CN107177034B - Allyl alcohol polyoxypropylene ether and preparation method thereof - Google Patents
Allyl alcohol polyoxypropylene ether and preparation method thereof Download PDFInfo
- Publication number
- CN107177034B CN107177034B CN201710413295.9A CN201710413295A CN107177034B CN 107177034 B CN107177034 B CN 107177034B CN 201710413295 A CN201710413295 A CN 201710413295A CN 107177034 B CN107177034 B CN 107177034B
- Authority
- CN
- China
- Prior art keywords
- allyl alcohol
- polyoxypropylene ether
- molecular weight
- reaction
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 341
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 250
- -1 polyoxypropylene Polymers 0.000 title claims abstract description 133
- 229920001451 polypropylene glycol Polymers 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 132
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 76
- 229920000570 polyether Polymers 0.000 claims abstract description 76
- 239000000047 product Substances 0.000 claims abstract description 60
- 239000006227 byproduct Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 47
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000009826 distribution Methods 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 10
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 60
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 26
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 25
- 229910052740 iodine Inorganic materials 0.000 description 25
- 239000011630 iodine Substances 0.000 description 25
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 229920002545 silicone oil Polymers 0.000 description 18
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 15
- 238000004811 liquid chromatography Methods 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- 238000006073 displacement reaction Methods 0.000 description 12
- 239000006260 foam Substances 0.000 description 11
- 238000009849 vacuum degassing Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 8
- 239000000391 magnesium silicate Substances 0.000 description 8
- 229910052919 magnesium silicate Inorganic materials 0.000 description 8
- 235000019792 magnesium silicate Nutrition 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 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
- C08G65/2603—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
-
- 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
- C08G65/2648—Alkali metals or 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
- C08G65/2642—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
- C08G65/2696—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 process or apparatus used
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to allyl alcohol polyoxypropylene ether and a preparation method thereof, belonging to the technical field of organic high molecular compound preparation. Using allyl alcohol and epoxypropane as raw materials, adding allyl alcohol and primary polymerization catalyst into a reaction kettle, and then adopting N2Replacing air in the kettle, heating to a certain temperature, and adding propylene oxide to react to synthesize an oligomer; adopting a reactor combining stirring and external circulation, and placing the oligomer and the final polymerization catalyst in the reactor to synthesize the product allyl alcohol polyoxypropylene ether with the molecular weight of 1000-5000-. The method is applied to the synthesis and preparation of polyether, and has the advantages of low content of byproducts, high double bond protection rate, less residual metal ions, narrow molecular weight distribution and the like.
Description
Technical Field
The invention relates to allyl alcohol polyoxypropylene ether and a preparation method thereof, belonging to the technical field of organic high molecular compound preparation.
Background
The allyl alcohol polyoxypropylene ether is allyl at one end and hydroxyl unsaturated polyether at the other end. The allyl alcohol polyoxypropylene ether mainly uses double bonds of polyether to react with various active groups to introduce special properties such as lubricating effect, softening effect, good spreadability, demulsification property, defoaming property and the like provided by a polyether chain segment into various novel multifunctional fine chemical products.
The allyl alcohol polyoxypropylene ether can be subjected to hydrosilylation reaction with polysiloxane containing active silicon hydrogen bonds under the action of a catalyst, and Si-C type polyurethane foam stabilizer, pesticide spreading agent, defoaming agent and the like can be obtained according to different molecular weights of allyl alcohol polyether.
There are some reports on allyl alcohol polyether. The patent CN 100999575A and CN 100999578A disclose a method for synthesizing random polyether of allyl alcohol, which uses KOH as catalyst to synthesize 150-1000 molecular weight allyl alcohol oligomer, uses the oligomer as initiator, and uses multi-metal cyanide (MMC) containing metal ions such as Co, Zn, Pb, etc. as catalyst to synthesize high molecular weight allyl alcohol polyether at 70-160 deg.C, the highest molecular weight can reach 20000. The method has the advantages that the polyether with high molecular weight can be synthesized, the shortage is that the synthesized polyether has a small amount of the polyether with ultra-high molecular weight, the molecular weight is about 50000-150000, and the weight percentage content is about 0.5-5%, which influences the viscosity quality of the product. Because the polyether has residual metal ions, when the polyether reacts with hydrogen-containing silicone oil, the catalytic activity of chloroplatinic acid is affected, the catalytic activity of the chloroplatinic acid is inactivated, the dosage of a catalyst needs to be increased, and when the synthesized polyether modified silicone oil is used as a foam stabilizer for foaming polyurethane soft foam, the foam is opened unevenly, and the product quality is affected.
Patent CN 1974630A discloses a preparation method of allyl alcohol polyether unit alcohol with medium and high molecular weight, which takes 300-1000 molecular weight monofunctional allyl polyether unit alcohol containing double bonds as initiator and Double Metal Cyanide (DMC) as catalyst, and can synthesize allyl alcohol polyether with molecular weight of 2000-5000-plus at the temperature of 100-plus 160 ℃, the method has the advantages of synthesizing polyether with high molecular weight, and the disadvantage that the synthesized polyether affects the catalytic activity of chloroplatinic acid when reacting with hydrogen-containing silicone oil due to residual metal ions, so that the catalytic activity of the chloroplatinic acid is inactivated, the dosage of the catalyst needs to be increased, and the synthesized polyether modified silicone oil as foam stabilizer is applied to polyurethane soft foam foaming, so that the foam has uneven open pores and affects the product quality.
Patent CN 101914200A discloses a preparation method of allyl alcohol polyoxyethylene ether, which adopts sodium allyl alcohol or potassium allyl alcohol as a catalyst and comprises two steps of reaction, wherein the reaction temperature in the first step is 50-100 ℃, the reaction temperature in the second step is 100-150 ℃, and the purpose is to improve the unsaturation degree of the product. Patent CN 102134313A discloses a preparation method of methallyl alcohol polyoxyethylene ether, which adopts sodium methallyl alcohol or potassium methallyl alcohol as a catalyst, and the reaction temperature is 100-150 ℃. According to the synthesis method disclosed in patent CN 101914200A and patent CN 102134313A, after an allyl alcohol polyoxypropylene ether product is synthesized by taking sodium allyl alcohol/sodium methyl allyl alcohol or potassium allyl alcohol/potassium methyl allyl alcohol as a catalyst, acid is adopted for direct neutralization, potassium and sodium metal ions are not removed, the allyl alcohol polyoxypropylene ether product cannot be directly used for modification of silicone oil polyether, the presence of the metal ions can inactivate a chloroplatinic acid catalyst in polyether modified silicone oil reaction, and the synthesized allyl alcohol random polyether has high allyl polyether byproduct content, so that the foaming quality of the product is affected.
In summary, the polyoxypropylene ether of the prior art is prepared in two ways: one is that double metal or multi-metal cyanide such as DMC, MMC, etc. is used as catalyst, can synthesize allyl alcohol polyether with high molecular weight, but because of the residual catalyst, applied to the modification industry of silicone oil polyether, the catalyst of the reaction of hydrogen-containing silicone oil and allyl alcohol is poisoned and deactivated, the dosage of the catalyst needs to be increased, and when the synthesized polyether modified silicone oil is used as foam stabilizer applied to the foaming of polyurethane soft foam, the foam opening is not uniform, and the product quality is influenced. The other is to synthesize allyl alcohol polyether by using alkali metal catalysts such as sodium allyl alcohol, potassium allyl alcohol, KOH and the like, allyl can be isomerized into allyl, allyl alcohol polyether is partially isomerized into allyl alcohol polyether under the alkaline and high-temperature conditions, propylene oxide can also be isomerized into allyl alcohol or allyl alcohol, particularly when the allyl alcohol polyether reaches a certain molecular weight, the growth speed of an allyl alcohol polyether chain is reduced, the isomerization speed of propylene oxide into allyl alcohol is relatively increased, and the allyl alcohol can react with ethylene oxide propylene oxide to promote the molecular weight of the allyl alcohol polyether to be more than 2000. And the allyl alcohol polyether can not react with the hydrogen-containing silicone oil, and the residual allyl alcohol polyether in the polyether modified silicone oil influences the foam homogenizing effect of the polyether modified silicone oil, so that the polyurethane soft foam plastic foam has uneven open pores, influences the product quality and seriously influences the product performance.
