CN113024795A - Method for synthesizing polyether polyol or monohydric alcohol - Google Patents
Method for synthesizing polyether polyol or monohydric alcohol Download PDFInfo
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- CN113024795A CN113024795A CN202110495864.5A CN202110495864A CN113024795A CN 113024795 A CN113024795 A CN 113024795A CN 202110495864 A CN202110495864 A CN 202110495864A CN 113024795 A CN113024795 A CN 113024795A
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- polyether polyol
- monohydric alcohol
- compound
- fluorine atom
- glycol
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 39
- 229920000570 polyether Polymers 0.000 title claims abstract description 39
- 229920005862 polyol Polymers 0.000 title claims abstract description 38
- 150000003077 polyols Chemical class 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Chemical group 0.000 claims abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000223 polyglycerol Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 4
- PLFFHJWXOGYWPR-HEDMGYOXSA-N (4r)-4-[(3r,3as,5ar,5br,7as,11as,11br,13ar,13bs)-5a,5b,8,8,11a,13b-hexamethyl-1,2,3,3a,4,5,6,7,7a,9,10,11,11b,12,13,13a-hexadecahydrocyclopenta[a]chrysen-3-yl]pentan-1-ol Chemical compound C([C@]1(C)[C@H]2CC[C@H]34)CCC(C)(C)[C@@H]1CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@@H]1[C@@H](CCCO)C PLFFHJWXOGYWPR-HEDMGYOXSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 12
- 230000033444 hydroxylation Effects 0.000 abstract description 9
- 238000005805 hydroxylation reaction Methods 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229920000178 Acrylic resin Polymers 0.000 abstract description 2
- 239000004925 Acrylic resin Substances 0.000 abstract description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 2
- 239000003945 anionic surfactant Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 229920001225 polyester resin Polymers 0.000 abstract description 2
- 239000004645 polyester resin Substances 0.000 abstract description 2
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 2
- 229920005749 polyurethane resin Polymers 0.000 abstract description 2
- -1 polyoxypropylene propylene glycol Polymers 0.000 description 15
- 238000007142 ring opening reaction Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 5
- DUBASSMOXQNSEZ-UHFFFAOYSA-N 2-methyloxirane;propane-1,2-diol Chemical compound CC1CO1.CC(O)CO DUBASSMOXQNSEZ-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- BJUPZVQSAAGZJL-UHFFFAOYSA-N 2-methyloxirane;propane-1,2,3-triol Chemical compound CC1CO1.OCC(O)CO BJUPZVQSAAGZJL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011903 deuterated solvents Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- ZMXDDKWLCZADIW-YYWVXINBSA-N DMF-d7 Substances [2H]C(=O)N(C([2H])([2H])[2H])C([2H])([2H])[2H] ZMXDDKWLCZADIW-YYWVXINBSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical class [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2654—Aluminium or boron; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing polyether polyol or monohydric alcohol, wherein in the presence of a binuclear compound represented by the formula (I), an active hydrogen-containing compound reacts with a heterocyclic compound to prepare the polyether polyol or the monohydric alcohol: x2Lm(I) In the formula (I), X is boron atom or chlorine atom, L is one or more of fluorine atom substituted naphthalene ring, fluorine atom substituted benzene ring and fluorine atom substituted polycyclic aromatic group; m is an integer of 1 to 6. According to the preparation method of the invention, polyether polyol or monohydric alcohol with high terminal primary hydroxylation rate can be prepared, and the catalyst has good reaction activity, so that the preparation method can be applied to many fields, such as polymer polyether, polyurethane resin, polyurethane prepolymer, polyurethane elastomer, epoxy resin, acrylic resin, polyester resin, various anionic surfactants and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing polyether polyol or monohydric alcohol.
Background
Polyether polyols, which can be obtained by ring-opening reaction of an alkylene oxide with an active hydrogen-containing compound, are widely used as raw materials for thermosetting resins such as polyurethanes, and also find applications in surfactants, lubricants and other fields. At present, the main preparation process of polyether polyols is ring-opening polymerization of alkylene oxides in the presence of basic catalysts. The alkali metal compounds used as the alkali catalyst are mainly sodium hydroxide, potassium hydroxide and the like. Another method comprises ring-opening polymerization of alkylene oxides using zinc hexacyanocobaltate or similar complex metal cyanide complexes as catalysts. However, most of products synthesized under the action of these catalysts are polyether polyols with secondary hydroxyl at the end, and the polyether polyols with secondary hydroxyl have low reactivity with isocyanate, and the ring-opening reaction of ethylene oxide is required to be continued, so that the proportion of the primary hydroxyl at the end is increased, and the polyether polyols with primary hydroxyl at the end are obtained, and the reactivity with isocyanate can be greatly improved. However, since polyoxyethylene ether obtained by the ring-opening reaction of ethylene oxide has hydrophilicity, the hydrophobicity of polyether polyol obtained correspondingly decreases, thereby decreasing the moisture resistance and various other physical properties of the polyurethane obtained. In other documents, a preparation method of polyether polyol with high primary hydroxyl is reported, but the preparation method is complex in preparation process, complicated in preparation process and has an improved space.
