Catalyst for preparing carbon dioxide-based multi-arm polycarbonate polyols

Abstract

Provided is a polyfunctional onium salt initiator having the following general formula (I): 'R (-L) n' '(MR'x) bHc' (I) wherein n = b + c; r (-L) n is an n-valent anionic group derived from (A) a nitrogen-free aliphatic or aromatic organic polycarboxylic acid, (B) a polyphenol, (C) a polyacrylic acid, an acrylic acid-methacrylic acid copolymer, or a polymaleic acid, (D) a hydroxyaromatic carboxylic acid, or (E) a nitrogen-containing aliphatic or aromatic organic polycarboxylic acid; -L is-COO <-> or-O <->; mR'x is an ammonium ion, sulfonium ion or phosphonium ion and H is a hydrogen ion (H +); r'is a C1-C30 hydrocarbyl group, x is 3 or 4, M is N, P or S; n is an integer from 2 to 30; b is an integer from 1 to 29, and c is an integer from 1 to 15. The incompletely onium salinized or incompletely salified initiator has high reaction activity and can be used for preparing carbon dioxide-based multi-arm polycarbonate with narrow molecular weight distribution, and the molecular weight is between hundreds of thousands and millions.

Description

TECHNICAL FIELD

[0001] The present application relates to a high-activity catalyst for preparing carbon dioxide-based multi-arm polycarbonate polyols and its use, belonging to the field of polycarbonates. BACKGROUND

[0002] Carbon dioxide-based polycarbonate polyols are prepared by anionic polymerization of carbon dioxide with an epoxide and optionally an anhydride, such as phthalic anhydride, in the presence of an initiator, such as a fully onium saltified ammonium salt, and an organic boron catalyst.

[0003] Chinese patent CN116003759A discloses a carbon dioxide-based polyester polycarbonate diol, which is obtained by one-pot one-step polymerization of an epoxy monomer, phthalic anhydride and carbon dioxide in the presence of a bifunctional organic boron catalyst and a chain transfer agent containing two active hydrogens. The carbon dioxide-based polyester polycarbonate diol can be used as a raw material to prepare degradable polyurethane materials.

[0004] However, when polycarbonate polyols are used to prepare polyurethanes, they can form multiple connected molecular chains, have better spatial structures, and significantly improve the strength of the prepared polyurethanes, but can result in excessively strong rigidity and insufficient toughness of the obtained polyurethane materials. For example, Chinese patent CN103827207A discloses an aliphatic polycarbonate for polyurethane, which involves the application of polycarbonate polyols. Although the invention can introduce a polyether segment in the form of a pre-polyether in the molecular structure, the polyether segment can only be introduced at the center of the structure by a chain transfer agent, which has a very limited effect on the overall toughness of the obtained polyurethane. As can be seen from the examples, this method does not solve the problems of material toughness and specific molding of polycarbonate polyol type polyurethanes.

[0005] CN110938087A discloses an organic metal-free catalyst with electrophilic nucleophilic bifunctionality. CN113087882A discloses an organic catalytic system with a polyboron center and applications. CN114308120A discloses a phosphonium salt amphiphilic bifunctional organic catalyst. CN115710288A discloses a phosphonium salt organic boron catalyst, a preparation method and applications thereof. CN115746034A discloses a trifunctional organic catalyst. CN115779962A discloses a two-component organic catalytic system composed of a hydrogen bond donor-nucleophilic bifunctional reagent and an organic boron reagent. CN116284520A discloses a polymer polynuclear boron organic catalyst. CN116284520A discloses a polymer polynuclear boron organic catalyst.

[0006] However, the existing initiator is a completely onium salt ammonium salt, which has low reactivity, resulting in low yield of product. During the use of the initiator, the onium salt ion is easily randomly separated, the initiator is unstable, the number of chains (the number of branches or arms) that can be initiated is unstable, and the molecular weight distribution of the polycarbonate product is too wide, and the product performance is random. SUMMARY

[0007] The object of the present application is to provide a stable multi-arm macromolecular onium salt initiator (I) with high reactivity and onium salt ions not easily separated during the reaction, which is used for preparing high molecular weight multi-arm carbon dioxide-based polycarbonate plastics, and can also be used for preparing lower molecular weight multi-arm polycarbonate polyols.

[0008] Therefore, according to the first embodiment of the present application, a multi-functional onium salt initiator (or called multi-arm macromolecular initiator) with the following general formula (I) is provided: +

[0009]

R(-L)n

(MR′x)bHc

[0010] n = b + c;

[0011] In the formula, R(-L)n is an n-valent anion group derived from (A) a nitrogen-free aliphatic or aromatic organic polycarboxylic acid, (B) a polyphenol, (C) a polyacrylic acid, an acrylic acid-methacrylic acid copolymer or a polymaleic acid, (D) a hydroxyaromatic carboxylic acid, or (E) a nitrogen-containing aliphatic or aromatic organic polycarboxylic acid; -L is -COO - (carboxylate) or -O - (oxygen); MR′x is a cationic group ammonium ion (quaternary ammonium cation), sulfonium ion (quaternary sulfonium cation) or phosphonium ion (quaternary phosphonium cation), and H is a hydrogen ion (H + ). R′ is a C1-C30 hydrocarbon group, preferably a C2-C20 hydrocarbon group, more preferably a C2-C10 hydrocarbon group, and more preferably a C2-C5 hydrocarbon group, such as ethyl, propyl or butyl.