The present application was made based on this.
Disclosure of Invention
Aiming at the defects in the synthesis of the conventional random polyether, the application provides the preparation method of the allyl alcohol polyoxypropylene ether, which is easy to implement industrially, and the obtained product has low content of side products of the allyl polyoxypropylene ether, high double bond protection rate, less residual metal ions and narrow molecular weight distribution, can synthesize the allyl alcohol polyoxypropylene ether with the molecular weight of less than 5000, can be used for modifying silicone oil polyether, and has stable quality.
In order to achieve the purpose, the technical scheme adopted by the application is as follows:
a preparation method of allyl alcohol polyoxypropylene ether takes allyl alcohol and propylene oxide as raw materials and adopts a two-step reaction: (1) initial polymerization: adding allyl alcohol and a primary polymerization catalyst into a reaction kettle, and then adopting N2Replacing air in the kettle, heating to a certain temperature, and adding propylene oxide to react to synthesize a low molecular weight allyl alcohol polyoxypropylene ether oligomer; (2) final polymerization: and (3) final polymerization adopts a reactor combining stirring and external circulation, and the product obtained in the step (1) and a final polymerization catalyst are placed in the reactor to synthesize the allyl alcohol polyoxypropylene ether with the molecular weight of 1000-5000-.
In order to achieve better use effect, the technical scheme is further set as follows:
the weight ratio of the allyl alcohol to the propylene oxide is 1: 10 to 110.
In the step (1), the initial polymerization catalyst is Lewis acid catalyst, the reaction temperature is 20-40 ℃, and the molecular weight of the allyl alcohol random polyether oligomer is 100-400. The Lewis acid has strong catalytic activity, can synthesize the allyl alcohol polyoxypropylene ether at relatively low temperature, and protects the double bond of the allyl alcohol from being damaged. And the propylene oxide is difficult to isomerize into allyl alcohol or allyl alcohol, and a good foundation is laid for preparing the high-unsaturation high-molecular-weight allyl alcohol polyoxypropylene ether.
In the step (1), the initial polymerization catalyst is boron trifluoride diethyl etherate or stannic chloride, and the using amount of the initial polymerization catalyst is 0.05-0.2% of the total amount of the oligomer in the first step. The boron trifluoride diethyl etherate and the stannic chloride catalyst do not have active hydrogen impurities to react with the propylene oxide to generate byproducts, and the generation of the byproducts can be avoided.
In the step (2), the final polymerization catalyst is any one of sodium methoxide, potassium methoxide, a mixture of sodium methoxide and potassium hydroxide, the using amount of the final polymerization catalyst is 0.1-0.8 percent of the total amount of the product, after the catalyst is added, the final polymerization catalyst is vacuumized until the vacuum degree is more than or equal to 0.098MPa, the temperature is raised to 80-100 ℃, and methanol produced by the reaction of allyl alcohol oligomer and the catalyst is removed; then cooling to 50-80 ℃, continuously adding propylene oxide to react and polymerize into high molecular weight allyl alcohol polyoxypropylene ether. The methanol formed by the reaction of the adopted sodium methoxide and potassium methoxide catalyst and allyl alcohol polyoxypropylene ether can be thoroughly removed under the vacuum of-0.098 MPa and at the temperature of 80-100 ℃, and the generation of other polyether byproducts without allyl groups is avoided. The allyl alcohol polyoxypropylene ether oligomer and the propylene oxide are reacted at the low temperature of 50-80 ℃, so that the isomerization of allyl to propenyl can be greatly reduced, the isomerization of the propylene oxide to the allyl alcohol or the allyl alcohol can be avoided, the reaction is more favorable for the chain growth reaction, the allyl alcohol polyether with high molecular weight and narrow distribution is formed, the generation of a propenyl polyoxypropylene ether byproduct is reduced, and the allyl alcohol polyoxypropylene ether with narrow distribution and high molecular weight can be synthesized.
Also comprises the following post-treatment procedures: adding deionized water, phosphoric acid, glacial acetic acid and the like into the product obtained in the step (2) for neutralization, adding polyether adsorbents such as magnesium silicate, kieselguhr and the like for adsorption, heating to 100-120 ℃ under the condition of vacuumizing for removing water, then cooling to 40-80 ℃ for filtering to remove formed crystal salts such as potassium dihydrogen phosphate, sodium dihydrogen phosphate and the like, so that the product metal ion K+、Na+The content is less than or equal to 2 ppm. .
The stirring and external circulation reactor structure comprises a kettle body, a stirrer and an external circulation pipeline arranged on the kettle body, wherein the stirrer extends into the kettle body and is driven by a motor; each pipeline bypasses from the bottom of the kettle body to the top of the kettle body, a delivery pump is arranged on the pipeline close to the bottom, and a condenser is arranged on the pipeline close to the top; the structure of each pipeline is the same, 1-5 pipelines are arranged along the periphery of the kettle body, more preferably, a ball valve is arranged on the pipeline between the condenser and the top of the kettle body, and a ball valve is arranged on the pipeline between the delivery pump and the bottom of the kettle body; the pipeline is provided with 2-4 paths along the periphery of the kettle body; the delivery pump is a canned motor pump or a magnetic pump. The stirring and external circulation reactor can greatly increase the mass transfer of reaction materials and increase the contact probability of propylene oxide and polyether hydroxyl, thereby accelerating the chain growth speed, greatly reducing the probability of isomerizing propylene oxide into allyl alcohol or allyl alcohol, ensuring that the molecular weight distribution of the synthesized product is narrower (the molecular weight distribution is less than or equal to 1.10) and the byproducts are less (the byproducts such as allyl alcohol polyether and the like are less than or equal to 1.0%).
Meanwhile, the application also provides the allyl alcohol random polyether prepared by the method, the molecular weight (molecular weight index average molecular weight, the same below) of the allyl alcohol random polyether is 1000-5000-.
The double bond protection rate calculation formula is as follows: molecular weight (hydroxyl value calculated) × 100%/molecular weight (iodine value calculated) = (56110 × iodine value) × 100%/(hydroxyl value × 25400) (the same applies hereinafter).
The reaction formula of the invention is as follows:
wherein n + m is 9-110.
