CN111225936A - 制造聚醚多元醇的连续工艺 - Google Patents
制造聚醚多元醇的连续工艺 Download PDFInfo
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- CN111225936A CN111225936A CN201880067172.7A CN201880067172A CN111225936A CN 111225936 A CN111225936 A CN 111225936A CN 201880067172 A CN201880067172 A CN 201880067172A CN 111225936 A CN111225936 A CN 111225936A
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- weight
- oxide
- glycol
- alkylene oxide
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- 229920000570 polyether Polymers 0.000 title claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 20
- 238000010924 continuous production Methods 0.000 title claims description 8
- 229920005862 polyol Polymers 0.000 title abstract description 17
- 150000003077 polyols Chemical class 0.000 title abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 36
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- -1 aryloxide Chemical class 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 125000006353 oxyethylene group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 41
- 239000006260 foam Substances 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
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- 239000011541 reaction mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- AZMMSEASPQHHTC-UHFFFAOYSA-N 2-[1,1-bis(2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=CC=C(O)C=1C(C=1C(=CC=CC=1)O)(C)C1=CC=CC=C1O AZMMSEASPQHHTC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010021639 Incontinence Diseases 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
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- C08G65/10—Saturated oxiranes characterised by the catalysts used
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- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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- C—CHEMISTRY; METALLURGY
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Abstract
包含按重量计大于50％的环氧乙烷的环氧烷混合物在双金属氰化物聚合催化剂和羟基当量为至多200的烷氧基化的引发剂的存在下连续地聚合。催化剂保持活性以快速的反应速率连续产生具有至多700的当量且具有高氧化乙烯含量的多元醇。
Description
本发明涉及一种在双金属氰化物(DMC)聚合催化剂的存在下连续共聚主要包含环氧乙烷的环氧烷混合物的方法。
DMC配合物是聚合环氧丙烷以形成聚(环氧丙烷)多元醇的有效的催化剂。聚(环氧丙烷)多元醇可用作制造聚氨酯的原材料。
环氧丙烷和环氧乙烷的混合物也已经使用DMC催化剂聚合。通常，这些混合物主要包含环氧丙烷和少量的环氧乙烷。在某些情况下，DMC催化剂已被描述用于聚合主要包含环氧乙烷的混合物。然而，这些聚合主要限于试图引入伯羟基的聚(环氧丙烷)的封端。例如，美国专利号6,884,826描述了一种工艺，其中使用DMC催化剂使环氧丙烷聚合。随着聚合的进行，环氧乙烷与环氧丙烷一起以逐渐增加的比例进料。在聚合的最后约15％期间，进料至反应的单体混合物中的环氧乙烷浓度增加按重量计50％以上。
美国专利号6,884,826的工艺具有明显的缺点。它本质上是分批或半分批工艺，并不适用于连续多元醇生产。另外，尽管DMC催化剂在环氧乙烷是主要存在的单体的相对短的时期内保持活性，但是它仅在短时间之后就失活，特别是当产物当量低时。这再次将美国专利号6,884,826的工艺限制为分批或半分批操作。
在某些聚氨酯应用中，主要含环氧乙烷和少量环氧丙烷的无规共聚物是有用的。这些多元醇已经被发现用于例如制造粘弹性泡沫。它们也可用作软质聚氨酯泡沫中的开孔剂。这些多元醇可以使用氢氧化钾或其他碱性催化剂分批或半分批制造，但是由于有单体进料中环氧乙烷高浓度的存在下催化剂失活的问题，尚未发现商业上可接受的使用DMC催化剂制造这些多元醇的方法。由于DMC催化提供的潜在优势，期望提供一种连续的工艺来制造这些无规共聚物。
WO 2016/209677描述了使用DMC催化剂制造这种无规共聚物的连续工艺。需要促进剂化合物以防止催化剂失活。
本发明是生产羟基当量为200至2000的聚醚产物的连续工艺，包括：
a)在连续反应器中形成以下的混合物：A)双金属氰化物催化剂；B)环氧烷混合物，包含环氧丙烷和基于环氧烷重量按重量计至少60％的环氧乙烷；C)至少一种烷氧基化的引发剂化合物，具有至少一个羟基且羟基当量为70至200但小于聚醚产物的羟基当量；以及D)聚合产物，由分子量大于引发剂化合物且至多为并包括聚醚产物的分子量的烷氧基化的物质组成，以及
b)连续地加入额外的催化剂、额外的环氧烷混合物(其包含环氧丙烷和基于环氧烷的重量按重量计至少60％的环氧乙烷)和额外的引发剂化合物到在聚合条件下的连续反应器中，并从所述连续反应器中连续地排出包含聚醚产物的产物流.