[0012] x is 3 or 4. When MR′x is an ammonium ion (quaternary ammonium cation) or a phosphonium ion (quaternary phosphonium cation), x is 4, and when MR′x is a sulfonium ion (quaternary sulfonium cation), x is 3. M is N (nitrogen), P (phosphorus) or S (sulfur).

[0013] ​n is the total number of carboxylic and / or phenolic hydroxyl groups in the polycarboxylic acid or polyphenol of (A) - (E) above (i.e. R(-L)nHn). n is generally an integer from 2 to 30, preferably from 3 to 29, more preferably from 4 to 28, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27.

[0014] b is an integer from 1 to 29, preferably from 2 to 28, more preferably from 3 to 27, for example 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26. c is an integer greater than or equal to 1 (i.e. the compound of general formula I contains at least one COOH or phenolic OH), more preferably c is from 1 to 15, preferably from 1 to 13, preferably from 1 to 10, preferably from 1 to 6, more preferably 1, 2 or 3.

[0015] Preferably, the aliphatic or aromatic polycarboxylic acid (A) which does not contain nitrogen is (or is selected from): (A1) a (hydroxyl group-free or hydroxyl group-containing) C6-C30 (preferably C8-C20, more preferably C10-C16) aliphatic or aromatic organic polycarboxylic acid (such as 1,4-succinic acid, pentane-1,3,5-tricarboxylic acid, citric acid, malic acid, o-, m-, p- phthalic acid, trimesic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, naphthalene pentacarboxylic acid, naphthalene hexacarboxylic acid).

[0016] Preferably, the polyphenol (B) is (or is selected from) a C6-C30 (preferably C6-C20) polyphenol. More preferably, the polyphenol (C) is (or is selected from): o-, m- and p- benzenediol, naphthalene-tetrol, bisphenol A, bisphenol F, bisphenol S.

[0017] Preferably, the polyacrylic acid, acrylic-methacrylic acid copolymer or polymaleic acid (C) is a polyacrylic acid, acrylic-methacrylic acid copolymer or polymaleic acid having a number average molecular weight of from 220 to 2000 (preferably from 290 to 1500, more preferably from 350 to 1000 or from 500 to 900, such as 216, 258, 348, 600, 700 or 800).

[0018] Preferably, the hydroxyaromatic carboxylic acid (D) is a hydroxyaromatic polycarboxylic acid or polyhydroxyaromatic carboxylic acid. Preferably, the hydroxyaromatic carboxylic acid (D) is (or is selected from): hydroxyphthalic acid, hydroxyphthaloic acid, hydroxybenzene-dipropionic acid, hydroxybenzene-dibutyric acid, hydroxybenzene-dipentanoic acid, hydroxybenzene-dihexanoic acid, or gallic acid.

[0019] Preferably, the nitrogen-containing aliphatic or aromatic organic polybasic carboxylic acid (E) is (or is selected from) (El) a C2-C30 (preferably C3-C28, more preferably C4-C24) alkylene diamine tetra(C2-C6)carboxylic acid, or a nitrilo tri(C2-C6)carboxylic acid; for example, ethylenediamine tetraacetic acid, ethylenediamine tetrapropionic acid, ethylenediamine tetrabutanoic acid, ethylenediamine tetrapentanoic acid, ethylenediamine tetrahexanoic acid, propylenediamine tetraacetic acid, propylenediamine tetrapropionic acid, propylenediamine tetrabutanoic acid, propylenediamine tetrapentanoic acid, propylenediamine tetrahexanoic acid, butylenediamine tetraacetic acid, butylenediamine tetrapropionic acid, butylenediamine tetrabutanoic acid, butylenediamine tetrapentanoic acid, butylenediamine tetrahexanoic acid, nitrilotriacetic acid, nitrilotripropionic acid, nitrilotributanoic acid, nitrilotripentanoic acid, or nitrilotrihexanoic acid; or, (E2) a N-Ci-C4alkyl-piperidine dicarboxylic acid (such as N-methyl-piperidine-3,5-dicarboxylic acid), a N-Ci-C4alkyl-piperidine tricarboxylic acid (such as N-ethyl-piperidine tricarboxylic acid), or a N-Ci-C4alkyl-piperidine tetracarboxylic acid (such as N-ethyl-piperidine tetracarboxylic acid).

[0020] Preferably, R is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a nitrogen-containing aliphatic hydrocarbon group, or a nitrogen-containing aromatic hydrocarbon group.

[0021] According to a second embodiment of the present application, there is provided a fully onium salted (i.e., fully salted, fully neutralized, and containing no H + ) multifunctional onium salt initiator (or called as a multi-armed macromolecular initiator) having the following general formula (II):

[0022]

R(-L)n

(MR′x)n

[0023] wherein MR'x is a cationic group, a sulfonium ion (quaternary sulfonium cation) or a phosphonium ion (quaternary phosphonium cation).

[0024] wherein R(-L)n, R, -L, M, R', n and x are as defined above.