The catalyst used at present can not enable the terminal primary hydroxyl in the polyether polyol to reach a high proportion, or the production period is long, the production cost is high, and the requirement of industrial production can not be met. Therefore, there is an urgent need to develop a novel catalyst system capable of more simply and efficiently increasing the proportion of terminal primary hydroxyl groups. The active center atoms of the currently used catalysts only contain a single atom, namely, the compounds are mononuclear atom compounds. A novel propylene oxide selective ring-opening polymerization catalytic system and a polymerization process are developed, so that propylene oxide can be subjected to selective ring-opening polymerization, polyether polyol with high terminal primary hydroxylation rate can be directly obtained, and the subsequent ring-opening reaction step of ethylene oxide in the conventional method is omitted. The higher the primary hydroxyl value of the polyether polyol, the more excellent the emulsifying property of the polyether polyol.
Disclosure of Invention
In order to overcome the above-mentioned deficiencies of the prior art, a method for synthesizing polyether polyol or monohydric alcohol is provided.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing polyether polyol or monohydric alcohol comprises the following steps of reacting an active hydrogen-containing compound with a heterocyclic compound in the presence of a binuclear compound represented by the formula (I) to prepare polyether polyol or monohydric alcohol:
X2Lm (I)
in the formula (I), X is boron atom or chlorine atom, L is one or more of fluorine atom substituted naphthalene ring, fluorine atom substituted benzene ring and fluorine atom substituted polycyclic aromatic group; m is an integer of 1 to 6.
Preferably, L is an aromatic group in which 50% of the hydrogen atoms of the aromatic group have been replaced with fluorine atoms, more preferably 80% of the hydrogen atoms have been replaced, and most preferably 100% of the hydrogen atoms have been replaced, i.e., a perfluoro-substituted aromatic group, and an aromatic group in which a perfluoro-substituted aromatic group has been replaced.
Preferably, the binuclear compound is:
preferably, the hetero atom of the heterocyclic compound is an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom or a phosphorus atom; the heterocyclic compound includes heterocyclic compounds containing a divalent group of-O-, -CO-, -S-, -NH-, -OCOO-, -OCOS-, -COO-and-CONH-.
Preferably, the heterocyclic compound is a heterocyclic compound in which the heteroatom is an oxygen atom, and includes ethylene oxide, propylene oxide, butylene oxide, and isobutylene oxide.
Preferably, the active hydrogen-containing compound is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, polyethylene glycol, polypropylene glycol, or polyglycerol.
Preferably, the polyether polyol or the monool has a terminal primary hydroxyl group content of not less than 70%.
Compared with the prior art, the invention has the following technical effects:
according to the method for preparing the polyether polyol or the monohydric alcohol, provided by the invention, through designing and preparing the central atom as the dinuclear atom, namely when the catalyst is a dinuclear compound, not only is the catalytic activity improved, but also the content of terminal hydroxyl of the prepared polyether polyol or the prepared monohydric alcohol can be improved to more than 70%, and the purpose of the invention is effectively realized.
By using the catalyst of the present invention, a polyether polyol or monool having a terminal primary hydroxyl group content of not less than 70% can be obtained by a ring-opening addition polymerization process of an alkylene oxide to an active hydrogen-containing compound.
The specific catalyst binuclear compound has high catalytic activity, and the yield of the cyclic compound in the ring-opening addition polymerization reaction in the presence of the specific catalyst is high.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The test methods used in the following experimental examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
About 30 mg of the sample was weighed into a5 mm diameter NMR sample tube and about 0.5 ml of deuterated solvent was added to dissolve the sample. Then, about 0.1 ml of trifluoroacetic anhydride was added, and the resulting solution was used as an analysis sample. The deuterated solvent can be deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide and the like, and a proper solvent is selected to dissolve the sample.
The 1H-NMR measurement was carried out under conventional conditions.
< calculation of the proportion of Primary hydroxyl groups >
After the above pretreatment, the terminal hydroxyl groups of the sample polyoxyalkylene polyol were reacted with added trifluoroacetic anhydride to form a trifluoroacetic anhydride derivative. Methylene groups of primary hydroxyl groups gave a signal of about 4.3ppm, while methylene groups of secondary hydroxyl groups gave a signal of about 5.2 ppm.