其中：
i)步骤a)和b)在基本上不存在键合至以下的镁、第3族-第15族金属或镧系金属的情况下进行：至少一种烷氧离子、芳氧基、羧酸根、酰基、焦磷酸根、磷酸根、硫代磷酸根、二硫代磷酸根、磷酸酯、硫代磷酸酯、酰胺、硅氧化物、氢负离子、氨基甲酸根或烃阴离子，并且不含卤素阴离子，和
ii)聚醚产物包含按重量计50至90％的聚合环氧乙烷。
令人惊讶地，该工艺在高的聚合速率和不失活的情况下连续操作，允许在不存在镁、第3族-第15族或镧系金属化合物的情况下持续连续操作。
基于氧化物混合物的重量，本发明中聚合的环氧烷混合物包含按重量计大于60％的环氧乙烷。它可以包含例如按重量计至少70％或至少75％的环氧乙烷，并且可以包含多达95％、多达90％或多达85％的环氧乙烷，在每种情况下按重量计。环氧烷混合物包含按重量计最多40％的1，2-环氧丙烷。它可以包含按重量计至多30％、至多25％、至多15％、至多10％或至多5％的1，2-环氧丙烷。环氧烷混合物可以包含少量，诸如按重量计至多25％、按重量计至多10％或按重量计至多5％的一种或多种其他环氧烷，但是可以省略这样的其他环氧烷。
引发剂化合物是烷氧基化的有机化合物，其将在聚合反应中进一步被烷氧基化。它包含1个或多个羟基，优选2个或更多个羟基。它可以包含12个或更多个羟基。优选的引发剂每分子包含2个至8个羟基。可以使用引发剂化合物的混合物。
引发剂化合物具有70至200的羟基当量但小于聚醚产物的羟基当量。在一些实施方式中，羟基当量为70至150或70至125。
合适的引发剂包括但不限于乙二醇、二甘醇、三甘醇、丙二醇、二丙二醇、三丙二醇、1，4-丁二醇、1，6-己二醇、1，8-辛二醇、环己烷二甲醇、丙三醇、三羟甲基丙烷、三羟甲基乙烷、季戊四醇、山梨醇、蔗糖、苯酚、C1-24烷醇和多酚引发剂，诸如双酚A或1，1，1-三(羟苯基)乙烷等中的一种或多种的烷氧基化物。烷氧基化物可以是乙氧基化物和/或丙氧基化物。
引发剂可以用少量的酸中和或包含少量的酸，特别是如果引发剂是在碱的存在下生产的。如果存在酸，如USP 6,077,978中所述，其基于引发剂的重量可以以约10至100ppm的量存在。可替换地，再次基于引发剂的重量，可以以更大的量使用酸，诸如100至1000ppm，如美国公布专利申请号2005-0209438中所述。
合适的双金属氰化物(DMC)催化剂包括那些描述于，例如，美国专利号3,278,457、3,278,458、3,278,459、3,404,109、3,427,256、3,427,334、3,427,335和5,470,813中的催化剂。一些合适的DMC催化剂可以用下式表示
Mb[M1(CN)r(X)t]c[M2(X)6]d·nM3 xAy
其中M和M3各自是金属；M1是与M不同的过渡金属，每个X表示与M1离子配位的除氰化物以外的基团；M2是过渡金属；A表示阴离子；b、c和d是反映静电中性配合物的数字；r是4到6；t是0到2；x和y是使金属盐M3 xAv中的电荷平衡的整数，并且n为零或正整数。上式没有反映出DMC催化剂配合物中通常存在的中性配合剂，诸如叔丁醇。
M和M3各自优选地是独立地选自由以下组成的组的金属离子：Zn2+、Fe2+、Co+2+、Ni2 +、Mo4+、Mo6+、Al+3+、V4+、V5+、Sr2+、W4+、W6+、Mn2+、Sn2+、Sn4+、Pb2+、Cu2+、La3+和Cr3+，其中Zn2+为优选的。
