Alkylene oxide polymerization using aluminum compounds and phosphorus-nitrogen bases

Abstract

The polyethers are prepared by polymerizing alkylene oxide in the presence of a starter, an aluminum compound having at least one hydrocarbyl substituent, and a phosphorus-nitrogen base. The phosphorus-nitrogen base is present in a small molar ratio relative to the amount of starter. The presence of such a small amount of phosphorus-nitrogen base greatly increases the catalytic activity of the system compared to when the aluminum compound is used by itself. The product polyethers have low amounts of unsaturated polyether impurities and little or no undesirable high molecular weight fractions. The polymers of propylene oxide have a very low proportion of primary hydroxyl groups.

Description

Technical Field

[0001] The present invention relates to a process for polymerizing one or more alkylene oxides or copolymerizing one or more alkylene oxides with one or more comonomers that are not alkylene oxides.

Background Art

[0002] Alkylene oxide polymers and copolymers are produced in large quantities worldwide. Polyether polyols, for example, are important raw materials for producing polyurethanes. In particular, they are used to produce highly elastic, molded, or rigid foams. Polyether monools are used, among other applications, as surfactants and industrial solvents, for example. Carbonate and ester-modified alkylene oxide polymers also find use in these and other applications.

[0003] Polyether monools and polyols are produced by polymerizing alkylene oxides in the presence of a starter compound. The starter compound has one or more functional groups to which the alkylene oxide can react to initiate the formation of polymer chains. The main function of the starter compound is to provide molecular weight control and to establish the number of hydroxyl groups that the polyether will have.

[0004] A catalyst is required to obtain an economical polymerization rate. The most commonly used catalysts are alkali metal hydroxides such as potassium hydroxide and so-called double metal cyanide (DMC) catalyst complexes, and its zinc hexacyanocobaltate catalyst complex is the most commercially important type.

[0005] Alkali metal hydroxides offer the benefits of low catalyst cost and acceptable polymerization rates. They are versatile in that they effectively polymerize many alkylene oxides. The resulting polyethers typically have a narrow molecular weight distribution, though not always. A particular advantage of these catalysts is that they can be used to polymerize ethylene oxide on an alcohol starter. This ability is industrially very important, as many polyether polyols produced as polyurethane raw materials are block copolymers made by polymerizing propylene oxide and then polymerizing ethylene oxide on a starter compound. Alkali metal hydroxide catalysts make this easy and inexpensive, as both polymerizations can be carried out in the same vessel using the same catalyst system without recovering the intermediate poly(propylene oxide) polyol.

[0006] Nevertheless, alkali metal hydroxides have well-known drawbacks. Alkali metal hydroxide catalysts promote a side reaction that forms unsaturated monoalcohols, which are then alkoxylated to form undesirable monofunctional species. The presence of these undesirable monofunctional species can also broaden the molecular weight distribution. Polyols produced using these catalysts need to be neutralized and purified to remove catalyst residue, which adds significant capital and operational costs to the manufacturing process. In addition, the resulting polyethers tend to have a broad molecular weight distribution when produced in a reverse-mixing continuous process.

[0007] DMC catalysts offer rapid polymerization rates compared to alkali metal catalysts, even when used at very low catalyst concentrations. In addition, they possess clear and significant advantages over alkali metal catalysts. DMC catalysts rarely promote side reactions that produce monofunctional byproducts, so the hydroxyl functional value of the product is close to the theoretical value (as defined by the starter). A second major advantage is the elimination of the neutralization step. Unlike when alkali metal hydroxides are used as polymerization catalysts, catalyst residues can often be left in the product. This can significantly reduce production costs. A third advantage is that, unlike alkali metal hydroxide catalysts, DMC catalyst complexes produce low polydisperse polymers when polymerization is carried out in a reverse-mixed continuous main reactor.

[0008] Nevertheless, DMC catalysts also have their drawbacks. They tend to perform poorly in the presence of high concentrations of hydroxyl groups, particularly in the presence of low molecular weight starter compounds such as glycerin, which have hydroxyl groups at the 1,2- or 1,3-positions relative to each other. Under these conditions, the catalyst is difficult to activate, the reaction proceeds slowly, and is often inactivated before polymerization is complete. This represents a significant limitation to the widespread adoption of DMC catalysts. Often, the polyether needs to be produced in two or more separate steps, with the initial stages of polymerization carried out in the presence of an alkali metal catalyst, and the resulting intermediate product washed, after which the remainder of polymerization is carried out using the DMC catalyst. This approach requires the intermediate to be neutralized and purified (because the DMC catalyst is inactivated by a strong base), thus reintroducing the cost that DMC catalyzed polymerization is intended to avoid.

[0009] Another very significant drawback of DMC catalysts is that they cannot be used on an industrial scale to produce ethylene oxide-capped polyethers. Instead of being added to the chain ends in a regular and controlled manner, ethylene oxide tends to produce very high molecular weight poly(ethylene oxide) polymers instead. Despite many attempts to solve this problem, it has not been adequately addressed, and ethylene oxide-capped polyethers are almost always produced on an industrial scale by carrying out a capping step using alkali metal hydroxide catalysts.

[0010] Another problem associated with DMC catalysts is the generation of small amounts of very high molecular weight (40,000+ g / mol) polymers. The presence of these polymers can negatively affect the ability of polyether polyols produced with DMC catalyst complexes to increase polyol viscosity, broaden the molecular weight distribution, and produce flexible polyurethane foams.

[0011] Certain Lewis acids have been evaluated as catalysts for alkylene oxide polymerization. While Lewis acids essentially require no activation time, they are rapidly deactivated and therefore cannot produce high molecular weight polymers or high conversion rates of alkylene oxide polymers. In addition, poly(propylene oxide) polymers produced by Lewis acid catalysts tend to have a large proportion of primary hydroxyl groups.

[0012] In addition, various aluminum compounds have been described for use as alkylene oxide polymerization catalysts.

[0013] Polym.Chem.2012,3,1189-1195 describes the polymerization of propylene oxide in the presence of a poly(propylene oxide) starter compound, triisobutylaluminum, and a phosphazene base. This polymerization is carried out in a toluene solution at 20°C. A large amount of phosphazene base is used, approximately 1 mole per equivalent of the starter. U.S. Patent Application Publication 2018 / 0237586 describes another solution polymerization of propylene oxide in the presence of trialkylaluminum and nitronium alkoxide, the latter described as the starter. In this case as well, a large amount of nitronium alkoxide is used. High molecular weight polyethers with a broad molecular weight distribution are obtained.

[0014] Macromolecules 2008, 41, 7058-7063 describes the polymerization of epichlorohydrins in the presence of tetraoctylammonium bromide using triisobutylaluminum compounds, in the absence of a starter, at temperatures up to room temperature.

[0015] U.S. Patent No. 6,919,486 describes the polymerization of propylene oxide in the presence of a polyether triol starter and an aluminum phosphonate catalyst. The capping of ethylene oxide is also described. This polymerization is carried out at a temperature of 110°C in the absence of a solvent.

[0016] Macromolecules 1974,7,153-160 describes the low-temperature polymerization of bulk propylene oxide in the presence of an aluminoxane such as (C2H5)2AlOAl(C2H5)2(TEDA). The starter is not mentioned. Polyethers with molecular weights of 100,000 to 1,000,000 are obtained. J.Polym.Sci. 1973,11,699-712 describes the polymerization of propylene oxide in solution at 40°C using TEDA in the absence of a starter.

[0017] Diethylaluminum chloride is described in U.S. Patent No. 3,029,216 as a catalyst for alkylene oxide polymerization in solution polymerization without a starter at temperatures up to 110°C, and in J.Polym.Sci. 1959, 34, 157-160 as a catalyst for alkylene oxide polymerization in bulk polymerization without a starter at 25°C. High molecular weight polymers can be obtained. [Overview of the project]

[0018] In one aspect, the present invention provides a method for producing an alkylene oxide polymer or copolymer, comprising: (i) at least one aluminum compound containing at least one trisubstituted aluminum atom, wherein at least one substituent of the at least one trisubstituted aluminum atom is hydrocarbyl; (ii) at least one starter; (iii) at least one alkylene oxide; (iv) at least one phosphazene-nitrogen base in an amount of 0.00005 to 0.1 moles per equivalent of the starter; and optionally (v) at least one comonomer that is not oxirane; and polymerizing the alkylene oxide or copolymerizing the alkylene oxide and comonomer to form an alkylene oxide polymer or copolymer.

[0019] The method of the present invention offers several advantages in terms of both process and product.

