1, preferably (7.5-12.5):1, preferably (8-12):1, preferably (8.5-11.5):1, preferably (9-11):1, preferably 10:1; The second epoxide monomer is selected from one, two, three, or four of ethylene oxide, propylene oxide, 1,2-epoxybutane, and cyclohexane oxide. 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the product.

9. A method for preparing the star-shaped carbon dioxide-based polycarbonate-polyester-polyether block copolymer or random copolymer polyol having general formula (II) as described in claim 6 or 7, the method comprising: 1) Add the second epoxide monomer, organoborane, organoquaternary ammonium salt and chain transfer agent together into a high-pressure reactor, and purge with carbon dioxide to 2-4 MPa (e.g. 2.5, 2.7, 3.0 or 3.5 MPa), raise the temperature (e.g. to 45-55°C) and maintain the pressure inside the reactor to carry out the reaction (e.g. 3-8 hours, e.g. 5-6 hours); The chain transfer agent is a C3-C12 organic polyol with a hydroxyl functionality of 3-8, preferably 3-7, preferably 3-6, preferably 3-5, preferably 3-4. The molar ratio of the second epoxide monomer to the chain transfer agent is (4.5-11.5):1, preferably (5-11):1, preferably (5.5-10.5):1, preferably (6-10):1, preferably (6.5-9.5):1, preferably (7-9):1; The molar ratio of borane to chain transfer agent is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100; The molar ratio of the organic quaternary ammonium salt to the chain transfer agent is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100; The molar ratio of carbon dioxide consumption (mol) to chain transfer agent is (4.5-11.5):1, preferably (5-11):1, preferably (5.5-10.5):1, preferably (6-10):1, preferably (6.5-9.5):1, preferably (7-9):1; The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide. Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron; Preferably, the organic quaternary ammonium salt is tetra(C1-C6 alkyl)ammonium halide, more preferably tetra(C2-C4 alkyl)ammonium halide, such as tetra-n-butylammonium halide; more preferably, the organic quaternary ammonium salt is tetra(C1-C6 alkyl)ammonium chloride, more preferably tetra(C2-C4 alkyl)ammonium chloride, such as tetra-n-butylammonium chloride; Preferably, the chain transfer agent (e.g., C3-C12 organic polyol) is selected from one or more of glycerol, trimethylolpropane (TMP), 1,2,3-butanetriol, triethylene glycol, pentaerythritol, sorbitol, 2,5-dehydro-D-glucanol, glucol and sucrose; 2) Release the carbon dioxide from the reactor, open the bottom valve, and use high-purity nitrogen to press the material in the reactor from the bottom into another high-pressure reactor, while trying to avoid the entry of carbon dioxide gas. Continue to add the first epoxide monomer into the reactor, raise the reaction temperature (for example, raise it to 45-60℃, such as 55℃), and continue the reaction (for example, 3-8 hours, such as 4-6 hours). The molar ratio of the first epoxide monomer feed amount (mol) to the chain transfer agent in step 1) is (2-6):1, preferably (2.5-5.5):1, preferably (2.8-5.2):1, preferably (3-5):1, preferably (3.2-4.7):1, preferably (3.5-4.5):1, preferably (3.8-4.2):1, preferably 4:1; The first epoxide monomer is selected from one or more (such as two, three or four) of ethylene oxide, propylene oxide, epichlorohydrin and 1,2-epoxybutane. 3) Add the second epoxide monomer and phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the reaction system, and purge with carbon dioxide to 2-4 MPa (e.g., 2.5, 2.7, 3.0, 3.2 or 3.5 MPa), raise the temperature (e.g., raise to 45-65℃, such as 50-60℃) and continue the reaction (e.g., 5-15 hours, such as 8-10 hours); The molar ratio of the second epoxide monomer to the chain transfer agent in step 1) is (13-47):1, preferably (14-46):1, preferably (15-45):1, preferably (16-44):1, preferably (17-43):1, preferably (18-42):1, preferably (19-41):1, preferably (20-40):1, preferably (21-39):1, preferably (22-38):1; The molar ratio of phthalic anhydride and / or 1,8-naphthalenedicarboxylic anhydride to the chain transfer agent in step 1) is (3.5-12.5):1, preferably (4-12):1, preferably (4.5-11.5):1, preferably (5-11):1, preferably (5.5-10.5):1, preferably (6-10):1; The molar ratio of carbon dioxide consumption (mol) to the chain transfer agent in step 1) is (12-32):1, preferably (12.5-31.5):1, preferably (13-31):1, preferably (13.5-30.5):1, preferably (14-30):1, preferably (14.5-29.5):1, preferably (15-29):1, preferably (15.5-28.5):1, preferably (16-28):1; The second epoxide monomer is selected from one or more (such as two, three, four or five) of ethylene oxide, propylene oxide, epichlorohydrin, 1,2-epoxybutane and cyclohexane oxide. 4) After terminating the reaction, remove excess monomer and discharge the material to obtain the product.

10. Star-shaped carbon dioxide-based polycarbonate-polyether random copolymer polyols having general formula (III): In the formula, s represents the number of branch chains and is an integer between 3 and 4; R 2 It is a polyvalent residue formed from C3-C12 organic polyols with hydroxyl functionality of 3-4, which act as chain transfer agents; in R 2 It connects to 3-4 branch chains; C3-C12 organic polyols are selected from one or more of glycerol, trimethylolpropane, 1,2,3-butanetriol, and pentaerythritol; Each branch of the star-shaped carbon dioxide-based polycarbonate-polyether random copolymer polyol (III) includes the following structure: 1-3 (preferably 2-3) polyether segments formed by the polymerization of epoxide monomers; and 1-2 polycarbonate segments formed by the copolymerization of epoxide monomers and CO2; Preferably, the copolyol of general formula (III) has a number average molecular weight of 800-2000, more preferably 900-1900, more preferably 1000-1800, and even more preferably 1100-1700. Preferably, the polyether segment is formed by the polymerization reaction of one or more (e.g., two, three, or four) epoxide monomers selected from propylene oxide, epichlorohydrin, 1,2-epoxybutane, and epicyclohexane, wherein the polyether segment has one or more (e.g., two, three, or four) of the following structural units: In the formula, n2 is the number of repeating units of the epoxide monomer and is 1-3, preferably 1-2; The polycarbonate segment is formed by reacting one, two, or three epoxide monomers selected from propylene oxide, epichlorohydrin, 1,2-epoxybutane, and epicyclohexane with carbon dioxide, and the polycarbonate segment has one or more (e.g., two, three, or four) of the following structural units: In the formula, m2 is the number of polycarbonate repeating units and is an integer from 1 to 3, preferably 1 to 2.

11. The star-shaped carbon dioxide-based polycarbonate-polyether random copolymer polyol according to claim 10, wherein... The aforementioned copolyol (III) has a random copolymer structure with a molecular weight of 1000–2000 Da. Its polyether content (based on the total number of repeating units in mol of epoxide monomer repeating units) is preferably 12–55 mol%, preferably 16–52 mol%, preferably 20–50 mol%, preferably 28–48 mol%, preferably 30–46 mol%. Its polycarbonate content (based on the total number of repeating units in mol of polycarbonate repeating units) is 45–88 mol%, preferably 48–84 mol%, preferably 50–80 mol%, preferably 52–72 mol%, preferably 54–70 mol%. And / or The kinematic viscosity (40°C) of the above-mentioned random copolymer polyol (III) is 300-2500 centipoise, preferably 350-2400 centipoise, preferably 400-2300 centipoise, preferably 500-2200 centipoise, preferably 600-2100 centipoise, preferably 700-2000 centipoise, preferably 800-1900 centipoise, preferably 900-1800 centipoise, preferably 1000-1700 centipoise, and preferably 1100-1600 centipoise.

12. A method for preparing a star-shaped carbon dioxide-based polycarbonate-polyether random copolymer polyol having general formula (III) according to claim 10 or 11, the method comprising: 1) Add the epoxide monomer, organoborane, organoammonium salt and C3-C12 organic polyol with hydroxyl functionality of 3-4 as chain transfer agent into a high-pressure reactor, heat (e.g., to 50℃-65℃), and maintain the pressure inside the reactor to carry out the reaction (e.g., 3-15 hours, e.g., 6-12 hours). The molar ratio of epoxide monomers to chain transfer agent C3-C12 organic polyols is (4.5-14):1, preferably (5-13):1, preferably (5.5-12.5):1, preferably (6-12):1, preferably (6.5-11):1, preferably (7-10):1; The molar ratio of borane to chain transfer agent C3-C12 organic polyol is (0.1-1):100, preferably (0.2-0.8):100, more preferably (0.3-0.7):100, more preferably (0.4-0.6):100, for example 0.5:100; The molar ratio of the organic ammonium salt to the chain transfer agent C3-C12 organic polyol is (0.02-0.4):100, preferably (0.04-0.3):100, preferably (0.08-0.2):100, preferably (0.09-0.15):100, for example 0.1:100; The epoxide monomer is selected from one, two, or three of the following: propylene oxide, epichlorohydrin, 1,2-epoxybutane, and cyclohexane oxide. Preferably, the organoborane is tri(C1-C6)boron, more preferably tri(C2-C4)boron, such as triethylboron; Preferably, the organic ammonium salt is a C1-C5 fatty acid ammonium (e.g., ammonium acetate), a tetra(C1-C6 alkyl) ammonium chloride, more preferably a tetra(C2-C4 alkyl) ammonium chloride, such as tetra-n-butylammonium chloride; Preferably, the chain transfer agent, C3-C12 organic polyol, is selected from one or more of glycerol, trimethylolpropane, 1,2,3-butanetriol, and pentaerythritol; The molar ratio of carbon dioxide consumption (mol) to chain transfer agent C3-C12 organic polyol is (3-12):1, preferably (3-11):1, preferably 3.5-10:1, preferably 4-9, preferably 5-8:1; 3) After terminating the reaction, remove excess monomer and discharge the material to obtain the product.

13. Use of the block copolymer diol according to any one of claims 1-3, or the copolymer polyol according to claim 6 or 7, or the copolymer polyol according to claim 10 or 11, wherein they are used to prepare rigid polyurethane foams, coatings, adhesives, sealants, leather, and elastomers (including synthetic leather, shoe soles, and plastic running tracks).

Images