M1和M2优选为Fe3+、Fe2+、Co3+、Co2+、Cr2+、Cr3+、Mn2+、Mn3+、Ir3+、Ni2+、Rh3+、Ru2+、V4+、V5 +、Ni2+、Pd2+和pt2+。在这些之中，更优选处于正三氧化态的作为M1和M2金属。Co+3和Fe+3是甚至更优选的，Co+3是最优选的。
合适的阴离子A包括但不限于卤素(诸如氯离子、溴离子和碘离子)、硝酸根、硫酸根、碳酸根、氰离子、草酸根、硫氰酸根、异氰酸根、高氯酸根、异硫氰酸根、烷磺酸根(诸如甲烷磺酸根)、亚芳基磺酸根(诸如对甲苯磺酸根)、三氟甲基磺酸根(三氟甲磺酸根)和C1-4羧酸根。氯离子是特别优选的。
r优选为4、5或6，优选为4或6，并且最优选为6；t优选为0或1，最优选为0。在大多数情况下，r+t将等于六。
合适类型的DMC催化剂配合物是六氰基钴酸锌催化剂配合物，如例如在美国专利号3,278,457、3,278,458、3,278,459、3,404,109、3,427,256、3,427,334、3,427,335和5,470,813中任何一个所述的。特别优选类型的DMC催化剂是与叔丁醇配合。
基于反应混合物的重量，该工艺的步骤b)中的DMC催化剂配合物的浓度可以为1至5000ppm。DMC催化剂配合物的浓度可以为至少2ppm、至少5ppm、至少10ppm或至少25ppm、至多500ppm、至多250ppm、至多150ppm或至多100ppm。排出的产物流将包含相同范围内的DMC催化剂残留物。
步骤a)和b)在基本不存在键合至以下的镁、第3族-第15族金属或镧系金属的情况下进行：至少一种烷氧离子、芳氧基、羧酸根、酰基、焦磷酸根、磷酸根、硫代磷酸根、二硫代磷酸根、磷酸酯、硫代磷酸酯、酰胺、硅氧化物、氢负离子、氧负离子、氨基甲酸根或烃阴离子，并且不含卤素阴离子。为了本发明的目的，当这样的化合物以每克DMC催化剂配合物最多0.1摩尔，并且优选每克DMC催化剂配合物最多0.001摩尔的量存在时，这样的化合物“基本上不存在”。这些量应用于相对于所有这样的镁，第3族-第15族金属或镧系金属的化合物的组合量。
在本发明中，环氧乙烷和1，2-环氧丙烷的混合物在DMC催化剂配合物和引发剂化合物的存在下聚合。聚合连续进行。这样的连续工艺包括步骤a)和步骤b)，在步骤a)中在反应器中建立材料的初始浓度，在步骤b)中将引发剂、环氧烷混合物和催化剂连续进料到反应器中，同时连续除去产物流。
催化剂通常在步骤b)之前被活化。优选地，在步骤b)之前建立稳态聚合条件。稳态条件包括例如温度和压力，引发剂、环氧烷混合物、催化剂和聚合产物的浓度，所有这些在步骤b)期间均在设备能力范围内恒定。“聚合产物”是指在步骤a)和步骤b)期间在引发剂化合物的烷氧基化中形成的聚醚，包括所有分子量大于引发剂化合物并且至多为并包括产物的分子量的那些聚醚。
在步骤b)中，在聚合条件下将催化剂、环氧烷混合物和引发剂连续进料到连续反应器中。催化剂、环氧烷和引发剂可以单独地进料，作为混合物进料，和/或以两种或更多种的次混合物的形式进料，其中每种次混合物均包含其任意两种或更多种。从连续反应器中连续除去产物流。一起选择一种或多种进料的进料速率和产物流的排出速率，以维持反应器中的稳态条件(在设备的能力范围内)，并生产具有所需分子量的产物。