[0020] The advantages of the process include a rapid polymerization rate, the ability to use alkoxylation starters with a wide range of molecular weights, particularly low molecular weight starters with hydroxyl equivalent weights of 30-75, the ability to use significantly lower levels of catalyst than required with alkali metal hydroxides, thereby reducing costs and, in some cases, allowing the use of polyols without the need to first remove catalyst residues, the ability to use higher URO (unreacted alkylene oxide) levels than those that can be used with DMC catalysts without forming undesirable high molecular weight polymers, and the catalyst's ability to uniformly polymerize ethylene oxide. This last advantage is of great industrial importance, given the difficulties encountered in polymerizing ethylene oxide with multimetallic cyanide catalysts. The ability to uniformly polymerize ethylene oxide allows the catalyst to be used to produce oxyethylene-capped polyols having a high proportion of primary hydroxyl groups, enabling the preparation of oxyethylene-capped poly(propylene oxide), oxyethylene-capped poly(butylene oxide), oxyethylene-capped poly(propylene oxide-co-ethylene oxide), and oxyethylene-capped poly(butylene oxide-co-ethylene oxide) polyols using a single catalyst for the polymerization of propylene oxide, butylene oxide, propylene oxide-co-ethylene oxide, and / or butylene oxide-co-ethylene oxide, as well as the capping (ethoxylation) step.

[0021] From the perspective of the products, the advantages of the present invention include i) low polydispersity (M w / M n ii) the absence of "high molecular weight tails" seen in DMC catalytic polymerization, iii) the formation of undesirable monofunctional species due to isomerization of alkylene oxide to unsaturated alcohols, and iv) the formation of polyethers with a very low proportion of primary hydroxyl groups when propylene oxide is monopolymerized.

[0022] The aluminum compound is an aluminum compound containing at least one trisubstituted aluminum atom. At least one, at least two, or all three substituents on the at least one trisubstituted aluminum atom are hydrocarbyl substituents. Two or more substituents on the trisubstituted aluminum atom may together form a ring structure.

[0023] The aluminum compound may contain one, two, three, four or more aluminum atoms (for example, up to 100, up to 50, up to 25, up to 12, or up to 5 aluminum atoms), at least one of which is trisubstituted.

[0024] Hydrocarbyl substituents can be aliphatic, alicyclic, aromatic, or any combination of two or more thereof, and are bonded to an aluminum atom via an aluminum-carbon bond. In some cases, hydrocarbyl substituents have up to 12, up to 6, or up to 4 carbon atoms. Hydrocarbyl groups can be linear or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl. Hydrocarbyl substituents may be unsubstituted or inertly substituted.

[0025] Non-hydrocarbyl substituents bonded to the aluminum atom may be, for example, halogens, phosphonates, hydrides, oxo (i.e., -O-), alkoxides, or phenoxides.

[0026] The halogen substituent may be, for example, fluorine, chlorine, bromine, or iodine.

[0027] Alkoxide or phenoxide substituents are -OR 2 or -O(-R 2 -O) z -R 2 -It may take the form of -OZ, in the formula, each R 2is, independently, a hydrocarbyl or substituted hydrocarbyl group, z is zero or a positive number, Z is a hydrocarbyl, inert substituted hydrocarbyl, hydrogen, or -AlY2, and each Y is a halogen, hydrocarbyl, phosphonate, hydrogen, oxo (i.e., -O-), or an alkoxide or phenoxide. The alkoxide or phenoxide may contain a polyether chain such as poly(oxyethylene) or poly(oxypropylene chain). Specific examples of alkoxide or phenoxide substituents include ethoxide, n-propoxide, isopropoxide, t-butoxide, n-butoxide, isobutoxide, phenoxide, 2,6-di-t-butyl-4-methylphenoxide, 2,6-diisopropylphenoxide, 2,6-diphenylphenoxide, 2,4,6-trimethylphenoxide, 4-fluorophenoxide, 4-chlorophenoxide, 3,4,5-trifluorophenoxide,

Chemical formula

Chemical formula

[0028] Any of these substituents, excluding hydrides, may form all or part of the bridges between aluminum atoms. Thus, for example, an oxo (-O-) group may bond two aluminum atoms to form an aluminoxane. Similarly, a divalent hydrocarbon radical may bond to two aluminum atoms to form a bridge between them, such that it may be an -O-R 2 -O-diradical, or -O-(R 2 -O) z -R 2 -O-diradical.

[0029] In some embodiments, at least one aluminum atom is substituted with one or two hydrocarbyl groups, and is substituted with one or two halogen, oxo, ether, hydride, or phosphonate groups. If two or more aluminum atoms are present in the aluminum compound, all of the aluminum atoms may be substituted in this manner.

[0030] Specific examples of aluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-t-butylaluminum, trioctadecylaluminum, dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride (DIBAL), isobutylaluminum dichloride, methylaluminum di[(2,6-di-t-butyl-4-methyl)phenoxide](Al(BHT)2Me), dimethylaluminum di(2,6-diisopropyl)phenoxide (AlBHTMe2), methylaluminum di[(2,6-diphenyl)phenoxide], dimethylaluminum (2,6-diphenyl)phenoxide, methylaluminum di[(2,4,6-trimethyl)phenoxide], dimethylaluminum (2,4,6-Trimethyl)phenoxide, tetraethylaluminane, tetramethylaluminane, diisobutylaluminum hydride, isobutylaluminum dihydrogen, dimethylaluminum hydride, methylaluminum dihydrogen, diethylaluminum hydride, ethylaluminum dihydrogen, diisopropylaluminum hydride, isopropylaluminum dihydrogen, diethylaluminum ethoxide, ethylaluminum diethoxide, dimethylaluminum fluoride, methylaluminum difluoride, diethylaluminum difluoride, diisobutylaluminum fluoride, isobutylaluminum difluoride, dimethylaluminum bromide, methylaluminum dibromide, diethylaluminum bromide, ethylaluminum dibromide, diisobutylaluminum bromide, isobutylaluminum dibromide, dimethylaluminum iodide, diio Examples include methylaluminum iodide, diethylaluminum iodide, ethylaluminum diiodide, diisobutylaluminum iodide, isobutylaluminum iodide, bis(dimethylaluminum)methylphosphonate, bis(diethylaluminum)methylphosphonate, bis(diethoxyaluminum)methylphosphonate, bis(di-n-propylaluminum)methylphosphonate, bis(diisopropylaluminum)methylphosphonate, bis(di-n-propoxylaluminum)methylphosphonate, bis(diisopropoxylaluminum)methylphosphonate, bis(di-t-butylaluminum)methylphosphonate, bis(di-t-butoxyaluminum)methylphosphonate, bis(diphenylaluminum)methylphosphonate, bis(diphenoxyaluminum)methylphosphonate, bis(diisobutylaluminum)methylphosphonate, and tetraalkylaluminoxanes, where each alkyl group of the tetraalkylaluminoxane independently contains 1 to 6 carbon atoms.

[0031] For the purposes of this invention, "inert" substituents are those that are not reactive to a hydroxyl group, an amino group, or an isocyanate group. Examples of inert substituents include, for example, hydrocarbyl substituents, ether groups, ester groups, tertiary amino groups, amide groups, halogens, and the like.

[0032] For the purposes of the present invention, a "phosphorus-nitrogen base" is a compound having at least one -NPN- linkage and / or at least one -PNP- linkage, wherein the bond between phosphorus and the adjacent nitrogen atom is independently a single bond or a double bond. For example, an -NPN- linkage may take the form of -NPN- (where both nitrogen-phosphorus bonds are single bonds) or -N=PN-, and a -PNP- linkage may take the form of -PNP-, -P=NP-, or -P=N + It can take the form of =P-. Alternating nitrogen and phosphorus atoms can form a ring structure having, for example, 3 to 10 phosphorus atoms and 3 to 10 nitrogen atoms.

[0033] A phosphorus-nitrogen base may contain, for example, 1 to 8, 1 to 4, or 1 to 2 phosphorus atoms and 1 to 12 or 1 to 8 nitrogen atoms, provided that the total number of nitrogen atoms + phosphorus atoms is at least 3. A phosphorus-nitrogen base may have a molecular weight of up to 1000, up to 750, or up to 650 g / mol (excluding any anionic counterions). In some embodiments, the molecular weight is up to 500 or up to 350 g / mol.

[0034] Phosphorus-nitrogen bases may be neutral or cationic. If cationic, the charge may reside on the nitrogen or phosphorus atom or be delocalized. When phosphorus-nitrogen bases are cationic, they are generally used in the form of salts having an anionic counterion. The counterion is preferably not alkoxylated under polymerization conditions of alkylene oxides, and particularly preferably not an alkoxide or aryl oxide. Examples of useful counterions include halogens (fluorides, chlorides, bromides, and iodides, etc.), nitrates, bisulfates, carbonates, hexafluorophosphates, bis(trifluoromethylsulfonyl)imides, and triflates. The counterion is preferably monovalent.