The method for synthesizing the high molecular weight allyl alcohol polyoxypropylene ether adopts a two-step method, firstly adopts a Lewis acid catalyst without active hydrogen to synthesize the allyl alcohol polyoxypropylene ether oligomer at a lower temperature of 20-40 ℃, the Lewis acid has strong catalytic activity, can synthesize the allyl alcohol polyoxypropylene ether at a relatively lower temperature, protects double bonds of allyl alcohol from being damaged, ensures that propylene oxide is not easily isomerized into allyl alcohol or allyl alcohol, and lays a good foundation for preparing the high molecular weight allyl alcohol polyoxypropylene ether with high unsaturation degree. And secondly, stirring and adding an external circulation reactor, taking sodium methoxide or potassium methoxide as a catalyst, removing methanol produced by reaction at 80-100 ℃, reacting at 50-80 ℃ to synthesize high molecular weight allyl alcohol polyoxypropylene ether, adding deionized water, phosphoric acid or glacial acetic acid, magnesium silicate and diatomite polyether adsorbent, removing water, and filtering to remove potassium dihydrogen phosphate or sodium dihydrogen phosphate and other salts to obtain the narrow-distribution high molecular weight allyl alcohol polyoxypropylene ether with the metal ion content of less than 2 ppm. The high molecular weight polyether is synthesized by adopting stirring and an external circulation reactor, the mass transfer effect of reactants in a kettle can be greatly increased, and the contact probability of propylene oxide and polyether hydroxyl is increased, so that the chain growth speed is accelerated, the probability of propylene oxide isomerization to allyl alcohol or allyl alcohol is greatly reduced, the mass transfer efficiency of the materials in the kettle can be ensured by reaction at a lower temperature of 50-80 ℃, the molecular weight distribution of the synthesized product is narrower (the molecular weight distribution is less than or equal to 1.10), fewer byproducts (byproducts such as allyl alcohol polyether and the like are less than or equal to 1.0%), and the quality of the product is ensured. The high molecular weight polyether synthesized by the method can directly react with hydrogen-containing silicone oil to form polyether modified silicone oil, and is used in allyl alcohol polyether modified organic silicon such as agricultural spreading agents, defoaming agents and the like.
Compared with the prior art, the method has the following outstanding advantages and positive effects:
1) the allyl alcohol polyoxypropylene ether, the propenyl polyoxypropylene ether and other byproducts synthesized by the technical scheme of the invention have low content, the content of the propenyl polyoxypropylene ether and other byproducts is below 1.0 percent, and the double bond protection rate is more than or equal to 96 percent. The invention adopts allyl alcohol as an initiator, and adopts two-step synthesis to prepare the hair, firstly adopts an acid catalyst to synthesize allyl alcohol polyoxypropylene ether oligomer, then adopts potassium methoxide or sodium methoxide as a catalyst, adopts a stirring and circulating reactor to synthesize an allyl alcohol polyoxypropylene ether crude product, adopts phosphoric acid and the like to neutralize, remove water and filter the obtained allyl alcohol polyoxypropylene ether with low metal ion content, narrow distribution and high molecular weight, and solves the problem that the prior art can not meet the high requirement of directly reacting with hydrogen-containing silicone oil to prepare polyether modified silicone oil which is used in agricultural spreading agents, defoaming agents and other allyl alcohol polyether modified silicone oils.
2) The molecular weight of the allyl alcohol polyoxypropylene ether synthesized by the technical scheme of the invention can be 1000-5000, and the content of metal ions is less than or equal to 2 ppm.
3) The process for preparing the allyl alcohol polyoxypropylene ether is simple, the reaction temperature is low, and the energy consumption in the whole preparation process is low.
Drawings
FIG. 1 is a schematic diagram of the reactor structure in the present application.
Wherein the reference numbers: A. a first pipeline; B. a second pipeline; 1. a kettle body; 2. a stirrer; 3. a motor; 4. a first ball valve; 5. a first condenser; 6. a first delivery pump; 7. a ball valve II; 8. a ball valve III; 9. a ball valve IV; 10. a second condenser; 11. a second delivery pump; 12. and a ball valve five.
Detailed Description
The reactor used in this embodiment, as shown in fig. 1, includes a kettle 1, a stirrer 2, and a first external circulation pipeline a and a second external circulation pipeline B (2 external circulation pipelines are shown in fig. 1) disposed on the kettle 1, wherein the lower end of the stirrer 2 extends into the kettle 1 and is driven by a motor 3; each pipeline bypasses from the bottom of the kettle body 1 to the top of the kettle body 1, a delivery pump is arranged on the pipeline close to the bottom, and a condenser is arranged on the pipeline close to the top; the pipeline A is provided with a ball valve I4, a condenser I5, a delivery pump I6 and a ball valve II 7; the pipeline B is provided with a ball valve IV 9, a condenser II 10, a delivery pump II 11 and a ball valve V12, the delivery pump I6 and the delivery pump II 11 can be selected from a shielding pump or a magnetic pump, the pipeline can also extend out of the bottom of the kettle body 1 according to production requirements, and the pipeline is provided with a ball valve IV 8 to form a new pipeline.
The stirring and external circulation reactor can greatly increase the mass transfer of reaction materials and increase the contact probability of propylene oxide, ethylene oxide and polyether hydroxyl, thereby accelerating the chain growth speed, greatly reducing the probability of isomerizing propylene oxide into allyl alcohol or allyl alcohol, leading the molecular weight distribution of the synthesized product to be narrower (the molecular weight distribution is less than or equal to 1.08) and leading the byproducts to be less (the byproducts such as allyl alcohol polyether and the like are less than or equal to 0.5%).
Preparation of the reaction kettle before implementation: washing a 2.5L high-pressure stirring reaction kettle, a 2.5L high-pressure stirring reaction kettle and a 2-path external circulation reaction kettle for several times by using distilled water until the reaction kettle is clean, drying the reaction kettle, and cooling to the normal temperature for later use.
Example 1: preparation of allyl alcohol polyoxypropylene ether oligomer
400g of allyl alcohol and 0.6g of boron trifluoride diethyl etherate are added into a 2.5L high-pressure stirring reaction kettle, vacuum pumping is carried out by a vacuum pump, and N is adopted2And (3) displacing air in the reaction kettle, after three times of displacement, closing the vacuum and starting to heat to 30 ℃ of the material under the condition that the vacuum degree is more than or equal to-0.096 MPa, and continuously adding 980g of propylene oxide. Controlling the reaction temperature at 20-40 ℃, controlling the pressure in the reaction kettle at-0.05-0.2 Mpa, keeping the temperature after the addition, and continuing the reaction until the pressure is not reduced any more, wherein the whole reaction addition time is about 6 hours. After the reaction is finished, vacuum degassing is carried out, the vacuum is more than or equal to-0.098 MPa, the reaction is kept for 10min, and then the materials are dischargedAnd obtaining a finished product for later use. The product is analyzed by a nuclear magnetic resonance analyzer: the content of propylene alcohol polyoxypropylene ether by-product is 0.02%, the hydroxyl value measured by chemical method is 280.1(mgKOH/g), the molecular weight is 200, and the iodine value is 126.2 (gI)2100g), the double bond protection rate is 99.5 percent (the calculation formula of the double bond protection rate is as follows: double bond protection rate (56110 iodine value) × 100%/(hydroxyl value 25400), the same applies below).
Comparative example 1
Adding 400g of allyl alcohol and 4g of sodium allyl alcohol into a 2.5L high-pressure stirring reaction kettle, vacuumizing by using a vacuum pump, and adopting N2And (3) displacing air in the reaction kettle, after three times of displacement, closing the vacuum and starting heating to 60 ℃ after the vacuum degree is more than or equal to-0.096 MPa, and continuously adding 980g of propylene oxide. Controlling the reaction temperature at 60-80 ℃, controlling the pressure in the reaction kettle at-0.05-0.4 Mpa, keeping the temperature after the addition, and continuing the reaction until the pressure is not reduced any more, wherein the whole reaction addition time is about 9 hours. After the reaction is finished, vacuum degassing is carried out, the vacuum is more than or equal to-0.098 MPa, the reaction is kept for 10min, and then discharging is carried out to obtain a finished product for later use. The product is analyzed by a nuclear magnetic resonance analyzer: the content of propylene alcohol polyoxypropylene ether by-product is 0.05%, and the chemically determined hydroxyl value is 286.2mgKOH/g, molecular weight is 196, iodine value is 128.1 (gI)2100g), the double bond protection rate is 99.1 percent.