环氧烷可以根据需要通过将具有环氧烷混合物的反应器连续加压至预定的内部反应器压力而进料到反应器中。在建立稳态操作时，未反应的环氧烷的浓度基于反应器内容物的重量，优选维持在按重量计0.01％至10％，更优选0.1％至5％，最优选0.5至3％或0.75至2％的水平。
聚合温度通常为至少80℃，优选至少120℃，更优选至少140℃。反应温度可以为200℃或更高，但优选温度至多190℃，更优选为180℃或至多165℃，以维持可工作的反应器压力，避免形成大量的挥发性杂质或其他副产物，以及在不使DMC催化剂失活或分解的情况下维持足够的催化剂活性。聚合反应通常在超大气压下进行，但是可以在大气压甚至低于大气压下进行。
聚合反应可以在适合遇到的压力和温度的任何类型的容器中进行。该容器应具有一个或多个入口以及至少一个出口，在反应期间可以通过该入口引入各种进料，通过该出口可以排出产物流。具有用于注入起始材料的多个点的管式反应器，回路反应器和连续搅拌釜反应器(CTSR)都是用于连续操作的合适的容器类型。反应器应配备有供热或除热的装置，因此反应混合物的温度可以维持在所需的范围内。合适的手段包括用于热流体的各种类型的护套，各种类型的内部或外部加热器等。对连续排出的产物进行的蒸煮步骤方便地在反应器中进行，该步骤可防止在进行步骤b)时反应器中的大量返混。在管子或管式反应器中进行活塞流操作是进行这种蒸煮步骤的优选方式。
聚醚产物基于总重量，可包含按重量计至多0.5％的未反应的环氧烷；分子量低于产物的少量的引发剂化合物及其烷氧基化物；以及少量的其他有机杂质和水。挥发性杂质应从聚醚中闪蒸或汽提。产物通常包含催化剂残留物。这些残留物通常留在产物中，但可以根据需要将其除去。水分和挥发物通过汽提多元醇除去。
本发明的工艺可用于制备具有低至200至高至约2000的羟基当量的聚醚产物。羟基当量可以例如至少225、至少250或至少275，并且可以例如至多2000、至多1750、至多1500、至多1200、至多1000、至多750、至多500、至多400或至多350。除非另有说明，本文提及的所有当量和分子量均为通过凝胶渗透色谱法的数均重量。
根据本发明制造的聚醚可用作制造聚氨酯的起始材料。因为它们包含大比例的聚合环氧乙烷，所以聚醚通常在某种程度上是亲水的并且具有高比例的伯羟基。它们聚醚特别可用作制造粘弹性聚氨酯泡沫的起始材料，以及用作制造块状料和模制的柔性常规和/或高弹性聚氨酯泡沫的开孔剂。它们也可用作表面活性剂，并用于吸水应用中，诸如海绵、尿布和失禁产品等。
以下实施例用以说明本发明，但无意限制其范围。除非另有说明，所有份数和百分数均以重量计。
比较运行A
在配备有加热的外部再循环回路和内部冷却盘管的500mL Autoclave Engineers连续搅拌釜反应器中进行连续聚合。再循环回路由齿轮泵驱动，用于再循环反应器内容物。反应器还配备有近红外分析仪流通池和用于引发剂、催化剂浆料和环氧烷的注入口。反应器具有出口，以允许反应器内容物通过加热的出口管线从反应器流出，进入样品收集系统。反应器压力由出口管线上的压力控制阀控制。
将六氰基钴酸锌催化剂配合物与450分子量的聚(环氧丙烷)三元醇混合以形成包含按重量计1％的催化剂配合物的催化剂浆料。
向反应器中装有205g的450分子量的丙三醇引发的聚(环氧丙烷)三元醇，其中包含335ppm的DMC催化剂，并用25ppm的磷酸进行酸化。将混合物在氮气喷射和连续搅拌的情况下加热到130℃持续90分钟，以干燥反应器内容物。然后将反应器加热至160℃，停止喷射，并密封反应器。将141g的1，2-环氧丙烷(PO)和275g的环氧乙烷(EO)进料到反应混合物中以活化催化剂并烷氧基化起始三元醇至约1000的分子量。一旦催化剂被活化，就开始进料环氧乙烷、环氧丙烷、DMC催化剂浆料和用75ppm磷酸酸化的丙三醇。环氧乙烷/环氧丙烷的重量比按重量计为66/34。一旦反应器达到其液体填满点，将产物流排出。调节进出反应器的流速以产生150ppm的DMC催化剂稳态浓度和12小时的停留时间。
监测反应器中未反应的环氧烷的浓度作为催化剂活性的指标。在丙三醇进料开始时，通过近红外分析仪实时测量的未反应氧化物的浓度为约2％。此后，由于催化剂的失活，未反应的氧化物的浓度历经10小时连续上升至6％。作为安全措施，当未反应的氧化物浓度达到6％时，反应器会自动关闭。操作10小时对应于形成的产物小于一个反应器的体积。最终的反应器产物包含142ppm的DMC催化剂。
实施例1
多元醇A的羟值为168(333当量，1000分子量)的三官能无规共聚物或环氧丙烷和环氧乙烷。多元醇A包含按重量计60％的氧化乙烯单元。将1kg的多元醇A装入通过外部夹套加热的1L Buchi反应器中。该反应器配备有用于引入反应物的注入口和用于除去产物流的排出口。压力控制通过安装在排出口的出口管线上的压力控制阀来维持。将近红外池设置在反应器出口处，以测量产物流中未反应的氧化物含量。
将反应器和多元醇A加热至160℃。在此温度下，(1)将由多元醇A中的0.1wt％的六氰基钴酸锌催化剂配合物组成的催化剂浆料以12g/小时的速率连续地进料到反应器中；(2)将分子量为260的丙氧基化丙三醇引发剂以75g/小时的速率连续进料到反应器中和(3)以223g/hr的速率连续进料80.5wt％环氧乙烷和19.5wt％环氧丙烷的混合物至反应器。一旦反应器达到其填满点，将产物流以310g/小时从反应器中排出。这些进料速率和排出速率在反应器中和排出的产物流中产生浓度为40ppm的DMC催化剂。
在这些条件下操作15小时后，在另外24小时的操作期间收集产物，直到实验被任意中断。在整个反应期间，产物流中未反应的氧化物的水平保持在1％，表明DMC催化剂始终保持活性。该产物的羟值为167(336当量，1008分子量)，并包含按重量计60％的氧化乙烯单元。
实施例2
重复实施例1，改变流速如下：(1)多元醇A中的催化剂混合物-15.9g/hr；分子量为260g/mol的丙氧基化丙三醇引发剂-38g/hr；环氧乙烷/环氧丙烷混合物-114g/hr；产物流-167.9g/hr。这些流速在反应器中和产物流中产生浓度为95ppm的DMC催化剂。将这些条件维持15小时，并再维持24小时收集这期间的产物，这之后任意中断实验。在整个运行期间，产物流中未反应的氧化物含量按重量计低于1％，再次表明没有DMC活性损失。该产物的羟值为168(333当量，1000分子量)，并含包含按重量计60％的氧化乙烯单元。
实施例2的产物如下表1所述被用于粘弹性泡沫制剂中。通过混合所有组分并立即将所得混合物放入到盒子中并使泡沫在大气压下上升来制造泡沫。其他类似的泡沫制剂被制造作为比较，其中将实施例2的产物用多元醇A代替。
表1
“吹脱”时间是通过观察泡沫上升来确定的，并且是从将泡沫混合物倒入盒子中的时间计算得出的。根据ASTM D3574-01测量气流、压缩永久变形(90％压缩，平行)、泡沫密度、压陷硬度、回弹力、拉伸强度和撕裂强度，并且根据BASF压缩恢复测试测量粘弹性恢复率(挠度分别为25％、65％和75％时的负载，支撑系数和恢复时间)。结果如表2所示。
表2
Claims (14)
1.生产羟基当量为200至2000的聚醚产物的连续工艺，包括：
a)在连续反应器中形成以下的混合物：双金属氰化物催化剂，包含环氧丙烷和基于环氧烷的重量按重量计至少60％的环氧乙烷的环氧烷混合物，至少一种具有至少一个羟基且羟基当量为70至200但小于所述聚醚产物的羟基当量的烷氧基化的引发剂化合物，和由具有分子量大于所述引发剂化合物且至多为并包括所述聚醚产物的分子量的烷氧基化的物质组成的聚合产物，和
b)连续地加入额外的催化剂、额外的环氧烷混合物(其包含环氧丙烷和基于环氧烷的重量按重量计至少60％的环氧乙烷)和额外的引发剂化合物到在聚合条件下的所述连续反应器中，并从所述连续反应器中连续地排出包含所述聚醚产物的产物流，
其中：
i)步骤a)和步骤b)在基本上不存在键合至以下的镁、第3族-第15族金属或镧系金属的情况下进行：至少一种烷氧离子、芳氧基、羧酸根、酰基、焦磷酸根、磷酸根、硫代磷酸根、二硫代磷酸根、磷酸酯、硫代磷酸酯、酰胺、硅氧化物、氢负离子、氧负离子、氨基甲酸根或烃阴离子，并且不含卤素阴离子，和
ii)所述聚醚产物包含按重量计50至90％的聚合环氧乙烷。
2.根据权利要求1所述的连续工艺，其中，在步骤b)之前，所述双金属氰化物催化剂、所述环氧烷混合物和所述引发剂化合物的稳态浓度被建立在聚合条件下的连续反应器中，并在步骤b)期间维持这种稳态浓度。
3.根据权利要求1或2所述的方法，其中，所述引发剂化合物具有70至150的羟基当量。
4.根据权利要求3所述的方法，其中，所述引发剂化合物是当量为70至150的乙二醇、二甘醇、三甘醇、丙二醇、二丙二醇、三丙二醇、丙三醇、三羟甲基丙烷、季戊四醇、蔗糖和山梨醇中的一种或多种的烷氧基化物。
5.根据权利要求4所述的方法，其中，所述引发剂化合物是当量为70至150的乙二醇、二甘醇、三甘醇、丙二醇、二丙二醇、三丙二醇、丙三醇、三羟甲基丙烷、季戊四醇、蔗糖和山梨醇中的一种或多种的烷氧基化物。
6.根据权利要求5所述的方法，其中，所述引发剂化合物是当量为70至125的丙三醇或三羟甲基丙烷的丙氧基化物。
7.根据任一前述权利要求所述的方法，其中，所述聚醚产物具有200至1750的羟基当量。
8.根据任一前述权利要求所述的方法，其中，所述聚醚产物具有200至700的羟基当量。
9.根据任一前述权利要求所述的方法，其中，所述聚醚产物具有275至400的羟基当量。
10.根据任一前述权利要求所述的方法，其中，步骤a)和步骤b)中的所述环氧烷混合物包含按重量计65至90％的环氧乙烷和相应的按重量计35至10％的环氧丙烷。
11.根据权利要求10所述的方法，其中，步骤a)和步骤b)中的所述环氧烷混合物包含按重量计70至85％的环氧乙烷和相应的按重量计30至15％的环氧丙烷。
12.根据权利要求11所述的方法，其中，步骤a)和步骤b)中的所述环氧烷混合物包含按重量计75至85％的环氧乙烷和相应的按重量计25至15％的环氧丙烷。
13.根据任一前述权利要求所述的方法，其中，所述双金属氰化物催化剂是六氰基钴酸锌催化剂配合物。
14.根据任一前述权利要求所述的方法，其中，双金属氰化物催化剂在步骤b)中的量以按重量计25至100ppm的浓度存在。
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