[0035] Nitrogen atoms are preferably hydrocarbyl-substituted, more preferably alkylated, insofar as they are bonded to substituents other than phosphorus; that is, all substituents on each non-phosphorus nitrogen atom are preferably hydrocarbyl-substituted, more preferably alkyl-substituted. Any hydrocarbyl group may be inertly substituted. The alkyl substituent may have, for example, 1 to 18 carbon atoms, with a preferred number being 1 to 8 carbon atoms or 1 to 4 carbon atoms. The substituents on the nitrogen atoms of the phosphorus-nitrogen base may all be the same, or there may be two or more different substituents. Furthermore, any two hydrocarbyl substituents on a single nitrogen atom or two different nitrogen atoms may form a ring structure containing the nitrogen atom or atoms.

[0036] Phosphorus atoms can be bonded to oxygen atoms (e.g., in the form of P=O linkages, or oxygen atoms of aryloxy, alkoxy, or phosphate substituents) or hydrocarbyl substituents, as long as they are bonded to substituents other than nitrogen. Any hydrocarbyl group can be inertly substituted. Hydrocarbyl substituents include phenyl; alkyl-substituted phenyl; alkyls preferably having 1 to 18, 1 to 8, or 1 to 4 carbon atoms, and phenyl-substituted alkyls having 1 to 18, 1 to 8, or 1 to 4 carbon atoms.

[0037] Among suitable phosphorus-nitrogen bases, structure I: [ka] There are such formulas, where each R is a hydrocarbyl, NH2, or -N=P-R3 having up to 18 or up to 8 carbon atoms, A is an anion, n is the valence of anion A, and the base has the above molecular mass (excluding the mass of counterion A). Any hydrocarbyl group may be substituted inertly. In some embodiments, each R is phenyl, and anion A is monovalent, especially halogen. Specific examples of this type of phosphorus-nitrogen base are bis(triphenylphosphoranylidene)ammonium salts, especially fluorides, chlorides, bromides, iodides, acetates, triflates, and BF4. - , or PF6 - These are salts of monovalent anion A, such as [examples of monovalent anions].

[0038] Another suitable class of phosphorus-nitrogen bases includes structure II: [ka] Examples of things that can be expressed are, in the formula, R 5 and each R 4 -P[N(R 4 )2]3 or hydrocarbyl (more preferably alkyl or alkylene), provided that any two hydrocarbyl R 4 The group is a nitrogen atom, or such R 4 The condition is that a divalent hydrocarbyl group can be formed, forming a ring containing the atom to which the group is bonded. The alkyl or alkylene substituent may have, for example, 1 to 18 carbon atoms, preferably 1 to 8 or 1 to 4 carbon atoms. Any hydrocarbyl group may be inertly substituted. 5 and each R 4 These can independently be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-octyl, isooctyl, 1,1,3,3,3-pentamethylpropyl, etc. In some embodiments, each R 4It is methyl, and R 5 is a linear or branched alkyl group of C1-C8. x is zero or a positive number, and R is such that the base has the molecular mass described above. 5 and R 4 It is selected by x, which is preferably 0, 1, 2, or 3.

[0039] Specific examples of phosphorus-nitrogen bases having structure II include methylimino-tris(dimethylamino)phosphorane, ethylimino-tris(dimethylamino)phosphorane, t-butylimino-tris(dimethylamino)phosphorane (PAZ-P1), tert-octylimino-tris(dimethylamino)phosphorane), and phosphazene base P2 (corresponding to structure II, where x is 1 and each R is 1). 4 and R 5 (where is methyl), phosphazene base P2-Et (corresponding to structure II, where x is 1 and each R 4 It is methyl, and R 5 (is ethyl), phosphazene base P2-t-Bu (corresponding to structure II, where x is 1 and each R 4 It is methyl, and R 5 (wherein is t-butyl), phosphazene base P2-tert-octyl (corresponding to structure II, where x is 1 and each R) 4 It is methyl, and R 5 (1,1,3,3,3-pentamethylpropyl), ethylimino-tris(pyrrollidino)phosphoran, t-butylimino-tris(pyrrollidino)phosphoran, tert-octylimino-tris(pyrrollidino)phosphoran, 2-ethylimino-2-diethylamino-1,3-dimethylperhydro-1,3,-2-diazaphosphorine, 2-t-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,-2-diazaphosphorine, 2-tert-octylimino-2-diethylamino-1,3-dimethylperhydro-1,3,-2-diazaphosphorine, phosphazene base P4(1-methyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2λ 5 ,4λ5 -Catenadi(phosphazene)), phosphazene base P4-Et(1-ethyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2λ) 5 ,4λ 5 -Catenagy(phosphazene)). and phosphazene base P4-t-bu(1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2λ 5 ,4λ 5 - Catenagy (phosphazene) is one example.

[0040] Furthermore, other useful phosphorus-nitrogen bases include structures III and / or IIIa: [ka] Phosphoramides represented by the formula are examples, where each R 4 This is as described above with respect to structure I, and R 10 The above-mentioned hydrocarbyl or inactively substituted hydrocarbyl groups are used, and the molecular weight of the phosphoramide is as described above. Each R 4 For example, these could be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 1,1,3,3,3-pentamethylpropyl, and any two R 4 The group is a nitrogen atom, or such R 4 They can form a divalent hydrocarbyl radical that forms a ring structure containing the atom to which the group is bonded. Specific examples of such phosphoramide compounds include hexamethylphosphoramide (tris(dimethylaminophosphine oxide)), hexaethylphosphoramide, hexa-t-butylphosphoramide, and tris(N,N-tetramethylene)phosphoramide.

[0041] Furthermore, other suitable phosphorus-nitrogen bases have structure IV: [ka] It is expressed as follows, where A and n are as described above with respect to structure II, and each R 6 These are independently hydrocarbyl (more preferably alkyl), or N=P-(NR 6 2) 3, however, any two R 6 The group is a nitrogen atom, or such R 6 The further condition is that it can form a divalent hydrocarbyl group that forms a ring containing the atom to which the group is bonded. The molecular mass (excluding the mass of counterion A) of the phosphorus-nitrogen base having structure IV is as described above.

[0042] Examples of phosphorus-nitrogen bases having structure IV include phosphazene base P2-F (1,1,1,3,3,3-hexakis(dimethylamino)diphosphazenium fluoride), phosphazene base P2-Cl (1,1,1,3,3,3-hexakis(dimethylamino)diphosphazenium chloride), phosphazene base P2-Br (1,1,1,3,3,3-hexakis(dimethylamino)diphosphazenium bromide), phosphazene base P5-F (tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium fluoride), phosphazene base P5-Cl (tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium chloride), and phosphazene base P5-Br (tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium bromide).

[0043] Another class of phosphorus-nitrogen bases has structures V and / or VI: [ka] Examples of phosphine compounds represented by the formula are, where each R 7 R is independently a hydrocarbyl, more preferably an alkyl, provided that any two R 7 The group is a nitrogen atom, or such R 7The condition is that a divalent hydrocarbyl group can be formed, which forms a ring containing the atom to which the group is bonded. Y is a halogen, and A is a monovalent anion, for example, as described above. The alkyl or alkylene substituent may have, for example, 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms or 1 to 4 carbon atoms. Each R 7 These can independently be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-octyl, isooctyl, 1,1,3,3,3-pentamethylpropyl, etc. In some embodiments, each R 4 This is methyl. Examples of phosphines having structure V include tris(dimethylamino)phosphine, tris(diethylamino)phosphine, and tris(di-t-butylamino)phosphine.

[0044] Furthermore, another suitable class of phosphorus-nitrogen bases includes structure VII: [ka] Examples of cyclic compounds represented by the formula are, where m is a number from 3 to 20, preferably 3 to 10, more preferably 3 to 5, and most preferably 3. Each Q is independently a hydrocarbyl having up to 18 or up to 8 carbon atoms; -N=P-R3, where R is preferably a hydrocarbyl having up to 18 or up to 8 carbon atoms; aryloxy; alkoxy; and [ka] Selected from, where c is a positive number, preferably zero or up to 4, and each R 9 Each R is independently a hydrocarbon having 1 to 18, 1 to 8, or 1 to 4 carbon atoms, or hydrogen, and each R 8 These are hydrocarbons that independently have 1 to 18, 1 to 8, or 1 to 4 carbon atoms. 9 is preferably hydrogen or methyl, and each R 8The atoms are preferably alkyl or phenyl having up to four carbon atoms. Examples of phosphorus-nitrogen bases having structure VII are described in U.S. Patent Application Publication 2011 / 0130497, which is incorporated herein by reference.

[0045] Polymerization is carried out in the presence of one or more starter compounds. The starter compounds have one or more functional groups that can be alkoxylated. The starter may contain any number of such functional groups. The functional groups may be, for example, primary, secondary, or tertiary hydroxyls, primary aminos, secondary aminos, or thiols. A preferred starter contains one or more such functional groups, preferably two or more of such functional groups, and may contain up to twelve or more of such functional groups.

[0046] In certain embodiments, all functional groups are hydroxyl groups, and the starter does not contain primary and / or secondary amino groups or thiol groups. In some embodiments, the starter compound may have 2 to 8, 2 to 4, or 2 to 3 hydroxyl groups.

[0047] In certain embodiments, all functional groups are primary and / or secondary amine groups, and the starter does not contain hydroxyl or thiol groups. In some embodiments, the starter compound may have 2-8, 2-4, or 2-3 primary and / or secondary amine groups.

[0048] The starter compound has fewer equivalent weights per functional group than the polyether product. It can have an equivalent weight of 9 (in the case of water) to 6000 or more. In some embodiments, the starter compound has an equivalent weight of 9 to 4000, 9 to 2500, 30 to 1750, 30 to 1400, 30 to 1000, 30 to 500, or 30 to 250.

[0049] The equivalent weight of an alcohol or polyol can be conveniently determined using a titration method such as ASTM 4274-16, which yields the hydroxyl value of the polyol in mgKOH / gram, which can be converted to equivalent weight using the relationship equivalent weight = 56,100 ÷ hydroxyl value.

[0050] Suitable starters include vinyl alcohol, propenyl alcohol, allyl alcohol, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, C 1~50 Alkanols, phenols, cyclohexanol, alkylphenols, water (considered to have two hydroxyl groups for the purposes of the present invention), ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, sucrose, phenols, polyphenol starters, such as bisphenol A or 1,1,1-tris(hydroxyphenyl)ethane.

[0051] Other suitable starters include amine compounds such as morpholine, piperazine, toluenediamine (any isomer or mixture of isomers), phenylenediamine (any isomer or mixture of isomers), diethyltoluenediamine, ethylenediamine, diethylenetriamine, higher polyethylene polyamines having up to eight nitrogen atoms, 1,3-propanediamine, 1,2-propanediamine, 1,4-butanediamine, cyclohexanediamine, isophoronediamine, bis(aminomethyl)cyclohexane, and bis(3-aminopropyl)methylamine.

[0052] Further preferred starters are hydroxyl-terminated polyethers (alkoxylates, in particular ethoxylates and / or propoxylates of hydroxyl-containing and / or amine starters, including those just described) having a smaller hydroxyl equivalent weight than the polymerization product. Such polyether starters may have, for example, a hydroxyl equivalent weight of at least 125 to a maximum of 6000, a maximum of 4000, a maximum of 2500, a maximum of 1750, a maximum of 1500, a maximum of 1000, a maximum of 500, or a maximum of 250 g / equivalent. In some embodiments, the polyether starter may be a homopolymer of propylene oxide and / or a random or block copolymer of propylene oxide with one or more other alkylene oxides (in particular ethylene oxide), which have a hydroxyl equivalent weight as described in this paragraph, with 25% or less, 15% or less, or 10% or less of hydroxyl groups being primary.

[0053] In some embodiments, the aluminum compound is soluble in the starter in proportion to its initial polymerization stage. Solubility is assessed by combining the aluminum compound with the starter in an appropriate proportion and stirring at a maximum temperature of 160°C, preferably 75°C, for 15 minutes. The formation of a clear fluid upon visual inspection indicates that the aluminum compound is soluble in the starter.

[0054] Similarly, in some embodiments, the phosphorus-nitrogen base is soluble in the starter in proportion to its presence at the start of polymerization, and its solubility is assessed in the manner just described with respect to the aluminum compound. Preferably, both the aluminum compound and the phosphorus-nitrogen base are soluble in the starter in proportion to their presence at the start of polymerization.

[0055] In alternative embodiments, the aluminum compound and / or the phosphorus-nitrogen base are provided in the form of a solution in a suitable solvent.

[0056] The alkylene oxide may be, for example, ethylene oxide, 1,2-propylene oxide, oxetane, 1,2-butene oxide, 2-methyl-1,2-butane oxide, 2,3-butane oxide, tetrahydrofuran, epichlorohydrin, hexene oxide, octen oxide, styrene oxide, divinylbenzene dioxide, glycidyl ether, for example, bisphenol A diglycidyl ether, epichlorohydrin, or other polymerizable oxiranes. In some embodiments, the alkylene oxide is 1,2-propylene oxide, ethylene oxide, or a mixture of at least 50% by weight (preferably at least 80% by weight) of propylene oxide and a corresponding up to 50% by weight (preferably up to 20% by weight) of ethylene oxide. In some embodiments, two or more alkylene oxides are polymerized simultaneously (to form a random copolymer), and / or the alkylene oxide composition is changed one or more times, or more continuously, throughout the polymerization process to form block and / or random / block copolymers.

[0057] In certain embodiments, the starter is a poly(propylene oxide) or random propylene oxide / ethylene oxy copolymer containing at least 50% by weight or at least 70% by weight of oxypropylene units and up to 50% or up to 30% of ethylene oxide units, where the alkylene oxide is ethylene oxide. In such embodiments, the starter may have, for example, 500-3000, 500-2500, or 500-1750 g / equivalent of hydroxyl equivalent weight. In such embodiments, the starter may be generated in the presence of the aluminum compound and phosphorus-nitrogen base according to the present invention, and the ethoxylation of the starter may be carried out and / or without further addition of the aluminum compound and phosphorus-nitrogen base, i.e., in the presence of the same aluminum compound and phosphorus-nitrogen base used for alkoxylation before the commencement of the final ethoxylation step, and without any steps of neutralization, catalyst removal, or catalyst deactivation after the starter is generated and before the ethoxylation step.

[0058] Polymerization is carried out by combining a starter, an aluminum compound, and a phosphorus-nitrogen base with an alkylene oxide and optionally with a comonomer, and then polymerizing the alkylene oxide. In many cases, it is convenient to combine at least a portion of the starter with at least a portion of the aluminum compound and at least a portion of the phosphorus-nitrogen base before contacting the aluminum compound and phosphorus-nitrogen base with the alkylene oxide. Polymerization proceeds over a wide temperature range of -100°C to 250°C or higher. In some embodiments, the reaction temperature is at least 80°C, at least 100°C, at least 120°C, or at least 130°C. The polymerization temperature preferably does not exceed 190°C, more preferably 180°C. The polymerization reaction is usually carried out under overpressure, but can be carried out at atmospheric pressure or even near-atmospheric pressure.

[0059] While sufficient aluminum compounds are used to provide a commercially viable polymerization rate, it is generally desirable to use as little aluminum compound as possible that does not contradict a viable polymerization rate, as this reduces the cost of the catalyst and eliminates the need to remove catalyst residues from the product. The amount of aluminum compound may be sufficient to provide 10 to 10,000 ppm of aluminum, for example, based on the weight of the alkylene oxide polymer or copolymer product of polymerization. In certain embodiments, the amount of aluminum compound may be sufficient to provide at least 25 ppm, at least 50 ppm, at least 100 ppm, or at least 250 ppm of aluminum, and again up to 5,000 ppm, up to 2,500 ppm, up to 1,500 ppm, or up to 1,000 ppm of aluminum, again up to 5,000 ppm, up to 2,500 ppm, up to 1,500 ppm, or up to 1,000 ppm, based on the aforementioned criteria.

[0060] The amount of aluminum compound may be sufficient to provide, for example, at least 0.00005 moles of aluminum, at least 0.00075 moles of aluminum, or at least 0.0001 moles of aluminum per equivalent of starter, and may be sufficient to provide, for example, up to 0.10 moles of aluminum, up to 0.075 moles of aluminum, up to 0.06 moles of aluminum, up to 0.05 moles of aluminum, or up to 0.025 moles of aluminum per equivalent of starter.

[0061] The amount of phosphorus-nitrogen base may be, for example, at least 0.00005 moles, at least 0.0001 moles, or at least 0.0002 moles per equivalent of starter, and may be, for example, up to 0.10 moles, up to 0.075 moles, up to 0.06 moles, up to 0.05 moles, up to 0.025 moles, or up to 0.01 moles per equivalent of starter.

[0062] The molar ratio of aluminum compound to phosphorus-nitrogen base can be, for example, 1:10 to 20:1. Preferred ratios are at least 1:3, at least 1:2, or at least 2:3 to a maximum of 6:1, a maximum of 5:1, a maximum of 4:1, a maximum of 3:1, a maximum of 2.5:1, a maximum of 2:1, a maximum of 3:2, a maximum of 4:3, or a maximum of 1:1. The optimal ratio may vary among specific aluminum compound / phosphorus-nitrogen base pairs.

[0063] Polymerization reactions can be carried out in batches, semi-continuously (including the continuous addition of starters as described in U.S. Patent No. 5,777,177), or continuously.

[0064] In batch polymerization, a reaction mixture is formed by combining an aluminum compound, a phosphorus-nitrogen base, a starter, an alkylene oxide, and an optional comonomer. The reaction mixture is then heated in a reaction vessel to the polymerization temperature until the desired molecular weight is obtained. A preferred method of carrying out batch polymerization involves dissolving the aluminum compound and the phosphorus-nitrogen base in the starter, then combining the resulting solution with the alkylene oxide, and subsequently subjecting the resulting mixture to polymerization conditions until the desired molecular weight is obtained and / or until the alkylene oxide is consumed. The aluminum compound, the phosphorus-nitrogen base, or both can be introduced in the form of a solution in an inert solvent such as toluene or a hydrocarbon such as hexane.