TABLE 1 comparison of the indices of the oligomers under different synthesis conditions
| Example 1 | Comparative example 1 | |
| Propenyl polyether by-product,% | 0.02 | 0.05 |
| Double bond protection rate,% | 99.5 | 99.1 |
| Hydroxyl group, gKOH/g | 280.1 | 286.2 |
| Iodine value, gI2/100g | 126.2 | 128.1 |
| Molecular weight | 200 | 196 |
As can be seen from the comparative data in table 1: the allyl polyoxypropylene ether byproduct of the allyl alcohol polyoxypropylene ether oligomer synthesized by the method is 2/5 of the method in the comparative example 1, and the double bond protection rate is 0.4% higher than that of the comparative example 1, which shows that the method can greatly reduce the allyl polyoxypropylene ether byproduct and improve the double bond protection rate compared with the comparative example method.
Example 2: experimental comparison with a theoretical molecular weight of 1500 charge
150g of allyl alcohol polyoxypropylene ether oligomer and 3.0g of sodium methoxide were added to a 2.5L stirred 2-way external circulation reactor using N2And (3) displacing air in the reaction kettle, vacuumizing and starting to heat to 90 ℃ to remove methanol generated by the reaction under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and keeping the reaction for 1 hour. After the dealcoholization was completed, the temperature was reduced to 65 ℃ and 975g of propylene oxide was continuously added. Controlling the reaction temperature at 60-70 ℃, controlling the pressure in the reaction kettle at-0.02-0.4 Mpa, keeping the temperature after the addition, and continuing the reaction until the pressure is not reduced any more, wherein the whole reaction addition time is about 12 hours. After the reaction is finished, vacuum degassing is adopted, the vacuum is maintained for 10min at the pressure of more than or equal to-0.098 MPa, 100g of deionized water, 6.3g of phosphoric acid and 10g of magnesium silicate are added,and 3g of diatomite is stirred for 20 minutes, heated to the temperature of 100-115 ℃, vacuumized to remove water, cooled to the temperature of 60 ℃ and filtered to obtain the finished product of the allyl alcohol polyoxypropylene ether. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propylene alcohol polyoxypropylene ether by-products is 0.03 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.05; the color of the sample is visually observed to be No. 15 (Pt-Co unit), the hydroxyl value is determined by a chemical method to be 37.78mgKOH/g, the molecular weight is 1485, and the iodine value is 15.73 (gI)2100g), the double bond protection rate is 99.2 percent; measuring Na by adopting ion detector ICP mass+The content was 0.5 ppm.
Comparative example 2
200g of starter (allyl alcohol polyether oligomer with molecular weight of 400) and 0.054g of double metal cyanide DMC catalyst are mixed and added into a 2.5L high-pressure stirring reaction kettle, the kettle is vacuumized to-0.095 Mpa, degassed by bubbling for 30 minutes, and then N is added2To 0.1MPa, vacuumizing to-0.095 MPa, heating to 100 deg.C, obviously reducing the pressure of the reactor after 25 min (which can be regarded as the induction period of the catalyst), and continuously adding 550g of propylene oxide while maintaining the temperature of the reactor at 105-110 deg.C. The pressure of the reactor is not more than 0.2Mpa, and after the epoxide is added, the pressure of the reactor is not reacted any more, the unreacted residual monomer is removed by vacuum pumping, and the allyl alcohol polyoxypropylene ether is obtained by cooling. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propylene alcohol polyoxypropylene ether by-products is 0.10 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.08; the color of the sample was visually observed to be No. 25 (Pt-Co unit), and the chemically determined hydroxyl value was 37.9mgKOH/g, the molecular weight was 1480, and the iodine value was 15.56 (gI)2100g), double bond protection 96.5%; the total content of Co and Zn elements was measured to be 18ppm by an ion detector ICP mass.
Comparative example 3
Adding 300g of allyl alcohol and 6g of sodium allyl alcohol into a 2.5L high-pressure stirring reaction kettle, vacuumizing by using a vacuum pump, and adopting N2And (3) displacing air in the reaction kettle, after three times of displacement, closing the vacuum and starting heating to 80 ℃ of the material under the condition that the vacuum degree is more than or equal to-0.096 MPa, and continuously adding 980g of propylene oxide. Controlling the reaction temperature to be 75-85 ℃, and controlling the pressure in the reaction kettle to be-0.05-0.4 Mpand a, after the addition is finished, keeping the temperature to continue the reaction until the pressure does not drop any more, wherein the whole reaction addition time is about 10 hours. After the reaction is finished, vacuum degassing is carried out, the vacuum is more than or equal to-0.098 MPa, the reaction is kept for 10min, and then discharging is carried out to obtain a finished product for later use. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propylene alcohol polyoxypropylene ether by-product is 0.06 percent, the hydroxyl value is 233.8mgKOH/g by chemical method determination, and the molecular weight is 240.
150g of the allyl alcohol polyoxypropylene ether oligomer obtained above was charged in a 2.5L high-pressure stirred tank reactor, 5g of sodium allyl alcohol was added, and N was used2Displacing air in the reaction kettle, heating to 115 ℃ under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and continuously adding 787g of propylene oxide. Controlling the reaction temperature at 113-. After the reaction is finished, vacuum degassing is adopted, the vacuum is maintained for 10min at the pressure of more than or equal to-0.098 MPa, 4g of glacial acetic acid is added for neutralization and stirring for 10min, and then the finished product of the allyl alcohol polyoxypropylene ether is obtained by discharging the materials. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propylene alcohol polyoxypropylene ether by-products is 2.5 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.11; the color of the sample was visually observed as No. 35 (Pt-Co units), and the chemically determined hydroxyl value was 39.23mgKOH/g, molecular weight was 1430, and iodine value was 16.5 (gI)2100g), the double bond protection rate is 93.0 percent; the Na + content was 1300ppm by ICP mass using an ion detector.
TABLE 2 comparison table of polyether indexes of theoretical molecular weight 1500 under different preparation conditions
| Example 2 | Comparative example 2 | Comparative example 3 | |
| Propenyl polyether by-product,% | 0.03 | 0.10 | 2.5 |
| Double bond protection rate,% | 99.2 | 96.5 | 93.0 |
| Molecular weight | 1485 | 1480 | 1430 |
| Iodine value, gI2/100g | 12.6 | 12.6 | 16.5 |
| Metal ion content, ppm | 0.5 | 18 | 1300 |
| Coefficient of molecular weight distribution | 1.05 | 1.05 | 1.11 |
As seen from the comparative data in table 2: the method is characterized in that the theoretical 1500 molecular weight is adopted, the molecular weight of the allyl alcohol polyoxypropylene ether synthesized by the method is 5% higher than that of comparative example 2, the molecular weight of the allyl alcohol polyoxypropylene ether synthesized by the method is 55% higher than that of comparative example 3, the content of the propenyl polyoxypropylene ether byproduct is only 30% of that of comparative example 2, the content of the propenyl polyoxypropylene ether byproduct is 1.2% of that of comparative example 3, the double bond protection rate is 2.8% higher than that of comparative example 2, and the double bond protection rate is 6.2% higher than that of comparative example 3, so that the method can greatly reduce the propenyl polyoxypropylene ether byproduct and improve the double.