The proportion of primary hydroxyl groups in the terminal hydroxyl groups is calculated according to the following formula:
primary hydroxyl group ratio in terminal hydroxyl group ═ a/2 xb) ] × 100
Wherein a is the integral of the signal at about 4.3ppm from methylene groups having primary hydroxyl groups; b is the integral of the signal at about 5.2ppm for methylene groups with secondary hydroxyl groups.
The content of the terminal primary hydroxyl of the polyether polyol D obtained by the invention is not less than 70%, preferably more than 85%, and more preferably more than 90%. The binuclear compound A is high in activity as a catalyst, a small amount of compound A is added as the catalyst (10-100 ppm) at a low temperature (40-90 ℃), the reaction can be completed quickly, and the molecular weight distribution of the obtained product is narrow.
The polyether polyol D obtained by the invention has a weight average molecular weight of 200-3000, preferably 400-15000 and a molecular weight distribution of 1.0-1.4.
Example 1
A500-ml autoclave equipped with a stirrer and a temperature control device was charged with 100.4 g of a propylene glycol-propylene oxide adduct (PPG-1000, weight-average molecular weight: about 1000) and 0.02 g of catalyst A1 [ 1,2- (C)10F7)2BC6F4B(C10F7)2And (c) a temperature sensor. Replacing air in the kettle with nitrogen, dehydrating at 100 deg.C under reduced pressure for two hours, adding 200.5 g of propylene oxide dropwise at 70-100 deg.C, maintaining the reaction pressure not more than 3 atm, and reactingIt takes about 5 hours. After completion of the polymerization, the reaction mixture was neutralized with an aqueous sodium hydroxide solution. 3.0 g of synthetic diatomaceous earth and water were added and the mixture was treated at 100 ℃ for 3 hours. The mixture was taken out from the autoclave and filtered and dehydrated to obtain 298.3 g of polyoxypropylene propylene glycol adduct D1 in liquid form, and the calculated yield was about 99.1% based on the weight of propylene glycol-propylene oxide adduct and propylene oxide charged. The weight average molecular weight Mw of the ring-opened polymer was 2890 and the molecular weight distribution Mw/Mn was 1.26 by GPC measurement. The terminal hydroxyl group content was determined by 1H-NMR to be 74%.
Example 2
Except that the catalyst is replaced by A2 [ 1,4- (C)10F7)2BC6F4B(C10F7)2In addition, 295.3 g of a liquid polyoxypropylene propylene glycol ring-opening polymer D2 was obtained under the same experimental conditions as in example 1, and the yield was about 98.2%, Mw 3059, Mw/Mn 1.32 and a terminal primary hydroxylation rate of 91%.
Example 3
280.3 g of a polyoxypropylene propylene glycol ring-opening polymer D3 in liquid form was obtained under the same experimental conditions as in example 1, except that A3 was used as the catalyst, and the yield was about 93.3%, Mw was 2850, Mw/Mn was 1.42, and the terminal primary hydroxylation rate was 83%.
Example 4
Using a glycerin-propylene oxide adduct (a product of trifunctional 306, having a weight average molecular weight of about 600) as a starting material, a liquid polyoxypropylene glycerin ring-opening polymer D4 was obtained under the same experimental conditions as in example 1, with a yield of about 97.5%, an Mw of 2890, an Mw/Mn of 1.32, and a proportion of terminal primary hydroxyl groups of 75%.
Example 5
The procedure was carried out in the same manner as in example 2 except that a glycerin-propylene oxide adduct (product 310) having a molecular weight of 1000 was used in place of the propylene glycol-propylene oxide adduct having a molecular weight of 1000, and A2 and propylene oxide were used in amounts of 0.25 g and 100.5 g, respectively, to give 195.2 g of polyoxypropylene triol D5 (weight-average molecular weight: about 2000) in a liquid state. The yield was 97.3%, and the proportion of terminal primary hydroxyl groups of the obtained polyoxypropylene triol was 92%.
Example 6
The procedure was carried out in the same manner as in example 2 except that a glycerin-propylene oxide adduct (product 330) having a molecular weight of 3000 was used in place of the propylene glycol-propylene oxide adduct having a molecular weight of 1000, and that A2 and propylene oxide were used in amounts of 0.36 g and 56.3 g, respectively, to give 152.1 g of polyoxypropylene triol D6 (weight-average molecular weight: about 4200) as a liquid. The yield was 96.3%, and the proportion of terminal primary hydroxyl groups of the obtained polyoxypropylene triol was 93%.
Example 7
270.5 g of a polyoxypropylene propylene glycol ring-opening polymer D7 in liquid form was obtained under the same experimental conditions as in example 1, except that A4 was used as the catalyst, and the yield was about 89.2%, Mw was 2780, Mw/Mn was 1.32, and the terminal primary hydroxylation rate was 92%.
Example 8
271.8 g of a polyoxypropylene propylene glycol ring-opening polymer D8 in liquid form was obtained under the same experimental conditions as in example 1, except that the catalyst was A5, and the yield was about 90.2%, Mw was 2970, Mw/Mn was 1.52, and the terminal primary hydroxylation rate was 94%.
Example 9
193.6 g of polyoxypropylene triol D9 (weight average molecular weight: about 1970) in liquid form was obtained under the same experimental conditions as in example 5 except that A6 was used as the catalyst. The yield was 93.3%, and the proportion of terminal primary hydroxyl groups of the obtained polyoxypropylene triol was 96%.
< measurement of emulsion Property >
Polyether polyol or monohydric alcohol is used for synthesizing AE-9, AE-10, AE-11 and MEO-5. The emulsifying performance of polyether polyol or monohydric alcohol is characterized by measuring the gel rate, solid content, ionic stability, centrifugal stability and particle size distribution of styrene-acrylic emulsion and hydroxypropyl emulsion in which AE-9, AE-10, AE-11 and MEO-5 are located. In the styrene-acrylic emulsion and the hydroxypropyl emulsion, the four products have better gel performance and stability. In the comparison of solid content and gel rate, the solid content is 38-48%; by centrifugation at 7000rpm for 3min and addition of 5ml of 5% CaCl2Under the condition that the solution is placed for 24 hours, no obvious phenomenon exists in all four products, and the performance is strongStability of (2); the particle sizes of the four products in the styrene-acrylic emulsion are within the range of 90-130nm and are smaller, and the particle sizes in the hydroxypropyl solution are within the range of 260-310nm and are larger.
Application prospect
According to the catalyst and the ring-opening polymer preparation method used by the invention, the heterocyclic ring-opening polymer with high terminal primary hydroxylation rate can be prepared, and the high primary hydroxylation polyether polyol or monohydric alcohol can be obtained. The heterocyclic ring-opening polymer with high terminal primary hydroxylation rate prepared by the invention is expected to be applied in many fields due to better reaction activity. For example, the polymer can be used in many fields such as polymer polyether, polyurethane resin, polyurethane prepolymer, polyurethane elastomer, epoxy resin, acrylic resin, polyester resin, various anionic surfactants, and the like.
Claims (6)
1. A method for synthesizing polyether polyol or monohydric alcohol is characterized in that in the presence of a binuclear compound represented by the formula (I), an active hydrogen-containing compound is reacted with a heterocyclic compound to prepare polyether polyol or monohydric alcohol:
X2Lm (I)
in the formula (I), X is boron atom or chlorine atom, L is one or more of fluorine atom substituted naphthalene ring, fluorine atom substituted benzene ring and fluorine atom substituted polycyclic aromatic group; m is an integer of 1 to 6.
2. A method for the synthesis of polyether polyols or monools according to claim 1 wherein said dinuclear compound is:
3. a process for the synthesis of a polyether polyol or a monool according to claim 1, characterised in that the hetero atoms of said heterocyclic compound are oxygen atoms, nitrogen atoms, sulphur atoms, silicon atoms or phosphorus atoms; the heterocyclic compound includes heterocyclic compounds containing a divalent group of-O-, -CO-, -S-, -NH-, -OCOO-, -OCOS-, -COO-and-CONH-.
4. A process for the synthesis of a polyether polyol or monol according to claim 3 wherein the heterocyclic compound is a heterocyclic compound in which the heteroatom is an oxygen atom, including ethylene oxide, propylene oxide, butylene oxide and isobutylene oxide.
5. A process for the synthesis of a polyether polyol or monol according to claim 3, wherein the active hydrogen-containing compound is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, polyethylene glycol, polypropylene glycol or polyglycerol.
6. The method of synthesizing polyether polyol or monool according to claim 1 wherein said polyether polyol or monool has a terminal primary hydroxyl group content of not less than 70%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308648A (en) * | 1998-07-10 | 2001-08-15 | 三洋化成工业株式会社 | Novel polyoxyalkylenepolyols and process for producing ring-opened polymer |
| CN101628974A (en) * | 2009-08-11 | 2010-01-20 | 华南师范大学 | Polyether glycol or polyether monohydric alcohol preparation method |
| CN102369232A (en) * | 2009-03-30 | 2012-03-07 | 三洋化成工业株式会社 | Polyoxyalkylene polyol or monool and polyurethane resin |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308648A (en) * | 1998-07-10 | 2001-08-15 | 三洋化成工业株式会社 | Novel polyoxyalkylenepolyols and process for producing ring-opened polymer |
| CN102369232A (en) * | 2009-03-30 | 2012-03-07 | 三洋化成工业株式会社 | Polyoxyalkylene polyol or monool and polyurethane resin |
| CN101628974A (en) * | 2009-08-11 | 2010-01-20 | 华南师范大学 | Polyether glycol or polyether monohydric alcohol preparation method |
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