[0025] The present inventors have found that, despite being fully onium salted, the general formula II initiator containing a sulfonium ion (quaternary sulfonium cation) or a phosphonium ion (quaternary phosphonium cation) still has a relatively high reactivity.

[0026] According to a third embodiment of the present application, there is provided a fully onium salted (i.e., fully salted, fully neutralized, and containing no H + ) multifunctional onium salt initiator (or called as a multi-armed macromolecular initiator) having the following general formula (III):

[0027]

R(-L)n

(MR′x)n

[0028] wherein R(-L)n is an n-valent anionic group derived from the above (E) nitrogen-containing aliphatic or aromatic organic polybasic carboxylic acid;

[0029] wherein R, -L, M, R', n and x are as defined above.

[0030] wherein MR'x is a cationic group ammonium ion (quaternary ammonium cation), sulfonium ion (quaternary sulfonium cation) or phosphonium ion (quaternary phosphonium cation).

[0031] Since the compound of general formula III contains N, which is a Lewis base, it is more active, and therefore, even if it is completely onium saltified, it still has high reactivity.

[0032] The following exemplify the initiators of the present application:

[0033] I. aromatic or aliphatic polyacid type (ammonium salt onium saltified initiators are all incomplete onium saltified initiators, while sulfonium salt and phosphonium salt include "incomplete onium saltified initiators" and "complete onium saltified initiators") initiator a1: initiator a2: initiator a3: initiator b1: initiator b2: initiator c: initiator d1:

[0034] initiator d2:

[0035] initiator e:

[0036] initiator f1:

[0037] initiator f2:

[0038] initiator g: citric acid

[0039] initiator j1:

[0040] initiator j2:

[0041] initiator j3:

[0042] initiator j4:

[0043] II. nitrogen-containing polyacid onium salt initiators (including complete onium saltification and incomplete onium saltification of ammonium salt, sulfonium salt, phosphonium salt): due to being a Lewis base, it is more active.

[0044] Such as diamines: ethylenediaminetetraacetic acid (1,3, 1,2), (butylenediaminetetraacetic acid, pentane, hexane, etc.) nitrilotriacetic acid

[0045] Initiator k1:

[0046] Initiator k2:

[0047] Initiator l:

[0048] Initiator m1:

[0049] Initiator m2:

[0050] Polyamines: diethylenetriamine pentaacetic acid onium salt, triethylenetetramine hexaacetic acid onium salt

[0051] Initiator p1:

[0052] Initiator p2:

[0053] Initiator q:

[0054] III. Polymethacrylic onium salts (including fully onium salted and not fully onium salted ammonium salts, phosphonium salts, phosphonium salts) polyacrylic onium salts, polymethacrylic onium salts, polyacrylate onium salts, polymethacrylate onium salts and copolymers thereof.

[0055] Initiator s1:

[0056] Initiator s2:

[0057] Initiator s3:

[0058] 2≤n1+n2≤120, 0≤n1, 2≤n2≤120; preferably 3≤n1+n2≤70, 2≤n2≤65; more preferably 3≤n1+n2≤20, 2≤n2≤15.

[0059] Initiator s4:

[0060] 3≤n1+n2+n3≤120, 3≤n3≤120; preferably 3≤n1+n2+n3≤70, 2≤n3≤65;

[0061] The preparation method of the initiator is as follows: during the preparation of the initiator, only the corresponding carboxylic acid and the corresponding base (ammonium base, sulfonium base or phosphonium base such as tetraalkylammonium hydroxide) are neutralized to form a salt, and then water is removed to obtain onium salt.

[0062] The molecular weight of the multi-arm polycarbonate polymer can reach several million, and can also be controlled to tens of thousands.

[0063] According to the fourth embodiment of the present application, the use of the above-mentioned initiator for preparing carbon dioxide-based multi-arm polycarbonates is also provided. The molecular weight distribution index of the polycarbonate polymer prepared using the initiator of the present application is between 1.08-1.25, preferably between 1.08-1.15. The tensile strength of the polymer is between 30MPa-50MPa, the elongation at break is between 1%-10%, and the Vicat softening point is between 28°C-45°C. DETAILED DESCRIPTION

[0064] The technical solutions of the present application will be described clearly and completely in combination with the embodiments of the present application.

[0065] Example 1

[0066] Synthesis of four-arm polymer

[0067] 1) Epoxypropane, triethylboron and initiator a 2 were added together into a high-pressure reaction kettle in a molar ratio of 480:0.5:0.5; the temperature was raised to 55°C, and the pressure in the kettle was maintained for 2.5h;

[0068] 2) Carbon dioxide was charged to 2.5MPa, and the reaction was continued for 5h; the molar ratio of the consumption of carbon dioxide to initiator a 2 was 420:0.5;

[0069] 3) The gas in the kettle was evacuated, and epoxypropane was continuously added into the reaction kettle; the molar ratio of the added epoxypropane to initiator a 2 in step 1) was 200:0.5, the reaction temperature was maintained at 55°C, and the reaction was continued for 1h.