Example 3: experiment comparison is carried out by feeding with 2500 theoretical molecular weight
100g of the allyl alcohol polyether oligomer obtained in example 1 and 2.5g of potassium methoxide were charged into a 2.5L stirred 2-way external circulation reactor, and N was used2And (3) displacing air in the reaction kettle, vacuumizing and starting to heat to 90 ℃ to remove methanol generated by the reaction under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and keeping the reaction for 1 hour. After the dealcoholization was completed, the temperature was reduced to 65 ℃ and 1150g of propylene oxide was continuously added. Controlling the reaction temperature at 65-75 ℃, controlling the pressure in the reaction kettle at-0.02-0.4 Mpa, keeping the temperature after the addition, and continuing the reaction until the pressure is not reduced any more, wherein the whole reaction addition time is about 15 hours. After the reaction is finished, vacuum degassing is adopted, the vacuum pressure is more than or equal to-0.098 MPa, the reaction is kept for 10min, then 140g of deionized water, 5.0g of phosphoric acid, 10g of magnesium silicate and 3g of diatomite are added, the temperature is raised to 100-115 ℃ after stirring for 20 min, the reaction solution is vacuumized to remove water, and then the reaction solution is cooled to 60 ℃ to obtain the finished product of the allyl alcohol polyoxypropylene ether. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 0.06 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.06; the color of the sample is visually observed to be No. 15 (Pt-Co unit), the hydroxyl value is determined by a chemical method to be 22.9mgKOH/g, the molecular weight is 2450, and the iodine value is 10.2 (gI)2100g), the double bond protection rate is 98.5 percent; measuring K by adopting ion detector ICP mass+The content was 0.3 ppm.
Comparative example 4
180g of starter (allyl alcohol polyoxypropylene ether oligomer with a molecular weight of 400) and 0.054g of double metal cyanide DMC catalyst are mixed and added into a 2.5L high-pressure stirring reaction kettle, the kettle is vacuumized to-0.095 Mpa, bubbling and degassing are carried out for 30 minutes, and then N is added2To 0.1MPa, vacuumizing to-0.095 MPa, heating to 100 deg.C for 25 min (the induction period can be regarded as catalyst), and keeping the pressure of reactor at high levelSignificantly lower, 945g of propylene oxide was continuously added while maintaining the reactor temperature at 105 ℃ and 110 ℃. The pressure of the reactor is not more than 0.2Mpa, and after the epoxide is added, the pressure of the reactor is not reacted any more, the unreacted residual monomer is removed by vacuum pumping, and the allyl alcohol polyoxypropylene ether is obtained by cooling. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 0.15 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.11; the color of the sample was visually observed to be No. 25 (Pt-Co unit), and the chemically determined hydroxyl value was 23.28mgKOH/g, the molecular weight was 2410, and the iodine value was 9.96 (gI)2100g), the double bond protection rate is 94.5 percent; the total content of Co and Zn elements was measured to be 20ppm by an ion detector ICP mass.
Comparative example 5
114g of the allyl alcohol polyoxypropylene ether oligomer synthesized in comparative example 2 of example 2, 6g of sodium allyl alcohol, and N in a 2.5L high-pressure stirred autoclave were charged2Displacing air in the reaction kettle, heating to 115 ℃ under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and continuously adding 1073g of propylene oxide. Controlling the reaction temperature at 113-. After the reaction is finished, vacuum degassing is adopted, the vacuum is maintained for 10min at the pressure of more than or equal to-0.098 MPa, 4.6g of glacial acetic acid is added for neutralization and stirring for 10min, and then the materials are discharged to obtain the finished product of the allyl alcohol polyoxypropylene ether. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 8.6 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.21; the sample was visually observed to have a color of No. 45 (Pt-Co units), a chemically determined hydroxyl value of 34.7mgKOH/g, a molecular weight of 1615, and an iodine value of 13.9 (gI)2100g), the double bond protection rate is 88.9 percent; measuring Na by adopting ion detector ICP mass+The content was 1300 ppm.
TABLE 3 comparison table of theoretical molecular weight 2500 polyether synthesis indexes under different conditions
| Example 3 | Comparative example 4 | Comparative example 5 | |
| Propenyl polyether by-product,% | 0.06 | 0.15 | 8.6 |
| Double bond protection rate,% | 98.9 | 94.5 | 88.9 |
| Molecular weight | 2450 | 2410 | 1610 |
| Iodine value, gI2/100g | 10.2 | 9.96 | 13.9 |
| Metal ion content, ppm | 0.5 | 20 | 1300 |
| Coefficient of molecular weight distribution | 1.06 | 1.11 | 1.21 |
From the comparative data of table 3, it is seen that: the method is characterized in that the theoretical 2500 molecular weight is adopted for feeding, the molecular weight of the allyl alcohol polyoxypropylene ether synthesized by the method is 40% higher than that of comparative example 4, the molecular weight of the allyl alcohol polyoxypropylene ether synthesized by the method is 840% higher than that of comparative example 5, the content of the propenyl polyoxypropylene ether byproduct is only 40% of that of comparative example 4, 0.7% of that of comparative example 5, the double bond protection rate is 4.4% higher than that of comparative example 4, and the molecular weight of the allyl alcohol polyoxypropylene ether synthesized by the method is 10.0% higher than that of comparative example 5. In the method of the comparative example 5, because a general reactor stirring kettle (such as patent CN 101914200A, CN 102134313A) is adopted, the viscosity is high when high molecular weight polyether is synthesized, the mass transfer of materials in the kettle is not good, the reaction temperature is high, allyl is easy to isomerize into allyl, propylene oxide is easy to isomerize into allyl alcohol or allyl alcohol, the by-product content of the synthesized product propenyl polyoxypropylene ether is high, and the molecular weight cannot be increased.
Example 4: experimental comparison with a theoretical molecular weight of 3500
75g of the allyl alcohol polyoxypropylene ether oligomer obtained in example 1 and 4g of sodium methoxide were put into a 2-path external circulation reaction vessel with stirring at 2.5L, and N was used as the solvent2And (3) displacing air in the reaction kettle, vacuumizing and starting to heat to 90 ℃ to remove methanol generated by the reaction under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and keeping the reaction for 1 hour. After the dealcoholization was completed, the temperature was reduced to 70 ℃ and 1237g of propylene oxide was continuously added. Controlling the reaction temperature at 70-80 ℃, controlling the pressure in the reaction kettle at-0.02-0.4 Mpa, keeping the temperature after the addition, and continuing the reaction until the pressure is not reduced any more, wherein the whole reaction addition time is about 10 hours. After the reaction is finished, vacuum degassing is adopted, the vacuum pressure is more than or equal to-0.098 MPa, the reaction is kept for 10min, then 140g of deionized water, 8.0g of phosphoric acid, 10g of magnesium silicate and 3g of diatomite are added, the temperature is raised to 100-115 ℃ after stirring for 20 min, the reaction solution is vacuumized to remove water, and then the reaction solution is cooled to 60 ℃ to obtain the finished product of the allyl alcohol polyoxypropylene ether. Product(s)And (3) analyzing by a nuclear magnetic resonance analyzer: the content of propenyl polyoxypropylene ether by-products is 0.07 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.07; the color of the sample was visually observed to be No. 10 (Pt-Co unit), and the hydroxyl value determined by a chemical method was 16.3mgKOH/g, the molecular weight was 3440, and the iodine value was 7.3gI2100g), the double bond protection rate is 98.7 percent; measuring Na by adopting ion detector ICP mass+The content was 0.4 ppm.