[0065] In a half-batch process, the aluminum compound, phosphorus-nitrogen base, and starter are combined, preferably by dissolving the catalyst and phosphorus-nitrogen base in the starter. A polyether monool or polyether polyol corresponding to the polymerization product, and / or a polyether with an intermediate molecular weight between the starter and the product, may be combined with the starter as needed. If necessary, the contents of the vessel are heated to the polymerization temperature and a portion of the alkylene oxide is introduced into the reaction vessel. Once polymerization begins (typically indicated by a decrease in internal reactor pressure), more alkylene oxide is supplied to the reactor under polymerization conditions. The supply of alkylene oxide is continued until sufficient is consumed to reach the molecular weight of the target product. Additional aluminum compounds and / or phosphorus-nitrogen bases may be added during the alkylene oxide addition process. In a half-batch process, the entire amount of starter is generally added at the start of the process. After the supply of alkylene oxide is complete, the reaction mixture can be boiled down to the polymerization temperature to consume any remaining alkylene oxide.

[0066] Continuous polymerization involves the continuous or intermittent addition of at least alkylene oxide and starter, and the continuous or intermittent removal of the product during polymerization. The continuous process is generally carried out in a continuous reactor, such as a loop reactor, plug-flow reactor, or continuous stirred-tank reactor, under polymerization conditions (within the operating capabilities of the polymerization apparatus), by establishing steady-state concentrations of the aluminum compound (or its reaction product), phosphorus-nitrogen base, starter (or its reaction product), alkylene oxide, and polymer. The "polymer" is a mixture of polyethers having a molecular weight greater than that of the starter and up to the molecular weight of the target product. Then, as polymerization progresses, additional aluminum compound, phosphorus-nitrogen base, starter, and alkylene oxide are continuously added to the reactor. These can be added as a single flow, as separate components, or in various subcombinations, but the aluminum compound and phosphorus-nitrogen base are preferably added in the form of a solution in the starter. The product fluid is continuously or intermittently withdrawn from the reactor during polymerization. The additional flow and product fluid velocity are selected to maintain a steady state within the reactor (within the operating performance of the apparatus) and to produce a product with the desired molecular weight.

[0067] The product fluid drawn from the continuous reactor may be boiled down for a certain period of time to consume any unreacted alkylene oxides in the fluid to a low level.

[0068] The continuous process is particularly suitable for producing polyether products having a hydroxyl equivalent weight of 150 to 5000, especially 350 to 2500, and even more preferably 500 to 2000 g / equivalent.

[0069] In the above-described semi-batch or continuous process, alkylene oxide can be supplied to the reactor as needed by continuously pressurizing the reactor containing alkylene oxide to a predetermined internal reactor pressure and / or alkylene oxide partial pressure.

[0070] Polymerization reactions can be carried out in any type of vessel suitable for the encountered pressure and temperature. In continuous or semi-continuous processes, the vessel must have one or more inlets from which alkylene oxides and additional starter compounds can be introduced during the reaction. In continuous processes, the reaction vessel should accommodate at least one spout from which a portion of the partially polymerized reaction mixture can be withdrawn. Tubular reactors, loop reactors, and continuous stirred tank reactors (CTSRs) with multiple points for injecting starting materials are all types of vessels suitable for continuous or semi-continuous operation. The reactor must be equipped with means to provide and / or remove heat so that the temperature of the reaction mixture can be maintained within the required range. Suitable means include various types of jackets for thermal fluids, various types of internal or external heaters, etc. A boiling step carried out on the continuously withdrawn product is conveniently performed within the reactor, thereby preventing significant backmixing. Plug-flow operation in pipe or tubular reactors is a preferred mode for carrying out such a boiling step.

[0071] The crude product obtained by any of the aforementioned processes may contain up to 0.5% by weight of unreacted alkylene oxide, small amounts of the starter compound and its low molecular weight alkoxylate, and small amounts of other organic impurities and water, based on total weight. Volatile impurities (including unreacted alkylene oxide) should be flushed or stripped from the product. The crude product typically contains catalyst residue and residues of aluminum compounds and / or phosphorus-nitrogen bases. It is typical to leave these residues in the product, but they may be removed if necessary. Water and volatiles can be removed by stripping the polyol.

[0072] The process of the present invention is useful for preparing polyether polyol products that can have hydroxyl equivalent weights ranging from as low as about 85 to as high as 6000 or more.

[0073] Polymerization reactions can be characterized by a "composition ratio," defined as the ratio of the number-average molecular weight of the polyether product to the number-average molecular weight of the starter compound. This composition ratio can be as high as 160, but more commonly it is in the range of 2.5 to about 65, and even more commonly, 2.5 to about 50. When the polyether product has a hydroxyl equivalent weight of 85 to 400 g / equivalent, the composition ratio is typically in the range of about 2.5 to about 15, or about 7 to about 11.

[0074] In some embodiments, alkylene oxides are polymerized by or in the presence of one or more copolymerizable monomers other than oxiranes. Examples of such copolymerizable monomers include carbonate precursors that copolymerize with alkylene oxides to form carbonate links in the product. Examples of such carbonate precursors include carbon dioxide, phosgene, linear carbonates, and cyclic carbonates. Other copolymerizable monomers include carboxylic anhydrides that copolymerize with alkylene oxides to form ester links in the product.

[0075] In some embodiments, the polyether polyols produced according to the present invention are random copolymers containing a homopolymer of propylene oxide, or at least 50% by weight, at least 70% by weight, or at least 90% by weight of oxypropylene units formed by polymerizing propylene oxide, and corresponding up to 50% by weight, up to 30% by weight, or up to 10% by weight of oxyethylene units formed by polymerizing a mixture of propylene oxide and ethylene oxide (in each case, without the presence of non-alkylene oxide copolymerizable monomers), having any one or more of the following characteristics: a) At least 500, at least 750, at least 1000, or at least 1200 to a maximum of 4000, a maximum of 3000, a maximum of 2500, a maximum of 2200, or a maximum of 2000 g / equivalent of hydroxyl equivalent weight, b) Nominal hydroxyl functional value of 2-8, c) Terminal unsaturated substances of 0.015 or less, 0.01 or less, and 0.007 meq / g or less. d) Polydispersion (M) by gel permeation chromatography of 1.15 or less, 1.10 or less, 1.07 or less, or 1.05 or less w / M n ), e) Fractions with a molecular weight of 40,000 g / mol or more, based on the weight of the polyether polyol, with a molecular weight of 2000 parts / million (ppm) or less, 1200 ppm or less, 1000 ppm or less, 750 ppm or less, 500 ppm or less, 250 ppm or less, 100 ppm or less, or 50 ppm or less, as determined by GPC, and f) 12% or less, 10% or less, 8% or less, 6% or less, or 5% or less of hydroxyl groups are primary hydroxyl groups as determined by ASTM D-4273 or an equivalent method. The polyether product may have all of characteristics a) to f).

[0076] In certain embodiments, the polyether polyol is a homopolymer of propylene oxide, or a random copolymer of a mixture of at least 85% by weight of propylene oxide and a corresponding up to 15% by weight of ethylene oxide, based on the total weight of all alkylene oxides, wherein in each case, the polyether polyol is prepared by polymerizing propylene oxide, or a mixture of propylene oxide and ethylene oxide, without the presence of copolymerizable monomers other than oxirane, and the polyether polyol has a) hydroxyl equivalent weight of 1000 to 2500 g / equivalent, b) a nominal functional value of 2 to 8, c) terminal unsaturation of 0.007 meq / g or less, and d) polydispersity (M) of 1.07 or less, preferably 1.05 or less. w / M n ) and contain a fraction having a molecular weight of 40,000 g / mol or more, determined by GPC, with a concentration of 1200 ppm or less, 1000 ppm or less, 250 ppm or less, or 50 ppm or less. Such polyether polyols may also have 12% or less, 10% or less, 8% or less, 6% or less, or 5% or less of primary hydroxyl groups.

[0077] Polyether polyols produced according to the present invention are particularly useful for producing polyurethanes. Polyether polyol products with higher equivalent weights (500-6000 g / equivalent) are useful for producing elastomers or semi-elastomer polyurethanes, including non-foaming or microporous elastomers and flexible polyurethane foams. Flexible polyurethane foams can be produced by slab stock or molding processes. Polyether polyol products with equivalent weights of about 225-400 are useful for producing semi-flexible foams and so-called viscoelastic or "memory" foams. Polyether polyols with equivalent weights of 85-400 are useful for producing rigid polyurethane foams such as thermal insulation foams for electrical appliances, buildings, and ship hulls, as well as for various coatings, adhesives, sealants, and elastomer products. Polyether polyols tend to have properties very similar to those produced by conventional DMC catalytic polymerization processes and alkali metal hydroxide catalytic polymerization processes.