[0070] 4) Epoxypropane and phthalic anhydride were added into the reaction system; the molar ratio of the added epoxypropane, phthalic anhydride and initiator a 2 in step 1) was 2600:800:0.5; carbon dioxide was charged to 3.5MPa, the temperature was raised to 65°C, and the reaction was continued for 12h; the molar ratio of the consumption of carbon dioxide to initiator a 2 in step 1) was 1800:0.5;

[0071] 5) After the reaction is completed, the product is dissolved in dichloromethane, poured into deionized water, stirred and purified, and finally separated, dried and obtained. The polyether content in the obtained polymer is 7.9 mol%, PE (polyester) is 24.4 mol%, and polycarbonate is 67.7 mol% as determined by nuclear magnetic resonance. The number average molecular weight of the polymer is 475,000, and the molecular weight distribution index is 1.10 as determined by GPC. The molecular weight distribution is very narrow, which indicates that the four arms of the polymer are basically equal in length.

[0072] The tensile strength of the polymer of Example 1 is 38 MPa, the elongation at break is 6.7%, and the Vicat softening point is 41°C.

[0073] Example 2

[0074] Synthesis of three-arm polymer

[0075] 1) Ethylene oxide, triethyl boron and initiator b 1 are added to a high-pressure reactor in a molar ratio of 480:1:0.5, carbon dioxide is charged to 2.0 MPa, the temperature is raised to 55°C, and the reaction is continued for 3 h; the molar ratio of carbon dioxide consumption to initiator b 1 is 470:0.5;

[0076] 2) The gas in the reactor is evacuated, and ethylene oxide is continuously added to the reactor, the molar ratio of ethylene oxide to initiator b 1 in step 1) is 300:0.5, the reaction temperature is maintained at 55°C, and the reaction is continued for 2 h.

[0077] 3) Ethylene oxide and phthalic anhydride are added to the reaction system, the molar ratio of ethylene oxide, phthalic anhydride and initiator b 1 in step 1) is 2600:600:0.5; carbon dioxide is charged to 3.5 MPa, the temperature is raised to 60°C, and the reaction is continued for 12 h; the molar ratio of carbon dioxide consumption to initiator b 1 in step 1) is 1990:0.5;

[0078] 4) After the reaction is completed, the product is dissolved in dichloromethane, poured into deionized water, stirred and purified, and finally separated, dried and obtained. The polyether content in the obtained polymer is 7.9 mol%, PE (polyester) is 24.4 mol%, and polycarbonate is 67.7 mol% as determined by nuclear magnetic resonance. The number average molecular weight of the polymer is 475,000, and the molecular weight distribution index is 1.10 as determined by GPC. The molecular weight distribution is very narrow, which indicates that the four arms of the polymer are basically equal in length.

[0079] The tensile strength of the polymer of Example 2 is 30 MPa, the elongation at break is 9.8%, and the Vicat softening point is 30°C.

[0080] Example 3

[0081] Synthesis of four-arm polymer

[0082] 1) The propylene oxide, triethyl boron and initiator c are added together into a high-pressure reactor in a molar ratio of 600:0.5:0.1, carbon dioxide is charged to 2.5 MPa, the temperature is raised to 50°C, and the pressure in the reactor is maintained for 3 h; the molar ratio of the consumption of carbon dioxide to initiator c is 592:0.1;

[0083] 2) The propylene oxide and epoxycyclohexane are continuously added to the reaction system, and carbon dioxide is charged to 3.5 MPa; the molar ratio of the propylene oxide, epoxycyclohexane and initiator c in step 1) is 2380:1020:0.1; the temperature is raised to 60°C, and the reaction is continuously carried out for 15 h; the molar ratio of the consumption of carbon dioxide to initiator c in step 1) is 3368:0.1;

[0084] 3) After the reaction is completed, the product is dissolved in dichloromethane, poured into deionized water, stirred and purified, and finally separated, dried to obtain the product, a multi-arm polymer. The polyether content in the obtained polymer is 1 mol%, and the polycarbonate is 99 mol% as determined by nuclear magnetic resonance. The number average molecular weight of the polymer is 3.152 million, and the molecular weight distribution index is 1.13 as determined by GPC.

[0085] The tensile strength of the polymer of Example 3 is 47 MPa, the elongation at break is 5.4%, and the Vicat softening point is 40°C.

[0086] Example 4

[0087] Synthesis of a four-arm polymer

[0088] 1) The propylene oxide, triethyl boron and initiator d2 are added together into a high-pressure reactor in a molar ratio of 500:0.5:0.5; the temperature is raised to 55°C, and the pressure in the reactor is maintained for 0.5 h;

[0089] 2) Carbon dioxide is charged to 1.5 MPa, and the reaction is continuously carried out for 2 h; the molar ratio of the consumption of carbon dioxide to initiator d2 is 460:0.5;

[0090] 3) The bottom valve of the reactor is opened, the material is transferred to another reactor by the pressure in the reactor, and propylene oxide is added; the molar ratio of the propylene oxide and initiator d2 in step 1) is 100:0.5, the reaction temperature is maintained at 55°C, and the reaction is continuously carried out for 1 h.

[0091] 4) The propylene oxide is added to the reaction system; the molar ratio of the propylene oxide and initiator d2 in step 1) is 3690:0.5; carbon dioxide is charged to 3.5 MPa, the reaction temperature is maintained at 55°C, and the reaction is continuously carried out for 16 h; the molar ratio of the consumption of carbon dioxide to trihydroxymethyl propane in step 1) is 3670:0.5;

[0092] 5) After the reaction, the product was dissolved in dichloromethane, poured into deionized water, stirred and purified, and finally separated, dried to obtain the product multi-arm polymer. The polyether content in the obtained polymer was 3.7 mol% and the polycarbonate content was 96.3 mol% as determined by nuclear magnetic resonance.

[0093] The polymer was a random structure, and the polyether content was greater than 0.3%.

[0094] The number average molecular weight of the polymer was 547,000 and the molecular weight distribution index was 1.21 as measured by GPC.

[0095] For phosphonium ions, the polymer obtained using the initiator d2 which was all onium salt had a narrower molecular weight distribution, which indicated that it still had higher reactivity.

[0096] The tensile strength of the polymer of Example 4 was 33 MPa, the elongation at break was 8.5%, and the Vicat softening point was 36°C.

[0097] Example 5

[0098] Synthesis of four-arm polymer

[0099] 1) Propylene oxide, phthalic anhydride, triethyl boron and initiator e were added to a high-pressure reactor in a molar ratio of 3500: 1000: 1: 0.5, and carbon dioxide was filled to 3.0 MPa, and the temperature was raised to 65°C, and the pressure in the reactor was maintained for 20 h, and the molar ratio of carbon dioxide consumption to initiator e was 2380: 0.5;

[0100] 2) After the reaction, the product was dissolved in dichloromethane, poured into deionized water, stirred and purified, and finally separated, dried to obtain the product multi-arm polymer. The polyether content in the obtained polymer was 3.4 mol%, PE 28.6 mol%, and polycarbonate 68 mol% as determined by nuclear magnetic resonance.

[0101] The number average molecular weight of the polymer was 756,000 and the molecular weight distribution index was 1.12 as measured by GPC.

[0102] The tensile strength of the polymer of Example 5 was 38 MPa, the elongation at break was 5.3%, and the Vicat softening point was 40°C.

[0103] Example 6

[0104] Synthesis of three-arm polymer

[0105] 1) Propylene oxide, ethylene oxide, 1,8-naphthalic anhydride, triethyl boron and initiator f2 were added into a high-pressure reactor in a molar ratio of 3050:2000:1600:0.5:0.5, and carbon dioxide was charged to 3.0 MPa, and the temperature was raised to 60°C, and the pressure in the reactor was maintained for 25 h. The molar ratio of the consumed carbon dioxide to initiator f2 was 3220:0.5;

[0106] 2) After the reaction was completed, the product was dissolved in dichloromethane, poured into deionized water, stirred and purified, and finally separated, dried to obtain the product multi-arm polymer. The polyether content in the obtained polymer was 4.6 mol%, PE 31.7 mol%, and polycarbonate 63.7 mol% as determined by nuclear magnetic resonance.

[0107] The number average molecular weight of the polymer was 1.391 million, and the molecular weight distribution index was 1.23 as determined by GPC.

[0108] For sulfonium ions, the polymer obtained using the initiator f2 which was all onium salt had a narrower molecular weight distribution, which indicated that it still had a higher reactivity.

[0109] The tensile strength of the polymer of Example 6 was 46 MPa, the elongation at break was 2.3%, and the Vicat softening point was 45°C.

[0110] Example 7

[0111] Synthesis of four-arm polymer

[0112] 1) Propylene oxide, triethyl boron and initiator K2 were added into a high-pressure reactor in a molar ratio of 600:0.5:0.1, and carbon dioxide was charged to 2.5 MPa; the temperature was raised to 50°C, and the pressure in the reactor was maintained for 3 h; the molar ratio of the consumed carbon dioxide to initiator K2 was 598:0.1;

[0113] 2) Propylene oxide and epicyclohexane were continuously added to the reaction system, and carbon dioxide was charged to 3.5 MPa. The molar ratio of the added propylene oxide, epicyclohexane and initiator K2 in step 1) was 2380:1020:0.1; the temperature was raised to 60°C, and the reaction was continued for 15 h. The molar ratio of the consumed carbon dioxide to initiator K2 in step 1) was 3344:0.1;

[0114] 3) After the reaction was completed, the product was dissolved in dichloromethane, poured into deionized water, stirred and purified, and finally separated, dried to obtain the product multi-arm polymer. The polyether content in the obtained polymer was 1.2 mol%, and polycarbonate 98.8 mol% as determined by nuclear magnetic resonance. The number average molecular weight of the polymer was 3.085 million, and the molecular weight distribution index was 1.18 as determined by GPC.

[0115] The tensile strength of the polymer of Example 7 was 44 MPa, the elongation at break was 6.2%, and the Vicat softening point was 39°C.