Comparative example 6
145g of starter (allyl alcohol polyoxypropylene ether oligomer having a molecular weight of 400) and 0.095g of double metal cyanide DMC catalyst were mixed and charged into a 2.5L high-pressure stirred tank reactor, evacuated to-0.095 MPa, degassed by bubbling for 30 minutes, and then charged with N2To 0.1MPa, further vacuumizing to-0.095 MPa, heating to 110 deg.C, obviously reducing the reactor pressure after 25 minutes (which can be regarded as the induction period of the catalyst), and continuously adding 1123g of propylene oxide while maintaining the reactor temperature at 115-120 deg.C. The pressure of the reactor is not more than 0.2Mpa, and after the epoxide is added, the pressure of the reactor is not reacted any more, the unreacted residual monomer is removed by vacuum pumping, and the allyl alcohol polyoxypropylene ether is obtained by cooling. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 0.3 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.13; the color of the sample was visually observed to be No. 25 (Pt-Co unit), and the chemically determined hydroxyl value was 16.5mgKOH/g, the molecular weight was 3390, and the iodine value was 7.0 (gI)2100g), the double bond protection rate is 93.2 percent; the total content of Co and Zn elements was measured to be 20ppm by an ion detector ICP mass.
Comparative example 7
86g of the allyl alcohol polyoxypropylene ether oligomer synthesized in comparative example 2 of example 2, 6g of potassium allyl alcohol, and N in the form of N were charged into a 2.5L high-pressure stirred autoclave2Displacing air in the reaction kettle, heating to 115 ℃ under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and continuously adding 1168g of propylene oxide. Controlling the reaction temperature at 113-. After the reaction is finished, vacuum dehydration is adoptedKeeping the vacuum of more than or equal to-0.098 MPa for 10min, adding 4.4g of glacial acetic acid, neutralizing, stirring for 10min, and discharging to obtain the finished product of the allyl alcohol polyoxypropylene ether. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 18 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.25; the sample was visually observed to have a color of No. 45 (Pt-Co units), a chemically determined hydroxyl value of 35.0mgKOH/g, a molecular weight of 1601, and an iodine value of 13.5 (gI)2100g), the double bond protection rate is 85.4 percent; measuring Na by adopting ion detector ICP mass+The content was 61ppm, K+1267 ppm.
TABLE 4 comparison table of index of 3500 theoretical molecular weight polyether under different preparation conditions
| Example 4 | Comparative example 6 | Comparative example 7 | |
| Propenyl polyether by-product,% | 0.07 | 0.3 | 18 |
| Double bond protection rate,% | 98.7 | 93.2 | 85.4 |
| Molecular weight | 3440 | 3390 | 1601 |
| Iodine value, gI2/100g | 7.3 | 7.0 | 13.5 |
| Metal ion content, ppm | 0.4 | 20 | 61+1267 |
| Coefficient of molecular weight distribution | 1.07 | 1.13 | 1.25 |
As seen from the comparative data in table 4: the method is characterized in that the theoretical molecular weight of 3500 is adopted for feeding, the molecular weight of the allyl alcohol polyoxypropylene ether synthesized by the method is 50 higher than that of comparative example 6 and 1839 higher than that of comparative example 7, the content of the propenyl polyoxypropylene ether byproduct is only 23.3 percent of that of comparative example 6, 0.39 percent of that of comparative example 7, the double bond protection rate is 5.5 percent higher than that of comparative example 6, and is 13.3 percent higher than that of comparative example 7, and the method can greatly reduce the propenyl polyoxypropylene ether byproduct and improve the double bond protection rate compared with the methods of comparative examples 6 and 7, and the synthesized molecular weight is closer to the theoretical value. In the method of comparative example 7, the adopted general reactor stirred tank (such as patent CN 1974630A and patent CN 101914200A, CN 102134313A) has high viscosity when synthesizing high molecular weight polyether, poor mass transfer of materials in the tank, high reaction temperature, easy allyl isomerization to propenyl, and easy isomerization of propylene oxide to allyl alcohol or allyl alcohol, so that the synthesized product propenyl polyoxypropylene ether has high by-product content and molecular weight which cannot be increased.
Example 5: selection of contrast for reactor
100g of the allyl alcohol polyether oligomer obtained in example 1 and 2.5g of potassium methoxide were charged into a 2.5L stirred 2-way external circulation reactor, and N was used2And (3) displacing air in the reaction kettle, vacuumizing and starting to heat to 90 ℃ to remove methanol generated by the reaction under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and keeping the reaction for 1 hour. After the dealcoholization was completed, the temperature was reduced to 65 ℃ and 1150g of propylene oxide was continuously added. Controlling the reaction temperature at 65-75 ℃, controlling the pressure in the reaction kettle at-0.02-0.4 Mpa, keeping the temperature after the addition, and continuing the reaction until the pressure is not reduced any more, wherein the whole reaction addition time is about 15 hours. After the reaction is finished, vacuum degassing is adopted, the vacuum pressure is more than or equal to-0.098 MPa, the reaction is kept for 10min, then 140g of deionized water, 5.0g of phosphoric acid, 10g of magnesium silicate and 3g of diatomite are added, the temperature is raised to 100-115 ℃ after stirring for 20 min, the reaction solution is vacuumized to remove water, and then the reaction solution is cooled to 60 ℃ to obtain the finished product of the allyl alcohol polyoxypropylene ether. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 0.06 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.06; the color of the sample is visually observed to be No. 15 (Pt-Co unit), the hydroxyl value is determined by a chemical method to be 22.9mgKOH/g, the molecular weight is 2450, and the iodine value is 10.2 (gI)2100g), the double bond protection rate is 98.5 percent; measuring K by adopting ion detector ICP mass+The content was 0.3 ppm.
Comparative example 8
Using a 2.5L stirred reactor, 100g of the allyl alcohol polyoxypropylene ether oligomer obtained in example 1, 2.5g of potassium methoxide were charged in the reactor, and N was used2And (3) displacing air in the reaction kettle, vacuumizing and starting to heat to 90 ℃ to remove methanol generated by the reaction under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and keeping the reaction for 1 hour. After the dealcoholization was completed, the temperature was reduced to 65 ℃ and 1150g of propylene oxide was continuously added. Controlling the reaction temperature at 65-75 ℃, controlling the pressure in the reaction kettle at-0.02-0.4 Mpa, keeping the temperature after the addition, and continuing the reaction until the pressure is not reduced any more, wherein the whole reaction addition time is about 18 h. After the reaction is finished, vacuum degassing is adopted, the vacuum pressure is more than or equal to-0.098 MPa and is kept for 10min, then 140g of deionized water, 5.0g of phosphoric acid, 10g of magnesium silicate and 3g of diatomite are added, after stirring for 20 min, the temperature is raised to 115 ℃, after vacuumizing and moisture removal, the mixture is cooled to 60 DEG CAnd filtering to obtain the finished product of the allyl alcohol polyoxypropylene ether. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 0.31 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.21; the sample was visually observed to have a color of No. 15 (Pt-Co units), a chemically determined hydroxyl number of 28.86mgKOH/g, a molecular weight of 1944, and an iodine number of 12.3 (gI)2100g), the double bond protection rate is 94.3 percent; measuring K by adopting ion detector ICP mass+The content was 0.3 ppm.
TABLE 5 comparison of theoretical molecular weight 4000 polyether indexes for different reactors
| Example 5 | Comparative example 8 | |
| Propenyl polyether by-product,% | 0.06 | 0.31 |
| Double bond protection rate,% | 98.5 | 94.5 |
| Molecular weight | 2450 | 1944 |
| Iodine value, gI2/100g | 10.2 | 12.3 |
| Metal ion content, ppm | 0.5 | 0.3 |
| Coefficient of molecular weight distribution | 1.06 | 1.21 |
As seen from the comparative data in table 5: the molecular weight of allyl alcohol polyoxypropylene ether synthesized by stirring and external circulation of the reactor adopting the method is 506 higher than that of the stirring reactor adopted in the comparative example 8, the content of the propenyl polyoxypropylene ether byproduct is only 19.3 percent of that of the comparative example 8, and the double bond protection rate is 4.0 percent higher than that of the comparative example 8, which shows that the content of the propenyl polyoxypropylene ether byproduct synthesized by the stirring and external circulation reactor of the method can be greatly reduced, the double bond protection rate is high, and the synthesized molecular weight is closer to the theoretical value than that of the propenyl polyoxypropylene ether byproduct synthesized by a conventional stirring reactor (such as patent CN 1974630A and patent CN 101914200A, CN 102134313A).