[0078] Among other uses, the polyether monools produced according to the present invention are useful as surfactants or industrial solvents.

[0079] The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the invention. All parts and percentages are by weight unless otherwise indicated.

[0080] Catalyst preparation procedure Heat the starter to 70°C, purge it with nitrogen, and / or pass it through an alumina plug before use. Transfer 20 g of starter to a 50 mL glass jar. Under nitrogen, combine the indicated amounts of aluminum compound and phosphorus-nitrogen base (if present) with the starter. Cover the jar and stir its contents for about 20 minutes. If the resulting mixture appears non-uniform, heat the contents of the jar at 70°C for an additional 5-10 minutes while continuing to stir, then allow to cool.

[0081] Parallel Pressure Reactor (PPR) Polymerization Procedure Polymerization of alkylene oxides and / or copolymerization of propylene oxide / carbon dioxide are carried out using a 48-well Symyx Technologies Parallel Pressure Reactor (PPR). Each of the 48 wells is equipped with an individually metered glass insert with an internal working fluid capacity of approximately 5 mL. Each well contains an overhead paddle stirrer.

[0082] 0.7 mL of starter / catalyst / phosphorus-nitrogen base mixture (approximately 0.72 g of starter (starteris)) is packed into each insert. Each well is pressurized with nitrogen at 50 psig (344.7 kPa) and then heated to the polymerization temperature. Once the polymerization temperature is reached, 1 mL of epoxide is injected into each well, where the epoxide reacts with the starter in the glass insert.

[0083] The internal pressure in the headspace of each well is monitored individually throughout the polymerization process. The internal pressure is observed every hour after the first injection of epoxide, and if the pressure in any particular well falls below 190 psig (1.31 MPa), an additional 1 mL of alkylene oxide is injected. This is repeated up to three times throughout the entire 4-hour run. Four hours after the first epoxide injection, the wells are cooled to room temperature and vented. The glass inserts are left to stand overnight under nitrogen at 40-50°C to volatilize any residual epoxide, and then the inserts are weighed to determine the amount of product.

[0084] The obtained product was analyzed by gel permeation chromatography to determine its molecular weight and polydispersity (M) relative to the polystyrene standard. w / M n The primary hydroxyl content is analyzed by functionalizing the product with trifluoroacetic anhydride and determining the resulting product according to standard methods such as ASTM D-4273. 19 The determination is made by evaluation using 1F NMR spectroscopy.

[0085] Examples 1-7 and Comparative Sample A The propoxylation of a trifunctional poly(propylene oxide) starter with a molecular weight of 700 is carried out in a half-batch reactor using various aluminum compounds and bis(triphenylphosphoranylidene(ammonium) chloride salt, PPNCl) as the phosphorus-nitrogen base. The polymerization temperature is 160°C.

[0086] The aluminum compounds are triethylaluminum (AlEt3), diethylaluminum chloride (Et2AlCl), diisobutylaluminum hydride (DIBAL), and tetraethyldialuminoxane (TEDA), as shown in Table 1.

[0087] Aluminum compounds: The molar ratio of PPNCl in each of Examples 1, 2, and 5-7 is 1:0.5, and in Examples 3 and 4, this ratio is 1:1. The molar ratios of PPNCl to aluminum provided by the aluminum compounds are shown in Table 1. PPNCl was excluded in comparative sample A.

[0088] The amount of 1,2-propylene oxide (propylene oxide, PO) supplied, the processing time, and the yield were recorded, along with the percentage of primary hydroxyl groups in the product, polydispersity, and M n This is shown in Table 1.

[0089] [Table 1]

[0090] Comparative sample A is a control where TEDA is itself an aluminum catalyst and no phosphorus-nitrogen base is present. Polymerization proceeds slowly. After approximately 20 hours, PO is hardly consumed, and the yield to the product is correspondingly low, as is the molecular weight of the product.

[0091] In each of Examples 1-7, an aluminum compound was paired with PPNCl. In each case, approximately five times more PO was consumed compared to comparative sample A, resulting in higher yields and higher molecular weight of the product. Runs prepared using triethylaluminum and TEDA were particularly noteworthy, as the run time was an order of magnitude shorter than the control. These combinations of aluminum compounds with PPNCl are particularly active polymerization catalysts.

[0092] In all cases, the polydispersity is low, and where it is measured, the primary hydroxyl percentage is also very low.

[0093] Examples 8-26 and Comparative Sample B Propylene oxide polymerization is carried out using the PPR procedure described above. The starter is a triol with a molecular weight of 700 as described in the previous examples. The amount of aluminum compound and the amount of aluminum compound by weight (parts per million, ppm) based on the amount of starter are as shown in Table 2 for each case. The phosphorus-nitrogen base is PPNCl in all cases. The initial molar ratio of aluminum compound to phosphorus-nitrogen base is as shown in Table 2. The polymerization temperature is 160°C. The amount of product produced, the percentage of primary hydroxyl groups, the number-average molecular weight, and the polydispersity (PDI, M) are as follows: w / M n ) are as reported in Table 2.

[0094] [Table 2]

[0095] As the data from Examples 8, 12, 16, 20-22, and 25 show, excess PPNCl of 2:1 or more hardly polymerizes under these conditions. When used in such excess, PPNCl can actually inhibit polymerization, as suggested by comparing comparative sample B with Example 25. Much higher yields and much higher molecular weights are obtained when the molar ratio of Al compound to PPNCl is 1:1 to 2:1. The results from Examples 20-24 suggest that for TEDA / PPNCl combinations, the molar ratio should be maintained at least below 4:1.

[0096] Examples 27-31 EO polymerization is carried out using the PPR procedure described above. The starter is a triol with a molecular weight of 700 as described in the previous examples. The aluminum catalyst is as shown in Table 3 below. In each case, the amount of the aluminum compound is as shown in Table 3, and the amount is in ppm by weight based on the starter. The phosphorus-nitrogen base is PPNCl. The aluminum compound and the phosphorus-nitrogen base are initially present in a molar ratio of 1:1 in Examples 27-29, which is 1:0.5 in Example 30 and 1:0.25 in Example 31. The polymerization temperature is 160°C. Amount of product produced, % of primary hydroxyl groups, number-average molecular weight, and polydispersity (PDI, M) are listed below. w / M n The results are as reported in Table 3.

[0097] [Table 3]

[0098] In each case, rapid polymerization is achieved, yielding high molecular weight, low polydispersity polymers.

[0099] Examples 32-36 Various combinations of aluminum compounds with PPNCl are evaluated in the propoxylation of small molecule starters. The molar ratio of PPNCl to aluminum provided by the aluminum compounds is 1:1 in all cases. As shown in Table 4, the starters are ortho-toluenediamine (oTDA), bis(3-aminopropyl)methylamine (BAPMA), glycerin, and sorbitol. Polymerization is carried out using the PPR procedure in the same general manner as in the previous examples. The aluminum compounds are as shown in Table 4, and the polymerization results are similar.

[0100] [Table 4]

[0101] As demonstrated by the data in Table 4, various combinations of aluminum compounds with TBD result in the effective propoxylation of various low molecular weight hydroxyl-containing and amine-containing starters. As mentioned above, polydispersity remains low.

[0102] Examples 37-45 and Comparative Samples C-E In these polymerizations, the starter is the same 700 molecular weight triol described in previous examples, and the alkylene oxide is propylene oxide. The aluminum compound and phosphorus-nitrogen base are as shown in Table 5.

[0103] In Table 5, "PAZ-P1" represents t-butylimino-tris(dimethylamino)phosphorane, and "HMPA" represents hexamethylphosphoramide (i.e., tris(dimethylaminophosphine oxide). "DCI16302" and "DCI16303" have their respective structures: [ka] PPNF, PPNOAc, and PPNPF6 are fluorine, acetate, and PF6 bis(triphenylphosphoranylidene)ammonium salt, respectively.

[0104] In each case, the amount of catalyst is parts per 2,000,000 based on the starter. The phosphorus-nitrogen base (if present) and aluminum compound are initially present in a 1:1 molar ratio, which also produces PPNCl to aluminum in a 1:1 molar ratio. The polymerization temperature is 160°C. The amount of product produced, the percentage of primary hydroxyl groups, the number-average molecular weight, and the polydispersity (PDI, M) are described below. w / M n ) are as shown in Table 5.