[0116] Example 8

[0117] Synthesis of the four-arm polymer

[0118] 1) 1,2-epoxybutane, oxirane, triethylboron and initiator S1 (molecular weight 4150 Da, n1 average value 3, n2 average value 12) were added together into a high-pressure reactor in a molar ratio of 3000:2000:0.5:0.2, carbon dioxide was charged to 3.5 MPa, the temperature was raised to 55°C, and the pressure in the reactor was maintained for 25 h, during which the molar ratio of carbon dioxide consumption to initiator S1 was 4985:0.2;

[0119] 2) After the reaction was completed, the product was dissolved in dichloromethane, poured into deionized water, stirred to purify, and finally separated, dried to obtain the product, a multi-arm polymer. Nuclear magnetic resonance was used to determine that the polyether content in the obtained polymer was 0.3 mol%, and the polycarbonate content was 99.7 mol%.

[0120] The number average molecular weight of the polymer was 1.776 million, and the molecular weight distribution index was 1.25, as measured by GPC.

[0121] The tensile strength of the polymer of Example 8 was 33 MPa, the elongation at break was 2.7%, and the Vicat softening point was 36°C.

[0122] Example 9

[0123] Synthesis of the four-arm polymer (simply by adjusting the content of polyether in the inner and outer sections by changing the CO2 pressure)

[0124] 1) Propylene oxide, phthalic anhydride, triethylboron and initiator c were added together into a high-pressure reactor in a molar ratio of 3800:1200:0.5:0.5, carbon dioxide was charged to 1.5 MPa, the temperature was raised to 65°C, and the pressure in the reactor was maintained for 10 h, during which the molar ratio of carbon dioxide consumption to initiator c was 560:0.5;

[0125] 2) Then the carbon dioxide pressure was adjusted to 3.5 MPa, the reaction temperature was adjusted to 60°C, and the pressure in the reactor was maintained for continued reaction for 10 h, during which the molar ratio of carbon dioxide consumption to initiator c in step 1) was 1870:0.5;

[0126] 3) After the reaction was completed, the product was dissolved in dichloromethane, poured into deionized water, stirred to purify, and finally separated, dried to obtain the product, a multi-arm polymer. Nuclear magnetic resonance was used to determine that the polyether content in the obtained polymer was 4.5 mol%, the PE content was 31.6 mol%, and the polycarbonate content was 63.9 mol%.

[0127] The number average molecular weight of the polymer was 884,000 and the molecular weight distribution index was 1.12 as measured by GPC.

[0128] The tensile strength of the polymer of Example 9 was 41 MPa, the elongation at break was 3.5%, and the Vicat softening point was 43°C.

Claims

1. A multifunctional onium salt initiator having the following general formula (I): 【R(-L)n】【(MR′x)bHc】(I), Where n = b + c; In the formula, R(-L)n is an n-valent anionic group derived from (A) a nitrogen-free aliphatic or aromatic organic polycarboxylic acid, (B) a polyphenol, (C) polyacrylic acid, acrylic acid-methacrylic acid copolymer or polymaleic acid, (D) a hydroxy aromatic carboxylic acid, or (E) a nitrogen-containing aliphatic or aromatic organic polycarboxylic acid. -L is -COO - or -O - ; MR′x is a cationic group consisting of ammonium ion (quaternary ammonium cation), sulfonium ion (quaternary strontium cation), or phosphonium ion (quaternary phosphonium cation), and H is a hydrogen ion (H+). + ); R′ is a C1-C30 hydrocarbon group, preferably a C2-C20 hydrocarbon group, more preferably a C2-C10 hydrocarbon group, and even more preferably a C2-C5 hydrocarbon group, such as ethyl, propyl or butyl; x is 3 or 4. When MR′x is an ammonium ion (quaternary ammonium cation) or a phosphonium ion (quaternary phosphonium cation), x is 4, while when MR′x is a sulfonium ion (quaternary strontium cation), x is 3. M is N (nitrogen), P (phosphorus), or S (sulfur); n is the total number of carboxylic acids and / or phenolic hydroxyl groups in the polycarboxylic acids or polyphenols of (A)-(E) above, and n is an integer from 2 to 30, preferably 3 to 29, more preferably 4 to 28, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27; b is an integer from 1 to 29, preferably from 2 to 28, more preferably from 3 to 27, for example 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26; c is an integer from 1 to 15, preferably 1 to 13, preferably 1 to 10, preferably 1 to 6, and more preferably 1, 2 or 3.