Example 6: influence of catalyst selection and reaction temperature on the finished product
100g of the allyl alcohol polyether oligomer obtained in example 1 and 2.5g of potassium methoxide were charged into a 2.5L stirred 2-way external circulation reactor, and N was used2And (3) displacing air in the reaction kettle, vacuumizing and starting to heat to 90 ℃ to remove methanol generated by the reaction under the condition that the vacuum degree is more than or equal to-0.096 MPa after three times of displacement, and keeping the reaction for 1 hour. After the dealcoholization was completed, the temperature was reduced to 65 ℃ and 1150g of propylene oxide was continuously added. Controlling the reaction temperature at 65-75 ℃, controlling the pressure in the reaction kettle at-0.02-0.4 Mpa, keeping the temperature after the addition, and continuing the reaction until the pressure is not reduced any more, wherein the whole reaction addition time is about 15 hours. After the reaction is finished, vacuum degassing is adopted, the vacuum pressure is more than or equal to-0.098 MPa, the reaction is kept for 10min, then 140g of deionized water, 5.0g of phosphoric acid, 10g of magnesium silicate and 3g of diatomite are added, the temperature is raised to 100-115 ℃ after stirring for 20 min, the reaction solution is vacuumized to remove water, and then the reaction solution is cooled to 60 ℃ to obtain the finished product of the allyl alcohol polyoxypropylene ether. The product is analyzed by a nuclear magnetic resonance analyzerAnd (3) analysis: the content of the propenyl polyoxypropylene ether by-product is 0.06 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.06; the color of the sample is visually observed to be No. 15 (Pt-Co unit), the hydroxyl value is determined by a chemical method to be 22.9mgKOH/g, the molecular weight is 2450, and the iodine value is 10.2 (gI)2100g), the double bond protection rate is 98.5 percent; measuring K by adopting ion detector ICP mass+The content was 0.3 ppm.
Comparative example 9
The procedure is as in example 6, except that the starting material is replaced with the allyl alcohol polyoxypropylene ether oligomer 100 obtained in comparative example 1 of example 1 (catalyzed by sodium allyl alcohol), and the other conditions are not changed. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 0.10 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.06; the color of the sample was visually observed to be No. 15 (Pt-Co units), and the chemically determined hydroxyl value was 24.8mgKOH/g, the molecular weight was 2264, and the iodine value was 10.84 (gI)2100g), the double bond protection rate is 96.6 percent; measuring K by adopting ion detector ICP mass+The content was 0.6 ppm.
Comparative example 10
The same procedure as in example 6 was repeated except that the starting materials such as the amounts of the initiator and propylene oxide were not changed, the methanol removal temperature was adjusted to 105 ℃ and the reaction temperature was adjusted to 110-115 ℃. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 1.0 percent; the molecular weight distribution coefficient of the allyl alcohol polyoxypropylene ether analyzed by liquid chromatography is as follows: 1.13; the color of the sample was visually observed to be No. 25 (Pt-Co unit), and the chemically determined hydroxyl value was 27.4mgKOH/g, the molecular weight was 2046, and the iodine value was 11.8 (gI)2100g), the double bond protection rate is 94.9 percent; measuring K by adopting ion detector ICP mass+The content was 0.5 ppm.
Comparative example 11
The same procedure as in example 6 was repeated except that the starting material was changed to the allyl alcohol polyoxypropylene ether oligomer 100 obtained in comparative example 1 in example 1 (using sodium allyl alcohol as a catalyst), the methanol elimination temperature was adjusted to 105 ℃ and the reaction temperature was adjusted to 110-115 ℃. The product is analyzed by a nuclear magnetic resonance analyzer: the content of the propenyl polyoxypropylene ether by-product is 1.6 percent; liquid chromatography analysis of allyl alcohol polyoxypropylene ether moleculesThe quantity distribution coefficient is: 1.15; the color of the sample was visually observed to be No. 30 (Pt-Co units), and the chemically determined hydroxyl value was 28.7mgKOH/g, molecular weight 1953, and iodine value was 12.2 (gI)2100g), the double bond protection rate is 93.8 percent; measuring K by adopting ion detector ICP mass+The content was 0.5 ppm.
TABLE 6 comparison of theoretical molecular weight 4000 polyether indexes under different catalysts
As seen from the comparative data in table 6: the theoretical 2500 molecular weight is used for feeding, the product comparative example 9 synthesized by the allyl alcohol polyoxypropylene ether oligomer catalyst is changed, the molecular weight is lower than that of the product comparative example 9 synthesized by the method disclosed by the patent, the double bond protection rate is lower than 1.9%, and the content of the propenyl polyoxypropylene ether by-product is high than 66.6%; the comparative example 10 changes and increases the reaction temperature, because the reaction temperature is high, allyl is easy to isomerize into allyl, and propylene oxide is easy to isomerize into allyl alcohol or allyl alcohol, the molecular weight of the synthesized allyl alcohol polyoxypropylene ether is 404 lower than that of the method, the content of the side product of the propenyl polyoxypropylene ether is 15.6 times higher, and the double bond protection rate is 3.6 percent lower; in comparative example 11, the catalyst for synthesizing oligomer is changed, the temperature for synthesizing in the second step is changed, the molecular weight of the synthesized polyether is only 1953 at the lowest, the double bond protection rate is only 93.8 at the lowest, and the by-product of the propenyl polyoxypropylene ether is 1.5 percent at the highest, which is 26.6 times of the method.
The above description is provided for the purpose of describing the preferred embodiments of the present invention in more detail, and it should not be construed that the embodiments of the present invention are limited to the description above, and it will be apparent to those skilled in the art that the present invention can be implemented in many different forms without departing from the spirit and scope of the present invention.
Claims (4)
1. A preparation method of allyl alcohol polyoxypropylene ether is characterized by comprising the following steps: allyl alcohol and propylene oxide are used as raw materials, and a two-step reaction method is adopted: (1) initial polymerization: adding allyl alcohol and a primary polymerization catalyst into a reaction kettle, and then adopting N2Replacing air in the kettle, heating to a certain temperature, and adding propylene oxide to react to synthesize a low molecular weight allyl alcohol polyoxypropylene ether oligomer; (2) final polymerization: the final polymerization adopts a reactor combining stirring and external circulation, the product of the step (1) and a final polymerization catalyst are placed in the reactor, the reactor is vacuumized until the vacuum degree is more than or equal to 0.098MPa, the temperature is raised to 80-100 ℃, and methanol produced by the reaction of allyl alcohol oligomer and the catalyst is removed; cooling to 50-80 ℃, continuously adding propylene oxide for reaction polymerization, adding water and phosphoric acid into the obtained product for neutralization, adding an adsorbent for adsorption, heating to 100-80 ℃ under the condition of vacuum pumping to remove water, cooling to 40-80 ℃, filtering to remove crystal salt, and finally obtaining the product of the allyl alcohol polyoxypropylene ether with the molecular weight of 1000-2271 or 2713-5000-containing-; the structural formula of the allyl alcohol polyoxypropylene ether is shown in the specification
Wherein n + m = 9-110, the content of allyl alcohol polyether by-products is lower than 1.0%, the content of metal ions is less than or equal to 2ppm, the double bond protection rate is more than or equal to 96%, the color is No. 5-20 (Pt-Co unit), and the molecular weight distribution coefficient is less than or equal to 1.10;
in the step (1), the initial polymerization catalyst is a Lewis acid catalyst, and the reaction temperature is 20-40 ℃;
the stirring and external circulation reactor structure comprises a kettle body, a stirrer and a plurality of external circulation pipelines arranged on the kettle body, wherein the stirrer extends into the kettle body and is driven by a motor; each pipeline bypasses from the bottom of the kettle body to the top of the kettle body, a delivery pump is arranged on the pipeline close to the bottom, and a condenser is arranged on the pipeline close to the top; each outer circulation pipeline has the same structure, and 1-5 pipelines are arranged along the periphery of the kettle body.