[0105] [Table 5]

[0106] PAZ-P1 exhibits a strong enhancing effect when used in combination with either Et2AlCl or EtAlCl2 catalysts. HMPA, DCI16302, and DCI16303 all show a mild enhancing effect when used with the DIBAL catalyst. Fluorides, acetates, and hexafluorophosphate bis(triphenylphosphoranylidene(ammonium)) salts all show a substantial enhancing effect. This application also relates to the following aspects. 〔1〕 A method for producing alkylene oxide polymers or copolymers, (i) at least one aluminum compound containing at least one trisubstituted aluminum atom, wherein at least one substituent of the at least one trisubstituted aluminum atom is hydrocarbyl, (ii) at least one starter, (iii) at least one alkylene oxide, (iv) 0.00005 to 0.1 moles of at least one phosphazene-nitrogen base per equivalent of starter, (v) A method comprising combining at least one comonomer that is not an oxirane with the alkylene oxide, and polymerizing the alkylene oxide or copolymerizing the alkylene oxide and the comonomer to form the alkylene oxide polymer or copolymer. 〔2〕 The method according to [1], wherein the aluminum atoms of the aluminum compound are substituted with one or two hydrocarbyl groups and are substituted with one or two halogen, oxo, ether, hydride, or phosphonate groups. 〔3〕 The method according to [1], wherein the aluminum compound comprises one or more of trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-t-butylaluminum, and trioctadecylaluminum. 〔4〕 The aforementioned aluminum compounds include dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, methylaluminum di[(2,6-di-t-butyl-4-methyl)phenoxide](Al(BHT)2Me), dimethyl 2,6-di-t-butyl-4-methylphenoxide (AlBHTMe2)methylaluminum di(2,6-diisopropyl)phenoxide, dimethylaluminum (2,6-diisopropyl)phenoxide methylaluminum di[(2,6-diphenyl)phenoxide], dimethylaluminum (2,6-diphenyl)phenoxide, methylaluminum di[(2,4,6-trimethyl)phenoxide], dimethylaluminum (2,4,6-trimethyl)phenoxide, tetraethylaluminan, tetramethylaluminan, diisobutylaluminum hydride, isobutylaluminum dihydrogen, and dimethylaluminum hydride. The method according to [1] above, comprising one or more of aluminum, methylaluminum dihydrogen, diethylaluminum hydride, ethylaluminum dihydrogen, diisopropylaluminum hydride, isopropylaluminum dihydrogen, diethylaluminum ethoxide, ethylaluminum diethoxide, dimethylaluminum ethoxide, methylaluminum difluoride, diethylaluminum fluoride, ethylaluminum difluoride, diisobutylaluminum fluoride, isobutylaluminum difluoride, dimethylaluminum bromide, methylaluminum dibromide, diethylaluminum bromide, ethylaluminum dibromide, diisobutylaluminum bromide, isobutylaluminum dibromide, dimethylaluminum iodide, methylaluminum diiodide, diethylaluminum iodide, ethylaluminum diiodide, diisobutylaluminum iodide, and isobutylaluminum iodide. 〔5〕 The method according to [1], wherein the aluminum compound comprises one or more of the following: bis(dimethylaluminum)methylphosphonate, bis(diethylaluminum)methylphosphonate, bis(diethoxyaluminum)methylphosphonate, bis(di-n-propylaluminum)methylphosphonate, bis(diisopropylaluminum)methylphosphonate, bis(di-n-propoxylaluminum)methylphosphonate, bis(diisopropoxylaluminum)methylphosphonate, bis(di-t-butylaluminum)methylphosphonate, bis(di-t-butoxyaluminum)methylphosphonate, bis(diphenylaluminum)methylphosphonate, bis(diphenoxyaluminum)methylphosphonate, bis(diisobutylaluminum)methylphosphonate, and each alkyl group independently contains 1 to 6 carbon atoms in a tetraalkylaluminoxane. 〔6〕 Phosphorus-nitrogen base, structure I:

change

change

change

[10] , wherein the phosphorus-nitrogen base is one or more of hexamethylphosphoramide (tris(dimethylaminophosphine oxide), hexaethylphosphoramide, hexa-t-butylphosphoramide, and tris(N,N-tetramethylene)phosphoramide). 〔12〕 The aforementioned phosphorus-nitrogen base has structure IV:

Chem.

[12] , wherein the phosphorus-nitrogen base is one or more 1,1,1,3,3,3-hexakis(dimethylamino)diphosphazenium fluoride, 1,1,1,3,3,3-hexakis(dimethylamino)diphosphazenium chloride, 1,1,1,3,3,3-hexakis(dimethylamino)diphosphazenium bromide, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium fluoride, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium chloride, and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium bromide. 〔14〕 The phosphorus-nitrogen base has structure V or structure VI:

Chem.

[14] , wherein the phosphine compound is one or more of tris(dimethylamino)phosphine, tris(diethylamino)phosphine, and tri(di-t-butylamino)phosphine. 〔16〕 The aforementioned phosphorus-nitrogen base has structure VI:

Chem.

Chem.

[16] , wherein the aluminum compound is present in an amount sufficient to provide 100 to 2,500 parts by weight of aluminum per 1 million parts by weight of the alkylene oxide polymer or copolymer. 〔18〕 The aluminum compound and the starter are combined in a ratio that provides 0.00005 to 0.05 moles of aluminum per equivalent of the starter, as in any of the above [1] to

[17] . One Methods used. 〔19〕 The method according to any one of [1] to

[18] , wherein the molar ratio of the aluminum compound to the phosphorus-nitrogen base is at least 1:3 to a maximum of 5:1. 〔20〕 The method according to any one of [1] to

[19] , wherein the starter contains one or more hydroxyl groups and has a hydroxyl equivalent weight of 30 to 6000 g / equivalent. 〔21〕 The method according to any one of [1] to

[20] , wherein the starter contains 2 to 8 hydroxyl groups and has an equivalent weight of 30 to 250 g / equivalent. 〔22〕 The method according to any one of [1] to

[21] , wherein the alkylene oxide is propylene oxide, ethylene oxide, or a mixture of propylene oxide and ethylene oxide. 〔23〕 The method according to any one of [1] to

[20] , wherein the starter is a homopolymer of propylene oxide and / or a random or block copolymer of propylene oxide, having at least 125 to a maximum of 4000 g / equivalent weight of hydroxyl groups and 25% or less of the hydroxyl groups being primary.

Claims

1. A method for producing alkylene oxide polymers or copolymers, (i) at least one aluminum compound containing at least one trisubstituted aluminum atom, wherein at least one substituent of the at least one trisubstituted aluminum atom is hydrocarbyl, (ii) at least one starter, (iii) at least one alkylene oxide, (iv) Combining at least one phosphorus-nitrogen base in an amount of 0.00005 to 0.1 moles per equivalent of starter, and polymerizing the alkylene oxide, or copolymerizing the alkylene oxide and comonomer to form the alkylene oxide polymer or copolymer, The phosphorus-nitrogen base is a phosphine compound represented by one of the structures I, II, III, IIIa, IV, or VI, or the phosphorus-nitrogen base is represented by structure (V) or (VIa). Structure I is, 【Chemistry 1】 It is expressed as follows, where each R is hydrocarbyl, NH ２ , or -N=P-(R') ３ Each R' is independently a hydrocarbyl, A is an anion, n is the valence of the anion A, and the phosphorus-nitrogen base has a molecular mass of up to 1000 g / mol. Structure II is, 【Chemistry 2】 It is expressed as, in the formula, R ５ and each R ４ This is independently -P[N(R 4')] ２ ] ３ or hydrocarbil, where R 4' is independently hydrocarbil, except for any two hydrocarbils R ４ The group or R4' group is the nitrogen atom, or such R ４ The condition is that a divalent hydrocarbyl group can be formed, which forms a ring containing the atom to which the group is bonded, x is 2 or more, and the phosphorus-nitrogen base has a molecular weight of up to 1000 g / mol. Structures III and IIIa are 【Transformation 3】 represented by, wherein each R ４ is independently -PN(R4') ３ or hydrocarbyl, and R4' is independently hydrocarbyl, However, any two R ４ The group or R4' group is the nitrogen atom, or such R ４ The condition is that a divalent hydrocarbyl group can be formed, which forms a ring containing the atom to which the group is bonded, R １０ It is a hydrocarbyl, and the phosphorus-nitrogen base has a molecular weight of up to 1000 g / mol. Structure IV is, 【Chemistry 4】 It is expressed as follows, where A is an anion, n is the valence of the anion A, and each R ６ It is independently hydrocarbyl, however any two R ６ The group is the nitrogen atom, or such R ６ The further condition is that the phosphorus-nitrogen base can form a divalent hydrocarbyl group that forms a ring containing the atom to which the group is bonded, It has a molecular weight of up to 1000 g / mol, Structure VI is, 【Transformation 5】 It is expressed as follows, where m is a number from 3 to 20, and each Q is independently hydrocarbyl, -N = P - R ３ Selected from, where each R is independently hydrocarbyl; aryloxy; Alkoxy; and 【Transformation 6】 In the formula, c is a positive number greater than or equal to zero and at most 4, and each R ９ These are hydrocarbons independently, and each R ８ are, independently, hydrocarbons, Structure V or Structure VIa is 【Transformation 7】 It is expressed as follows, and in the formula, each R ７ It is independently hydrocarbyl, however any two R ７ The group is the nitrogen atom, or such R ７ The condition is that a divalent hydrocarbyl group can be formed, which forms a ring containing the atom to which the group is bonded, Y is a halogen, A is a monovalent anion, and the phosphorus-nitrogen base has a molecular weight of up to 1000 g / mol. method.

2. The method according to claim 1, wherein the aluminum atoms of the aluminum compound are substituted with one or two hydrocarbyl groups and are substituted with one or two halogen, oxo, ether, hydride, or phosphonate groups.

3. The method according to claim 1, wherein the aluminum compound comprises one or more of trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-t-butylaluminum, and trioctadecylaluminum.

4. The aluminum compound is dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, methylaluminum di[(2,6-di-t-butyl-4-methyl)phenoxide](Al(BHT) ２ Me), dimethyl 2,6-di-t-butyl-4-methylphenoxide (AlBHTMe ２ ) Methylaluminum di(2,6-diisopropyl)phenoxide, Dimethylaluminum (2,6-diisopropyl)phenoxide, Methylaluminum di[(2,6-diphenyl)phenoxide], Dimethylaluminum (2,6-diphenyl)phenoxide, Methylaluminum di[(2,4,6-trimethyl)phenoxide], Dimethylaluminum (2,4,6-trimethyl)phenoxide, Tetraethylaluminan, Tetramethylaluminan, Diisobutylaluminum hydride, Isobutylaluminum dihydrogen, Dimethylaluminum hydride, Methylaluminum dihydrogen, Diethylaluminum hydride, Ethylaluminum dihydrogen, Diisopropylaluminum hydride, Isopropylaluminum dihydrogen, Diethylaluminum The method according to claim 1, comprising one or more of muethoxide, ethylaluminum diethoxide, dimethylaluminum ethoxide, methylaluminum difluoride, diethylaluminum fluoride, ethylaluminum difluoride, diisobutylaluminum fluoride, isobutylaluminum difluoride, dimethylaluminum bromide, methylaluminum dibromide, diethylaluminum bromide, ethylaluminum dibromide, diisobutylaluminum bromide, isobutylaluminum dibromide, dimethylaluminum iodide, methylaluminum diiodide, diethylaluminum iodide, ethylaluminum diiodide, diisobutylaluminum iodide, and isobutylaluminum iodide.

5. The method according to claim 1, wherein the aluminum compound comprises one or more of the following: bis(dimethylaluminum)methylphosphonate, bis(diethylaluminum)methylphosphonate, bis(diethoxyaluminum)methylphosphonate, bis(di-n-propylaluminum)methylphosphonate, bis(diisopropylaluminum)methylphosphonate, bis(di-n-propoxylaluminum)methylphosphonate, bis(diisopropoxylaluminum)methylphosphonate, bis(di-t-butylaluminum)methylphosphonate, bis(di-t-butoxyaluminum)methylphosphonate, bis(diphenylaluminum)methylphosphonate, bis(diphenoxyaluminum)methylphosphonate, bis(diisobutylaluminum)methylphosphonate, and tetraalkylaluminoxanes in which each alkyl group independently contains 1 to 6 carbon atoms.

6. Phosphorus-nitrogen base, structure I: 【Transformation 8】 It is expressed as follows, where each R is hydrocarbyl, NH ２ , or -N=P-(R') ３ The method according to any one of claims 1 to 5, wherein R' is independently a hydrocarbyl, A is an anion, n is the valence of the anion A, and the phosphorus-nitrogen base has a molecular mass of up to 1000 g / mol.

7. The method according to claim 6, wherein the phosphorus-nitrogen base is a fluoride, chloride, bromide, iodide, acetate, triflate, BF4-, or PF6-salt of bis(triphenylphosphoranylidene)ammonium.

8. The aforementioned phosphorus-nitrogen base has structure II: 【Chemistry 9】 It is expressed as, in the formula, R ５ and each R ４ This is independently -P[N(R 4')] ２ ] ３ or hydrocarbil, where R 4' is independently hydrocarbil, except for any two hydrocarbils R ４ The group or R4' group is the nitrogen atom, or such R ４ The condition is that a divalent hydrocarbyl group can be formed, which forms a ring containing the atom to which the group is bonded, x is 2 or more, and the phosphorus-nitrogen base has a molecular weight of up to 1000 g / mol. The method according to any one of claims 1 to 5.

9. The phosphorus-nitrogen bases are methyliminotris(dimethylamino)phosphorane, ethyliminotris(dimethylamino)phosphorane, t-butyliminotris(dimethylamino)phosphorane, tert-octyliminotris(dimethylamino)phosphorane, phosphazene base P2, phosphazene base P2-Et, phosphazene base P2-t-Bu, phosphazene base P2-tert-octyl, ethyliminotris(pyrrolidino)phosphorane, t-butyliminotris(pyrrolidino)phosphorane, tert-octyliminotris(pyrrolidino)phosphorane, 2-ethylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorin, and 2-t-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3 The method according to claim 8, wherein one or more of the following are selected: ,-2-diazaphosphorine, 2-tert-octylimino-2-diethylamino-1,3-dimethylperhydro-1,3,-2-diazaphosphorine, phosphazene base P4 (1-methyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2λ5,4λ5-catenadi(phosphazene)), 1-ethyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2λ5,4λ5-catenadi(phosphazene)), and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2λ5,4λ5-catenadi(phosphazene).

10. The phosphorus-nitrogen base has structure III or IIIa: 【Chemistry 10】 It is expressed as follows, and in the formula, each R ４ It is independently -PN(R 4') ３ , is hydrocarbyl, and R 4' is independently hydrocarbyl, however any two R ４ The condition is that the group can form a divalent hydrocarbyl group which forms a ring containing the nitrogen atom or an atom to which such an R4 group or R4' group is bonded, １０ The method according to any one of claims 1 to 5, wherein is hydrocarbyl, and the phosphorus-nitrogen base has a molecular weight of up to 1000 g / mol.

11. The method according to claim 10, wherein the phosphorus-nitrogen base is one or more of hexamethylphosphoramide (tris(dimethylaminophosphine oxide), hexaethylphosphoramide, hexa-t-butylphosphoramide, and tris(N,N-tetramethylene)phosphoramide).

12. The phosphorus-nitrogen base has structure V or structure VI: 【Chemistry 11】 A phosphine compound represented by the formula, where each R ７ It is independently hydrocarbyl, however any two R ７ The group is the nitrogen atom, or such R ７ The method according to any one of claims 1 to 5, provided that a divalent hydrocarbyl group can be formed which forms a ring containing an atom to which the group is bonded, Y is a halogen, A is a monovalent anion, and the phosphorus-nitrogen base has a molecular weight of up to 1000 g / mol.

13. The method according to claim 12, wherein the phosphine compound is one or more of tris(dimethylamino)phosphine, tris(diethylamino)phosphine, and tri(di-t-butylamino)phosphine.

14. The aforementioned phosphorus-nitrogen base has structure VI: 【Chemistry 12】 It is expressed as follows, where m is a number from 3 to 20, and each Q is independently hydrocarbyl; -N = P - R ３ Selected from, where each R is independently hydrocarbyl; aryloxy; Alkoxy; and 【Chemistry 13】 In the formula, c is a positive number that is zero or at most 4, and each R ９ These are hydrocarbons independently, and each R ８ The method according to any one of claims 1 to 5, wherein is independently a hydrocarbon.

15. The method according to any one of claims 1 to 14, wherein the aluminum compound is present in an amount sufficient to provide 100 to 2,500 parts by weight of aluminum per 1 million parts by weight of the alkylene oxide polymer or copolymer.

16. The method according to any one of claims 1 to 15, wherein the aluminum compound and the starter are combined in a ratio that provides 0.00005 to 0.05 moles of aluminum per equivalent of the starter.

17. The method according to any one of claims 1 to 16, wherein the molar ratio of the aluminum compound to the phosphorus-nitrogen base is at least 1:3 to a maximum of 5:

1.

18. The method according to any one of claims 1 to 17, wherein the starter contains one or more hydroxyl groups and has a hydroxyl equivalent weight of 30 to 6000 g / equivalent.

19. The method according to any one of claims 1 to 18, wherein the starter contains 2 to 8 hydroxyl groups and has an equivalent weight of 30 to 250 g / equivalent.

20. The method according to any one of claims 1 to 19, wherein the alkylene oxide is propylene oxide, ethylene oxide, or a mixture of propylene oxide and ethylene oxide.

21. The method according to any one of claims 1 to 18, wherein the starter is a homopolymer of propylene oxide and / or a random or block copolymer of propylene oxide having at least 125 to a maximum of 4000 g / equivalent weight of hydroxyl groups, and 25% or less of the hydroxyl groups being primary.

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