2. The multifunctional onium salt initiator according to claim 1, wherein... The nitrogen-free aliphatic or aromatic polycarboxylic acid (A) is (or selected from): C6-C30 (preferably C8-C20, more preferably C10-C16) aliphatic or aromatic organic polycarboxylic acids, such as 1,4-succinic acid, pentane-1,3,5-tricarboxylic acid, citric acid, malic acid, ortho-, meta-, and tere-phthalic acid, triphenylcarboxylic acid, tetraphenylcarboxylic acid, naphthalenedicarboxylic acid, triphenylcarboxylic acid, tetraphenylcarboxylic acid, pentaphenylcarboxylic acid, and hexaphenylcarboxylic acid; and / or The polyphenol (B) is (or selected from) C6-C30 (preferably C6-C20) polyphenols; more preferably, the polyphenol (C) is (or selected from): ortho-, meta-, and para-hydroxybenzene, naphthol, bisphenol A, bisphenol F, bisphenol S; and / or Polyacrylic acid, acrylic acid-methacrylic acid copolymer, or polymaleic acid (C) is a polyacrylic acid, acrylic acid-methacrylic acid copolymer, or polymaleic acid with a number average molecular weight of 220-2000 (preferably 290-1500, more preferably 350-1000 or 500-900, such as 216, 258, 348, 600, 700, or 800); and / or The hydroxy aromatic carboxylic acid (D) is a hydroxy aromatic polycarboxylic acid or a polyhydroxy aromatic carboxylic acid; preferably, the hydroxy aromatic carboxylic acid (D) is (or selected from): hydroxyphthalic acid, hydroxyphthalic acid, hydroxyphthalopropyl acid, hydroxyphthalobutyl acid, hydroxyphthaloyl valerate, hydroxyphthalic acid, or gallic acid; and / or Nitrogen-containing aliphatic or aromatic organic polycarboxylic acids (E) are (or selected from): (E1) C2-C30 (preferably C3-C28, more preferably C4-C24) alkylene diaminetetra(C2-C6)carboxylic acids, or nitrotri(C2-C6)carboxylic acids; for example, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminetetrabutyric acid, ethylenediaminetetravalanoic acid, ethylenediaminetetrahexanoic acid, propylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetrabutyric acid, propylenediaminetetravalanoic acid, propylenediaminetetrahexanoic acid, butylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetrabutyric acid, propylenediaminetetravalanoic acid, butylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetravalanoic acid, propylenediaminetetrahexanoic acid, propylenediaminetetraacetic ... Acids, including butanediaminetetrapropionic acid, butanediaminetetrabutyric acid, butanediaminetetravalanoic acid, butanediaminetetrahexanoic acid, nitrotriacetic acid, nitrotripropionic acid, nitrotributyric acid, nitrotrivalanoic acid, or nitrotrihexanoic acid; or (E2)N-C1-C4 alkyl-piperidine dicarboxylic acid (e.g., N-methyl-piperidine-3,5-dicarboxylic acid), N-C1-C4 alkyl-piperidine tricarboxylic acid (e.g., N-ethyl-piperidine tricarboxylic acid), or N-C1-C4 alkyl-piperidine tetracarboxylic acid (e.g., N-ethyl-piperidine tetracarboxylic acid).

3. The multifunctional onium salt initiator according to claim 1 or 2, wherein... R is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a nitrogen-containing aliphatic hydrocarbon group, or a nitrogen-containing aromatic hydrocarbon group.

4. Fully onium-treated multifunctional onium salt initiators having the following general formula (II): 【R(-L)n】【(MR′x)n】(II), In the formula, R(-L)n is an n-valent anionic group derived from (A) a nitrogen-free aliphatic or aromatic organic polycarboxylic acid, (B) a polyphenol, (C) polyacrylic acid, acrylic acid-methacrylic acid copolymer or polymaleic acid, (D) a hydroxy aromatic carboxylic acid, or (E) a nitrogen-containing aliphatic or aromatic organic polycarboxylic acid. -L is -COO - or -O - ; MR′x is a cationic group consisting of sulfonium ion (quaternary strontium cation) or phosphonium ion (quaternary phosphonium cation); R′ is a C1-C30 hydrocarbon group, preferably a C2-C20 hydrocarbon group, more preferably a C2-C10 hydrocarbon group, and even more preferably a C2-C5 hydrocarbon group, such as ethyl, propyl or butyl; x is 3 or 4. When MR′x is a phosphonium ion (quaternary phosphonium cation), x is 4, while when MR′x is a sulfonium ion (quaternary strontium cation), x is 3. M is either P (phosphorus) or S (sulfur); n is the total number of carboxylic acids and / or phenolic hydroxyl groups in the polycarboxylic acids or polyphenols of (A)-(E) above. n is an integer from 2 to 30, preferably 3 to 29, more preferably 4 to 28, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27.

5. The multifunctional onium salt initiator according to claim 4, wherein... The nitrogen-free aliphatic or aromatic polycarboxylic acid (A) is (or selected from): C6-C30 (preferably C8-C20, more preferably C10-C16) aliphatic or aromatic organic polycarboxylic acids, such as 1,4-succinic acid, pentane-1,3,5-tricarboxylic acid, citric acid, malic acid, ortho-, meta-, and tere-phthalic acid, triphenylcarboxylic acid, tetraphenylcarboxylic acid, naphthalenedicarboxylic acid, triphenylcarboxylic acid, tetraphenylcarboxylic acid, pentaphenylcarboxylic acid, and hexaphenylcarboxylic acid; and / or The polyphenol (B) is (or selected from) C6-C30 (preferably C6-C20) polyphenols; more preferably, the polyphenol (C) is (or selected from): ortho-, meta-, and para-hydroxybenzene, naphthol, bisphenol A, bisphenol F, bisphenol S; and / or Polyacrylic acid, acrylic acid-methacrylic acid copolymer, or polymaleic acid (C) is a polyacrylic acid, acrylic acid-methacrylic acid copolymer, or polymaleic acid with a number average molecular weight of 220-2000 (preferably 290-1500, more preferably 350-1000 or 500-900, such as 216, 258, 348, 600, 700, or 800); and / or The hydroxy aromatic carboxylic acid (D) is a hydroxy aromatic polycarboxylic acid or a polyhydroxy aromatic carboxylic acid; preferably, the hydroxy aromatic carboxylic acid (D) is (or selected from): hydroxyphthalic acid, hydroxyphthalic acid, hydroxyphthalopropyl acid, hydroxyphthalobutyl acid, hydroxyphthaloyl valerate, hydroxyphthalic acid, or gallic acid; and / or Nitrogen-containing aliphatic or aromatic organic polycarboxylic acids (E) are (or selected from): (E1) C2-C30 (preferably C3-C28, more preferably C4-C24) alkylene diaminetetra(C2-C6)carboxylic acids, or nitrotri(C2-C6)carboxylic acids; for example, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminetetrabutyric acid, ethylenediaminetetravalanoic acid, ethylenediaminetetrahexanoic acid, propylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetrabutyric acid, propylenediaminetetravalanoic acid, propylenediaminetetrahexanoic acid, butylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetrabutyric acid, propylenediaminetetravalanoic acid, butylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetravalanoic acid, propylenediaminetetrahexanoic acid, propylenediaminetetraacetic ... Acids, including butanediaminetetrapropionic acid, butanediaminetetrabutyric acid, butanediaminetetravalanoic acid, butanediaminetetrahexanoic acid, nitrotriacetic acid, nitrotripropionic acid, nitrotributyric acid, nitrotrivalanoic acid, or nitrotrihexanoic acid; or (E2)N-C1-C4 alkyl-piperidine dicarboxylic acid (e.g., N-methyl-piperidine-3,5-dicarboxylic acid), N-C1-C4 alkyl-piperidine tricarboxylic acid (e.g., N-ethyl-piperidine tricarboxylic acid), or N-C1-C4 alkyl-piperidine tetracarboxylic acid (e.g., N-ethyl-piperidine tetracarboxylic acid).

6. Fully onium-treated multifunctional onium salt initiators having the following general formula (III): 【R(-L)n】【(MR′x)n】(III), In the formula, R(-L)n is an n-valent anionic group derived from (E) nitrogen-containing aliphatic or aromatic organic polycarboxylic acids; -L is -COO - or -O - ; MR′x is a cationic group consisting of ammonium ion (quaternary ammonium cation), sulfonium ion (quaternary strontium cation), or phosphonium ion (quaternary phosphonium cation). R′ is a C1-C30 hydrocarbon group, preferably a C2-C20 hydrocarbon group, more preferably a C2-C10 hydrocarbon group, and even more preferably a C2-C5 hydrocarbon group, such as ethyl, propyl or butyl; x is 3 or 4. When MR′x is a phosphonium ion (quaternary phosphonium cation), x is 4, while when MR′x is a sulfonium ion (quaternary strontium cation), x is 3. M is N (nitrogen), P (phosphorus), or S (sulfur); n is the total number of carboxylic acids and / or phenolic hydroxyl groups in the polycarboxylic acids or polyphenols of (A)-(E) above. n is an integer from 2 to 30, preferably 3 to 29, more preferably 4 to 28, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27.

7. The multifunctional onium salt initiator according to claim 6, wherein... Nitrogen-containing aliphatic or aromatic organic polycarboxylic acids (E) are (or selected from): (E1) C2-C30 (preferably C3-C28, more preferably C4-C24) alkylene diaminetetra(C2-C6)carboxylic acids, or nitrotri(C2-C6)carboxylic acids; for example, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminetetrabutyric acid, ethylenediaminetetravalanoic acid, ethylenediaminetetrahexanoic acid, propylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetrabutyric acid, propylenediaminetetravalanoic acid, propylenediaminetetrahexanoic acid, butylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetrabutyric acid, propylenediaminetetravalanoic acid, butylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetravalanoic acid, propylenediaminetetrahexanoic acid, propylenediaminetetraacetic ... Acids, including butanediaminetetrapropionic acid, butanediaminetetrabutyric acid, butanediaminetetravalanoic acid, butanediaminetetrahexanoic acid, nitrotriacetic acid, nitrotripropionic acid, nitrotributyric acid, nitrotrivalanoic acid, or nitrotrihexanoic acid; or (E2)N-C1-C4 alkyl-piperidine dicarboxylic acid (e.g., N-methyl-piperidine-3,5-dicarboxylic acid), N-C1-C4 alkyl-piperidine tricarboxylic acid (e.g., N-ethyl-piperidine tricarboxylic acid), or N-C1-C4 alkyl-piperidine tetracarboxylic acid (e.g., N-ethyl-piperidine tetracarboxylic acid).

8. Use of the initiator of any one of claims 1-7 for the preparation of carbon dioxide-based multi-arm polycarbonate.

9. The use according to claim 8, wherein the molecular weight distribution index of the carbon dioxide-based multi-arm polycarbonate prepared using the initiator of any one of claims 1-7 is between 1.08 and 1.25, preferably between 1.08 and 1.

15.

10. The use according to claim 8 or 9, wherein the carbon dioxide-based multi-arm polycarbonate prepared using the initiator of any one of claims 1-7 has a tensile strength of 30 MPa to 50 MPa, an elongation at break of 1% to 10%, and a Vicat softening point of 28°C to 45°C.

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