2. The process for producing an allyl alcohol polyoxypropylene ether according to claim 1, wherein the weight ratio of allyl alcohol to propylene oxide is 1: 10 ~ 110.
3. The process according to claim 1, wherein in the step (1), the initial polymerization catalyst is boron trifluoride diethyl etherate or tin tetrachloride and is used in an amount of 0.05 ~ 0.2.2% based on the total amount of the oligomer.
4. The process according to claim 1, wherein in the step (2), the final polymerization catalyst is any one of sodium methoxide, potassium methoxide, a mixture of sodium methoxide and potassium methoxide, and potassium hydroxide, and the amount of the final polymerization catalyst is 0.1 ~ 0.8.8% of the total amount of the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710413295.9A CN107177034B (en) | 2017-06-05 | 2017-06-05 | Allyl alcohol polyoxypropylene ether and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710413295.9A CN107177034B (en) | 2017-06-05 | 2017-06-05 | Allyl alcohol polyoxypropylene ether and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107177034A CN107177034A (en) | 2017-09-19 |
| CN107177034B true CN107177034B (en) | 2020-01-10 |
Family
ID=59835186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710413295.9A Active CN107177034B (en) | 2017-06-05 | 2017-06-05 | Allyl alcohol polyoxypropylene ether and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107177034B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922579B (en) * | 2019-12-06 | 2021-12-03 | 浙江皇马科技股份有限公司 | Synthesis method of polyether for low-modulus sealant |
| CN110804170A (en) * | 2019-12-06 | 2020-02-18 | 浙江皇马新材料科技有限公司 | Preparation method of propylene glycol polyoxypropylene ether |
| CN112126055B (en) * | 2020-09-30 | 2023-05-05 | 浙江皇马科技股份有限公司 | Preparation method for reducing content of butynediol polyether sodium |
| CN114479056B (en) * | 2022-03-31 | 2023-05-23 | 连云港石化有限公司 | Process control method for methallyl alcohol polyoxyethylene ether |
| CN115894890A (en) * | 2022-12-05 | 2023-04-04 | 华南理工大学 | Selective functionalized modification method of primary alcohol compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504241A (en) * | 2011-11-02 | 2012-06-20 | 浙江皇马科技股份有限公司 | Method for synthetizing diallyl polyether |
| CN102911353A (en) * | 2012-10-25 | 2013-02-06 | 浙江皇马科技股份有限公司 | Fluoro alkyl alcohol polyoxyethylene ether preparation method |
| CN103289073A (en) * | 2013-06-05 | 2013-09-11 | 三江化工有限公司 | Preparation method of polycarboxylate water-reducing agent macromonomer methylallyl alcohol polyethenoxy ether |
| CN105061750A (en) * | 2015-08-05 | 2015-11-18 | 扬州晨化新材料股份有限公司 | High-double bond content allyl polyether production method |
| CN105801832A (en) * | 2014-12-31 | 2016-07-27 | 上海东大化学有限公司 | Degradable polyether polyol, and raw-material composition and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5099042A (en) * | 1989-03-14 | 1992-03-24 | Thiokol Corporation | Synthesis of tetrafunctional polyethers and compositions formed therefrom |
-
2017
- 2017-06-05 CN CN201710413295.9A patent/CN107177034B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504241A (en) * | 2011-11-02 | 2012-06-20 | 浙江皇马科技股份有限公司 | Method for synthetizing diallyl polyether |
| CN102911353A (en) * | 2012-10-25 | 2013-02-06 | 浙江皇马科技股份有限公司 | Fluoro alkyl alcohol polyoxyethylene ether preparation method |
| CN103289073A (en) * | 2013-06-05 | 2013-09-11 | 三江化工有限公司 | Preparation method of polycarboxylate water-reducing agent macromonomer methylallyl alcohol polyethenoxy ether |
| CN105801832A (en) * | 2014-12-31 | 2016-07-27 | 上海东大化学有限公司 | Degradable polyether polyol, and raw-material composition and preparation method thereof |
| CN105061750A (en) * | 2015-08-05 | 2015-11-18 | 扬州晨化新材料股份有限公司 | High-double bond content allyl polyether production method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107177034A (en) | 2017-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107177034B (en) | Allyl alcohol polyoxypropylene ether and preparation method thereof | |
| CN107266673B (en) | Allyl alcohol polyoxypropylene polyoxyethylene random polyether and preparation method thereof | |
| CN101243119B (en) | Process for producing polyester ether poly(mono)alcohols | |
| KR101866599B1 (en) | Alkylene oxide polymerization using a double metal cyanide catalyst complex and a magnesium, group 3-group 15 metal or lanthanide series metal compound | |
| CN110885435B (en) | Process for preparing high functionality polyether polyols | |
| CN1636989B (en) | Single reactors synthesis method of KOH-capped polyols based on DMC-synthesized intermediates | |
| CN102453253A (en) | Preparation process of polyether polyol with high primary hydroxyl | |
| JPWO2011034030A1 (en) | Method for producing polyethers | |
| CN105579491B (en) | Method for manufacturing poly- (epoxy butane) polyalcohol | |
| CN113773483A (en) | Carbon dioxide-based polycarbonate ether polyol for slow-rebound polyurethane foam and preparation method thereof | |
| CN112724395A (en) | Preparation method of polyether polyol with low unsaturation degree and high activity | |
| KR20080065232A (en) | Highly productive alkoxylation method | |
| CN1300216C (en) | Method for preparing low-unsaturation-degree polyether polylol | |
| CN112679721B (en) | Preparation method of high-molecular-weight low-viscosity sorbitol-based polyether polyol and obtained polyether polyol | |
| CN109593190B (en) | Synthesis method of butanol polyether with low unsaturation degree, high molecular weight and high activity | |
| CN111087597B (en) | Preparation method of high-activity polyether polyol | |
| CN110684187B (en) | Multi-metal cyanide complex catalyst and preparation method and application thereof | |
| CN112708125A (en) | Preparation method of sorbitol-based polyether polyol | |
| CN100430136C (en) | Double metal cyanide catalysts | |
| CN111040148B (en) | Preparation method of polyether glycol with stable viscosity and high molecular weight | |
| CN110804170A (en) | Preparation method of propylene glycol polyoxypropylene ether | |
| CN113234218A (en) | Preparation method of acetyl terminated allyl alcohol polyether | |
| CN114479051A (en) | Preparation method of sorbitol-based polyether polyol and obtained polyether polyol | |
| CN119931018A (en) | A kind of synthetic method of propylene glycol polyether | |
| CN117164842B (en) | Preparation method of narrow-distribution isomeric alcohol polyoxyethylene ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191203 Address after: 312000 Hangzhou Bay Shangyu economic and Technological Development Zone, Shangyu District, Zhejiang, Shaoxing Applicant after: Zhejiang Real Madrid New Material Technology Co., Ltd. Address before: 312000 new industrial zone, Shaoxing Town, Shangyu District, Zhejiang Applicant before: Zhejiang Huangma Technology Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |