CN115010917B - Allyl polyether, preparation method and application thereof in preparation of foam stabilizer - Google Patents
Allyl polyether, preparation method and application thereof in preparation of foam stabilizer Download PDFInfo
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- CN115010917B CN115010917B CN202210663990.1A CN202210663990A CN115010917B CN 115010917 B CN115010917 B CN 115010917B CN 202210663990 A CN202210663990 A CN 202210663990A CN 115010917 B CN115010917 B CN 115010917B
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- 229920000570 polyether Polymers 0.000 title claims abstract description 85
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 80
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 56
- 239000003381 stabilizer Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000006260 foam Substances 0.000 title abstract description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 56
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 44
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 44
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 41
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 20
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920002323 Silicone foam Polymers 0.000 claims 2
- 239000013514 silicone foam Substances 0.000 claims 2
- 238000012423 maintenance Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- -1 polysiloxane Polymers 0.000 abstract description 16
- 229920001296 polysiloxane Polymers 0.000 abstract description 14
- 238000011112 process operation Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 8
- 230000035699 permeability Effects 0.000 abstract description 4
- 230000000087 stabilizing effect Effects 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 229920002545 silicone oil Polymers 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012467 final product Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012974 tin catalyst Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 4
- 238000004581 coalescence Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- GAGSAAHZRBTRGD-UHFFFAOYSA-N oxirane;oxolane Chemical compound C1CO1.C1CCOC1 GAGSAAHZRBTRGD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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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)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of polyurethane materials, and particularly relates to allyl polyether and a preparation method thereof, and further discloses application of the allyl polyether in preparation of polyether modified polysiloxane polyurethane foam stabilizer. The allyl polyether in this example is based on the traditional synthesis process, and finally forms an allyl polyether with a Propylene Oxide (PO)/Butylene Oxide (BO) -Ethylene Oxide (EO) gradient heteropolymeric structure by linearly controlling the feeding procedure of propylene oxide/butylene oxide and ethylene oxide in the reaction process, and the allyl polyether is used for the synthesis of polyether modified polysiloxane after being capped by alkyl, so that the allyl polyether has excellent process operation latitude, pore opening capability, balanced foam stabilizing capability and better foam homogenizing capability, and has better pore opening air permeability and finer and more uniform cell structure.
Description
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to allyl polyether and a preparation method thereof, and further discloses application of the allyl polyether in preparation of polyether modified polysiloxane polyurethane foam stabilizer.
Background
Polyurethane foam stabilizers generally belong to organosilicon nonionic surfactants, and the main structure of the polyurethane foam stabilizer is polysiloxane-polyoxyalkylene block copolymers, and can have AB type linear block structures, ABA type linear block structures, single-side chain type structures and multi-side chain type structures according to the connection mode of polysiloxane and polyoxyalkylene. In addition, the use requirements of different polyurethane foam systems on the organic silicon surfactants can be realized by adjusting the chain link length of polysiloxane and polyoxyalkylene and the proportion of polysiloxane and polyoxyalkylene. The structure, the composition proportion and the molecular weight of the polyoxyalkylene part play important roles in emulsifying reactive components with different polarities, improving the bubble viscoelastic strength, balancing the interfacial tension of each phase, controlling the particle size of an insoluble polyurea aggregate, improving the dispersity and the solubility of the insoluble polyurea aggregate and the like in the synthesis of polyurethane foam, and are particularly represented by the foam stability, the foam uniformity degree, the open-cell capability and the operation process stability of a formula system.
Therefore, the comprehensive application characteristics of the polyurethane foam stability can be greatly influenced by adjusting the structure of the polyoxyalkylene chain segment part. The conventional polyoxyalkylene chain unit mainly adopts an ethylene oxide propylene oxide random copolymer structure, however, the actual synthesis stage finds that EO and PO do not show a uniformly distributed structure on a polyether chain obtained by random copolymerization according to a preset feeding ratio due to the difference of polymerization reaction rates of ethylene oxide and propylene oxide. As EO reaction rate is faster, EO chain segments are more easily formed by polymerization at the beginning, and PO reaction rate is slower, PO proportion of formed polymerized chain segments is higher due to accumulation in the later polymerization period. Therefore, when the polyurethane foam stabilizer and the polyurethane foam stabilizer are used for preparing polyurethane foam stabilizer products with allyl polyether graft modified polysiloxane structures, irregular distribution states of hydrophilic chain segments (EO) and lipophilic chain segments (PO) and even excessive aggregation of partial sections EO or PO occur, so that the synthesized polyether graft modified siloxane is discontinuous in liquid-gas interface distribution of the stabilizer in the polyurethane foam growth process or rapid migration and interface coverage protection of the whole area cannot be realized when the polyurethane foam stabilizer is used for polyurethane foam application, and finally, the process operation latitude of foam products is narrow, the system boundary is fragile, and slight raw material quality fluctuation, process operation errors or environmental factors are all caused, so that abnormal conditions such as cracking or shrinkage and the like of the polyurethane sponge products are generated, or the pore size distribution of polyurethane foam is generally relatively nonuniform and large. In view of the fact that the morphology and the pore size distribution of the foam structure are the most fundamental influencing factors of the physical properties of the polyurethane foam material in the field of polyurethane foam, in addition, the process operation latitude of the stabilizer products is also a crucial performance quality evaluation index for realizing the mass production of the polyurethane foam on an industrial production site, and therefore, the optimization of the parameter index can greatly improve the production qualification rate and the economic benefit of downstream production application, and the development of allyl polyether with a regular chain segment structure has positive significance for the performance optimization of the polyurethane foam.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a novel Propylene Oxide (PO)/Butylene Oxide (BO) -Ethylene Oxide (EO) tapered heteropoly allyl polyether, wherein the tapered heteropoly allyl polyether has an alkyl end-capped structure, and the polyether graft modified polysiloxane used for preparation has better process operation latitude and finer and more uniform cell structure in polyurethane foam application;
the second technical problem to be solved by the invention is to provide a preparation method of the novel Propylene Oxide (PO)/Butylene Oxide (BO) -Ethylene Oxide (EO) tapered heteropoly allyl polyether;
the third technical problem to be solved by the invention is to provide the application of the novel Propylene Oxide (PO)/Butylene Oxide (BO) -Ethylene Oxide (EO) graded hybrid polyallylmethylpolyether in preparing polyurethane foam stabilizer or polyurethane foam.
In order to solve the technical problems, the preparation method of the allyl polyether is characterized by comprising the following steps:
(1) Taking small molecular allyl alcohol as an initiator, adding propylene oxide or butylene oxide and ethylene oxide as raw materials in the presence of an alkaline catalyst to carry out ring-opening polymerization reaction, and in the feeding process, under the condition of maintaining the total feeding amount of the epoxy alkane in unit time constant, reducing the feeding amount of the propylene oxide or butylene oxide by controlling the feeding rate, and synchronously and equivalently improving the feeding amount of the ethylene oxide; obtaining hydroxyl-terminated PO/BO-EO tapered hybrid polyallylpolyether;
(2) And (3) carrying out alkyl end capping on the hydroxyl-terminated PO/BO-EO tapered polyallylate polyether.
Specifically, the feeding process in the step (1) includes the following procedures: a first stage of feeding only the propylene oxide or the butylene oxide, a second stage of linearly decreasing the feeding amount of the propylene oxide or the butylene oxide and simultaneously increasing the feeding amount of the ethylene oxide by equal amounts, and a third stage of feeding only the ethylene oxide.
Preferably, in the step (1), the feeding amount of propylene oxide or butylene oxide and ethylene oxide is linearly controlled according to the following feeding procedure, based on 100% of the feeding amount of alkylene oxide, while maintaining the constant feeding amount of alkylene oxide in the unit interval:
initially, PO or BO: EO is 100wt%:0wt%;
in the middle of the reaction, PO or BO: EO is 100wt%:0wt% to 0wt%:100wt%;
end of reaction, PO or BO: EO is 0wt%:100wt%.
Specifically, in the feeding procedure, the initial stage of the reaction comprises 1/15-1/10 of the total time of the reaction from the start of the reaction to the total time of the reaction, the middle stage of the reaction comprises 9/10-14/15 of the total time of the reaction from the 1/15-1/10 of the total time of the reaction to the total time of the reaction, and the final stage of the reaction comprises 9/10-14/15 of the total time of the reaction to the end of the reaction.
Preferably, in the feeding procedure, the initial stage of the reaction comprises 1/12 of the total time of the reaction from the start of the reaction to the total time of the reaction, the middle stage of the reaction comprises 1/12 of the total time of the reaction to 11/12 of the total time of the reaction, and the final stage of the reaction comprises 11/12 of the total time of the reaction to the end of the reaction.
Preferably, the total time of the feeding process is 8-10 hours.
Specifically, in the step (1), the mass ratio of the allyl alcohol to the total alkylene oxide is 1:7-100.
Specifically, the mass ratio of PO or BO to EO is 4:6-6:4.
specifically, the temperature of the ring-opening polymerization reaction step is 110-115 ℃, the reaction pressure is lower than 0.15Mpa, and the reaction time is preferably 30-50min.
Specifically, in the step (2), the alkyl end capping step includes a step of reacting the hydroxyl-terminated PO/BO-EO tapered polyallylpolyether in the presence of tetrabutylammonium and sodium methoxide, and a step of introducing a haloalkane for reaction.
Specifically, according to the preparation method of the allyl polyether, the mol ratio of the hydroxyl-terminated PO/BO-EO graded hybrid polyallylmethylpolyether to the tetrabutylammonium and sodium methoxide is 1: (0.01-0.03): (1.1-1.3).
Specifically, the molar ratio of the hydroxyl-terminated PO/BO-EO tapered polyallylpolyether to the haloalkane is 1: (1.1-1.3).
Specifically, the preparation method of the allyl polyether comprises the following steps:
in the reaction of the hydroxy PO/BO-EO graded hybrid polyallylpolyether, tetrabutylammonium and sodium methoxide, the reaction temperature is controlled to be 105-115 ℃ for 2-4 hours under the protection atmosphere, and the vacuum pumping desolventizing and the dehydration are synchronously carried out;
the reaction temperature of the introduced halogenated alkane is 90-95 ℃ until the pressure in the kettle is not changed.
The invention also discloses alkyl end capped PO/BO-EO tapered polyallylmethylpolyether prepared by the method, which has a number average molecular weight ranging from 500 to 6000, wherein the mass ratio of PO or BO to EO is 4:6-6:4.
the invention also discloses application of the alkyl end capped PO/BO-EO tapered hybrid polyallylpolyether in preparing an organosilicon foam stabilizer and/or a polyurethane foam material.
The invention also discloses an organosilicon foam stabilizer, which comprises side chain grafting modified polyether modified polysiloxane synthesized by adopting the alkyl end capped PO/BO-EO gradient hybrid polyallylmethylether through hydrosilylation reaction.
Preferably, the foam stabilizer adopts at least two alkyl-capped PO/BO-EO graded hybrid polyallylmelamine polyethers with different molecular weights according to requirements, and the side chain grafting modified polyether polysiloxane is synthesized through hydrosilylation reaction.
The invention also discloses a method for preparing the organosilicon foam stabilizer, which is characterized by comprising the step of preparing low-hydrogen silicone oil by taking cyclooctamethyltetrasiloxane, hexamethyldisiloxane and high-hydrogen silicone oil as raw materials and reacting in the presence of an acid catalyst, and the step of reacting at least two alkyl-terminated PO/BO-EO gradient hybrid polyallylpolyethers with different molecular weights and the low-hydrogen silicone oil as raw materials in the presence of a noble metal catalyst.
The invention also discloses a polyurethane foam material, and the preparation raw materials of the polyurethane foam material comprise the organosilicon foam stabilizer.
Preferably, the polyurethane foam material is prepared from polyether polyol, amine catalyst, organometallic catalyst, isocyanate and organosilicon foam stabilizer.
The invention also discloses a method for preparing the polyurethane foam material, which comprises the steps of mixing and curing the polyether polyol, the amine catalyst, the organometallic catalyst, the isocyanate and the organosilicon foam stabilizer.
According to the allyl polyether disclosed by the embodiment, on the basis of a traditional synthesis process, through linearly controlling the feeding procedure of propylene oxide/butylene oxide and ethylene oxide in the reaction process, under the condition of keeping the total alkylene oxide feeding amount constant, the feeding speed of propylene oxide/butylene oxide-ethylene oxide is controlled along with time, the feeding amount of propylene oxide/butylene oxide is controlled to be reduced according to a certain linear speed, simultaneously, the feeding amount of ethylene oxide is synchronously increased by equal weight, and finally, the allyl polyether with a Propylene Oxide (PO)/Butylene Oxide (BO) -Ethylene Oxide (EO) tapered heteropoly structure is formed.
The allyl polyether with the alkyl end-capped structure is novel allyl polyether with a Propylene Oxide (PO)/Butylene Oxide (BO) -Ethylene Oxide (EO) gradient hybrid structure, the number average molecular weight range is 500-6000, and the mass ratio of PO or BO to EO is 4:6-6:4, compared with the existing random copolymerization or block copolymerization allyl polyether, the polyether grafting modified polysiloxane has better process operation latitude and finer and more uniform cell structure in polyurethane foam application.
The invention also discloses a polyurethane foam material, which is synthesized by adding the organosilicon foam stabilizer on the basis of the traditional polyurethane foam material, compared with the traditional polyether modified polysiloxane synthesized by PO/EO allyl polyether with random or block structure, the polyether modified polysiloxane synthesized by PO/EO allyl polyether with the gradient hetero-polymer structure disclosed by the invention has more excellent foam stabilizing performance (sponge height), foam homogenizing performance (foam hole number) and open pore air permeability on the preparation of polyurethane soft foam sponge, and particularly has the advantages that the operation latitude of the process is far due to the two structures, the operational dosage range of silicone oil and tin catalyst in the formula is wider, extremely high convenience and product qualification rate can be brought to downstream polyurethane soft sponge production enterprises, and the commercial value is high.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 shows the propylene oxide/butylene oxide-ethylene oxide dosing procedure for examples 1-4.
Detailed Description
In the following examples and comparative examples of the present invention, the procedures and conditions for carrying out the invention are not specified, and may be referred to the conventionally known procedures and conditions recorded in the technical literature in the field; the reagents and instruments used are available through conventional market purchasing behavior without the manufacturer's attention.
In the following embodiment of the invention, the preparation method of the allyl polyether comprises the following steps:
in the first stage, propylene oxide/butylene oxide-ethylene oxide ring-opening polymerization is carried out by taking small molecular allyl alcohol as an initiator and in the presence of a basic catalyst comprising potassium hydroxide:
(1) Adding a small molecular allyl alcohol initiator into a reactor, and adding a potassium hydroxide catalyst;
(2) Propylene oxide or butylene oxide-ethylene oxide is added at 110-115 ℃, in the process of feeding, the feeding speed of propylene oxide (or butylene oxide) -ethylene oxide is controlled along with time under the condition of keeping the total feeding amount of the total alkylene oxide constant, the feeding amount of propylene oxide (or butylene oxide) is reduced according to a certain linear speed, the feeding amount of ethylene oxide is synchronously increased by equal weight, and the pressure in a kettle is kept within 0.15Mpa in the feeding process; continuously reacting until the pressure in the kettle is stable, and after the reaction is continued for 30-50 minutes, ending the reaction;
(3) After polymerization, cooling the materials, neutralizing phosphoric acid, adding a refining agent, and filtering and dehydrating to obtain a finished hydroxyl-terminated gradient hybrid polyallylpolyether product;
and a second stage, converting the hydroxyl-terminated tapered polyallylpolyether in the first stage into alkyl end-capped polyether, and simultaneously reserving double bonds to the greatest extent:
(4) Sequentially adding the hydroxyl-terminated tapered hybrid polyallylpolyether, tetrabutylammonium, sodium methoxide and methanol into a reactor, reacting for 2-4 hours at 105-115 ℃ in a nitrogen protection atmosphere, and synchronously vacuumizing to remove methanol and dehydrate;
(5) Introducing methyl chloride at 55-70 ℃, and heating to 90-95 ℃ for reaction until the pressure in the kettle is no longer changed;
(6) After the reaction is finished, the temperature is reduced, the neutralization is carried out, the filtration and the dehydration are carried out, and the product can be added with a conventional antioxidant to improve the storage stability.
EXAMPLE 1 allyl polyether Synthesis
The feeding procedure shown in fig. 1 is the feeding procedure of propylene oxide and ethylene oxide in the present embodiment, and in the whole feeding process, the feeding amount of propylene oxide is reduced and the feeding amount of ethylene oxide is synchronously and equally increased while the feeding amount of the alkylene oxide (the total amount of propylene oxide and ethylene oxide) is maintained to be constant in unit time.
In the feeding curve shown in fig. 1, the whole feeding cycle is equally divided into 12 equally divided stages based on the total time of the whole feeding reaction cycle, and the PO is controlled in the 0-1/12 (total time) stage of the whole cycle: EO is 100wt%:0wt%; PO is controlled during the 1/12-11/12 (total time) phase of the whole cycle: EO is 100wt%:0wt% to 0wt%:100wt% of the mixture is subjected to uniform gradient change; control PO from 11/12 (total time) stage of the whole cycle to the end of the reaction: EO is 0wt%:100wt%.
The first stage: adding 6.3g allyl alcohol and 0.42g potassium hydroxide into a high-pressure reaction kettle, stirring and heating to 105 ℃, and feeding 187.1g propylene oxide and 187.1g ethylene oxide according to a feeding program shown in the attached figure 1, wherein the total time of the whole feeding process is 8 hours, and the pressure in the kettle is maintained at 0.15Mpa in the feeding process; after the pressure in the kettle is stabilized after the feeding is finished, the reaction is continued for 40 minutes, the residual monomer is removed under reduced pressure, the temperature is reduced, the material is discharged, and the allyl hydroxyl polyether with the gradient hybrid coalescence structure is obtained through neutralization, refining and filtration.
And a second stage: sequentially adding 300g of hydroxyl-terminated tapered hybrid polyallylpolyether, 0.22g of tetrabutylammonium, 5.5g of sodium methoxide and 9.0g of methanol into a reactor, uniformly stirring in a nitrogen protection atmosphere, heating to 110 ℃ for reaction for 3 hours, and synchronously carrying out vacuum methanol removal and dehydration; cooling the system to 60 ℃, adding 5.2g of methyl chloride, heating to 90-95 ℃ to react until the pressure is stable, and stopping heating; neutralizing with phosphoric acid solution, filtering, dewatering, and adding antioxidant to the product to improve storage stability.
The final product obtained in this example was methyl capped allyl polyether of tapered heteropolymeric structure, noted DB-3800, and determined to have a molecular weight of 3800 and an EO/PO mass ratio of 1:1, the methyl end-capping rate was 93%.
Comparative example 1
The preparation method of the allyl polyether in this comparative example is the same as that in example 1, and only differs in that the feeding modes of ethylene oxide and propylene oxide are as follows: selected amounts of the ethylene oxide and propylene oxide were blended and fed simultaneously for the same total feed time as in example 1, with other process operations remaining consistent.
The final product obtained in this comparative example is a random structure methyl capped allyl polyether, designated WG-3800, and has a measured molecular weight of 3800 and an EO/PO mass ratio of 1:1, the methyl end-capping rate was 92%.
Comparative example 2
The preparation method of the allyl polyether in this comparative example is the same as that in example 1, and only differs in that the feeding modes of ethylene oxide and propylene oxide are as follows: other process operations were maintained consistent with the same time control of the feed stage as in example 1, with a feed of 50wt% ethylene oxide-100 wt% propylene oxide-the remainder of 50wt% ethylene oxide.
The final product obtained in this comparative example is a block-structured methyl-capped allyl polyether, noted QD-3800, and has a measured molecular weight of 3800 and an eo/PO mass ratio of 1:1, the methyl end-capping rate was 93%.
EXAMPLE 2 allyl polyether Synthesis
The feeding procedure shown in fig. 1 is the feeding procedure of propylene oxide and ethylene oxide in the present embodiment, and in the whole feeding process, the feeding amount of propylene oxide is reduced and the feeding amount of ethylene oxide is synchronously and equally increased while the feeding amount of the alkylene oxide (the total amount of propylene oxide and ethylene oxide) is maintained to be constant in unit time.
In the feeding curve shown in fig. 1, the whole feeding cycle is equally divided into 12 equally divided stages based on the total time of the whole feeding reaction cycle, and the PO is controlled in the 0-1/12 (total time) stage of the whole cycle: EO is 100wt%:0wt%; PO is controlled during the 1/12-11/12 (total time) phase of the whole cycle: EO is 100wt%:0wt% to 0wt%:100wt% of the mixture is subjected to uniform gradient change; control PO from 11/12 (total time) stage of the whole cycle to the end of the reaction: EO is 0wt%:100wt%.
The first stage: 18.3g of allyl alcohol and 1.0g of potassium hydroxide are added into a high-pressure reaction kettle, the temperature is raised to 105 ℃ by stirring, 172.5g of propylene oxide and 172.5g of ethylene oxide are fed according to the feeding procedure shown in the attached figure 1, the total time of the whole feeding process is 9 hours, and the pressure in the kettle is maintained at 0.15Mpa in the feeding process; after the pressure in the kettle is stabilized after the feeding is finished, continuing to react for 40 minutes, decompressing, removing residual monomers, cooling, discharging, neutralizing, refining and filtering to obtain the tapered hybrid coalescing structure allyl hydroxyl polyether.
And a second stage: 300g of hydroxyl-terminated gradient hybrid polyallylpolyether, 0.7g of tetrabutylammonium, 17.6g of sodium methoxide and 34g of methanol are sequentially added into a reactor, stirred uniformly in a nitrogen protection atmosphere and heated to 110 ℃ for reaction for 3 hours, and then vacuum methanol removal and dehydration are carried out; cooling to 60 ℃, adding 16.4g of methyl chloride, heating to 90-95 ℃ to react until the pressure is stable, and stopping heating; neutralizing with phosphoric acid solution, filtering, dewatering, and adding antioxidant to the product to improve storage stability.
The final product obtained in this example was methyl capped allyl polyether of tapered heteropolymeric structure, noted DB-1200, having a molecular weight of 1200, EO/PO mass ratio of 1:1, the methyl end-capping rate was 95%.
Comparative example 3
The preparation method of the allyl polyether in this comparative example is the same as that in example 2, and only differs in that the feeding modes of ethylene oxide and propylene oxide are as follows: selected amounts of the ethylene oxide and propylene oxide were blended and fed simultaneously for the same total feed time as in example 2, with other process operations remaining consistent.
The final product obtained in this comparative example is a random structure methyl capped allyl polyether, designated WG-1200, having a molecular weight of 1200, EO/PO mass ratio of 1:1, the methyl end-capping rate was 94%.
Comparative example 4
The preparation method of the allyl polyether in this comparative example is the same as that in example 2, and only differs in that the feeding modes of ethylene oxide and propylene oxide are as follows: other process operations were maintained consistent with the same time control of the feed stage as in example 2, with a feed of 50wt% ethylene oxide-100 wt% propylene oxide-the remainder of 50wt% ethylene oxide.
The final product obtained in this comparative example is a block-structured methyl-terminated allyl polyether, noted QD-1200, having a molecular weight of 1200, eo/PO mass ratio of 1:1, the methyl end-capping rate was 95%.
Example 3
The feeding procedure shown in fig. 1 is a feeding procedure of the butylene oxide and the ethylene oxide according to the present embodiment, and in the whole feeding process, the feeding amount of the butylene oxide is reduced and the feeding amount of the ethylene oxide is synchronously and equivalently increased under the condition that the total feeding amount of the alkylene oxide in unit time is maintained constant.
In the feeding curve shown in fig. 1, the whole feeding cycle is equally divided into 12 equally divided phases based on the total time of the whole feeding reaction cycle, and BO is controlled in the 0-1/12 (total time) phase of the whole cycle: EO is 100wt%:0wt%; control BO during 1/12-11/12 (total time) of the whole cycle: EO is 100wt%:0wt% to 0wt%:100wt% of the mixture is subjected to uniform gradient change; control BO during the whole cycle 11/12 (total time) phase to the end of the reaction: EO is 0wt%:100wt%.
The first stage: 23.2g of allyl alcohol and 1.2g of potassium hydroxide are added into a high-pressure reaction kettle, the temperature is raised to 115 ℃ by stirring, 202.2g of butylene oxide and 134.8g of ethylene oxide are fed according to the feeding procedure shown in the attached figure 1, the total time of the whole feeding process is 10 hours, and the pressure in the kettle is maintained at 0.15Mpa in the feeding process; after the pressure in the kettle is stabilized after the feeding is finished, the reaction is continued for 46 minutes, the residual monomer is removed under reduced pressure, the temperature is reduced, the material is discharged, and the allyl hydroxyl polyether with the gradient hybrid coalescence structure is obtained through neutralization, refining and filtration.
And a second stage: sequentially adding 300g of hydroxyl-terminated tapered hybrid polyallylpolyether, 0.93g of tetrabutylammonium, 23.4g of sodium methoxide and 12.0g of methanol into a reactor, uniformly stirring in a nitrogen protection atmosphere, heating to 105 ℃ for reaction for 3.5 hours, and synchronously carrying out vacuum methanol removal and dehydration; cooling the system to 65 ℃, adding 21.9g of methyl chloride, heating to 90-95 ℃ to react until the pressure is stable, and stopping heating; neutralizing with phosphoric acid solution, filtering, dewatering, and adding antioxidant to the product to improve storage stability.
The final product obtained in this example was methyl capped allyl polyether of tapered heteropolymeric structure, noted DB-900, having a molecular weight of 900, EO/BO mass ratio of 4:6, the methyl end-capping rate was 92%.
Example 4
The feeding procedure shown in fig. 1 is a feeding procedure of propylene oxide and ethylene oxide according to the present embodiment, and in the whole feeding process, the feeding amount of propylene oxide is reduced and the feeding amount of ethylene oxide is synchronously and equivalently increased while maintaining the total feeding amount of alkylene oxide in a unit time constant.
In the feeding curve shown in fig. 1, the whole feeding cycle is equally divided into 12 equally divided stages based on the total time of the whole feeding reaction cycle, and the PO is controlled in the 0-1/12 (total time) stage of the whole cycle: EO is 100wt%:0wt%; PO is controlled during the 1/12-11/12 (total time) phase of the whole cycle: EO is 100wt%:0wt% to 0wt%:100wt% of the mixture is subjected to uniform gradient change; control PO from 11/12 (total time) stage of the whole cycle to the end of the reaction: EO is 0wt%:100wt%.
The first stage: adding 40.6g allyl alcohol and 1.0g potassium hydroxide into a high-pressure reaction kettle, stirring and heating to 110 ℃, and feeding 123.8g propylene oxide and 185.6g ethylene oxide according to a feeding program shown in the attached figure 1, wherein the total time of the whole feeding process is 8-10 hours, and the pressure in the kettle is maintained at 0.15Mpa in the feeding process; after the pressure in the kettle is stabilized after the feeding is finished, the reaction is continued for 30 minutes, the residual monomer is removed under reduced pressure, the temperature is reduced, the material is discharged, and the allyl hydroxyl polyether with the gradient hybrid coalescence structure is obtained through neutralization, refining and filtration.
And a second stage: sequentially adding 300g of hydroxyl-terminated tapered hybrid polyallylpolyether, 1.66g of tetrabutylammonium, 42.2g of sodium methoxide and 21.0g of methanol into a reactor, uniformly stirring in a nitrogen protection atmosphere, heating to 105 ℃ for reaction for 2.5 hours, and synchronously carrying out vacuum methanol removal and dehydration; cooling the system to 55 ℃, adding 39.4g of methyl chloride, heating to 90-95 ℃ to react until the pressure is stable, and stopping heating; neutralizing with phosphoric acid solution, filtering, dewatering, and adding antioxidant to the product to improve storage stability.
The final product obtained in this example was a methyl capped allyl polyether of tapered heteropolymeric structure, noted DB-500, having a molecular weight of 500, EO/BO mass ratio of 6:4, the methyl end-capping rate was 94%.
Application example 1 Synthesis of polyurethane foam stabilizer
684.2g of cyclooctamethyltetrasiloxane (D4), 18.3g of hexamethyldisiloxane (MM), 44.6g of high-hydrogen silicone oil (hydrogen content 1.60%) and 14.4g of concentrated sulfuric acid catalyst are added into a reactor, and the reaction is carried out for 10 hours at 38 ℃ under the protection of nitrogen; after the telomerization, the pH value is adjusted to 6.6 by sodium carbonate, and the low hydrogen silicone oil (hydrogen content 0.12%) is obtained by filtration.
44.5g of the low-hydrogen silicone oil, 56.8g of allyl polyether DB-3800, 54.2g of allyl polyether DB-1200 and 0.02g of stabilizer dibutyl ethanolamine (DBAE) are added into a reactor, stirred and heated to 78 ℃, 0.2g of chloroplatinic acid/ethanol solution is added, after the reaction is carried out for 2.5 hours, the reaction is stopped when the hydrogen content of the reactant is less than 0.1mL/g, and the obtained product is diluted by a small molecular solvent, thus obtaining the polyurethane foam stabilizer with the required gradient-transition coalescence structure, which is marked as DB-Si.
Comparative application example 1
The polyurethane foam stabilizer of this comparative example was synthesized in the same manner as in example 1 except that the allyl polyethers of random structures WG-3800 and WG-1200 were replaced with equivalent amounts of allyl polyethers of random structures DB-3800 and DB-1200, respectively, and other process operations were maintained consistent. The obtained product is diluted by a small molecular solvent to obtain the required polyurethane foam stabilizer which is named as WG-Si.
Comparative application example 2
The polyurethane foam stabilizer of this comparative example was synthesized in the same manner as in application example 1, except that the allyl polyether DB-3800 and DB-1200 of the tapered heteropolymeric structure were replaced with the allyl polyether QD-3800 and QD-1200 of the equivalent block structure, respectively, and the other process operations remained consistent. The obtained product is diluted by a small molecular solvent to obtain the required polyurethane foam stabilizer which is marked as QD-Si.
Experimental example
The polyurethane foam material is prepared according to the following system composition, and the specific proportions of the raw material components are shown in the following table 1:
polyether polyol:F3050D, triol starting, molecular weight about 3000, PO content>90%, for optimized chemical production of polyethersA product;
polyurethane foam stabilizer: polyurethane foam stabilizers DB-Si, WG-Si and QD-Si prepared in application example 1 and comparative application examples 1-2, respectively, were designated as experimental groups 1-3, respectively;
amine catalyst:a33 A dipropylene glycol solution of 33% triethylenediamine, a product produced by the win-win group (Evonik);
organometallic catalysts:stannous octoate, organotin-based catalyst, a product produced by the winning group (Evonik);
toluene diisocyanate: TDI 80/20 was a Wanhua chemically produced product having an NCO content of 48% for a mixture of 80% 2, 4-toluene diisocyanate and 20% 2, 6-toluene diisocyanate.
TABLE 1 polyurethane foam System composition
The specific preparation method of the polyurethane foam material comprises the following steps:
(1) All raw materials except TDI in a formula list, namely polyether, water, silicone oil, an amine catalyst and a tin catalyst are weighed into the same plastic cup according to a design proportion, and the polyether pre-compound is pre-stirred for 1 minute at 1500 rpm;
(2) Separately weigh TDI to another plastic cup;
(3) The temperature of the polyether pre-compound and TDI is controlled to 22-23 ℃ respectively;
(4) Pouring TDI into polyether pre-compound, immediately stirring for 8 seconds at 2000 rpm, and rapidly pouring the uniformly mixed reactant into a die with a square body of 20cm in inner diameter and provided with a film or kraft paper;
(5) After 48 hours of curing at room temperature, demolding, preparing samples and detecting the physical properties of the sponge according to the test standard.
The foaming stirring instrument, the sponge testing instrument and the detection standard adopted by the polyurethane foam material synthesis are consistent.
Typical test items corresponding to the functional merits of the evaluation silicone oil in the polyurethane foam application related to the above experimental groups 1-3 include 6 items, including basic physical properties (1 density), evaluation of foam stabilizing performance of the silicone oil (2 sponge height), evaluation of process latitude of the silicone oil (3 tin catalyst operating range, 4 silicone oil operating range), open pore capability of the silicone oil (5 air permeability), foam fineness (foam homogenizing capability of the silicone oil) (6 cell number). The test results are shown in table 2 below.
Table 2 polyurethane sponge application test results
Note that: (1) the 4 marked data are all experimental values when the silicon oil dosage and the tin catalyst are standard dosages;
(2) and (3) the upper limit of the marked data range represents the limit value of the occurrence of micro-cracking of the sponge, the lower limit represents the limit value of the occurrence of micro-closed pores of the sponge, and the wider the numerical range is, the wider the operable process latitude of the silicone oil is, and the better the silicone oil performance is
As can be seen from the above table data, compared with the traditional polyether modified polysiloxane synthesized by the PO/EO allyl polyether with random or block structure, the polyether modified polysiloxane synthesized by the PO/EO allyl polyether with the tapered heteropolymeric structure disclosed by the invention has more excellent foam stabilizing performance (sponge height), foam homogenizing performance (foam hole number) and open pore air permeability in the preparation of polyurethane soft foam sponge, and more importantly, the performance of the process operation latitude is far better than that of the two comparative product structures, particularly, the operational dosage range of silicone oil and tin catalyst in the formula is wider, extremely high convenience and product qualification rate can be brought to downstream polyurethane soft sponge production enterprises, the commercial value is high, and the root cause of the advantage is benefited by the EO/PO tapered heteropolymeric structure of polyether. It can be seen that the EO/PO tapered hybrid coalescing structure allyl polyether of the present invention has a great performance advantage in the synthesis of polyurethane foam materials.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (9)
1. A process for preparing allyl polyethers for preparing silicone foam stabilizers, comprising the steps of:
(1) Taking small molecular allyl alcohol as an initiator, adding propylene oxide or butylene oxide and ethylene oxide as raw materials in the presence of an alkaline catalyst to carry out ring-opening polymerization reaction, and in the feeding process, under the condition of maintaining the constant total weight of the epoxy alkane fed in unit time, reducing the feeding amount of the propylene oxide or butylene oxide by controlling the feeding rate, and synchronously increasing the feeding amount of the ethylene oxide by equal weight; obtaining hydroxyl-terminated PO/BO-EO tapered hybrid polyallylpolyether;
the feeding process comprises the following procedures: a first stage of feeding only the propylene oxide or the butylene oxide, a second stage of linearly reducing the feeding amount of the propylene oxide or the butylene oxide and synchronously increasing the feeding amount of the ethylene oxide by equal weight, and a third stage of feeding only the ethylene oxide;
(2) And (3) carrying out alkyl end capping on the hydroxyl-terminated PO/BO-EO tapered polyallylate polyether.
2. The method for producing allyl polyether according to claim 1, wherein in the step (1), the feeding amount of propylene oxide or butylene oxide and ethylene oxide is linearly controlled in accordance with the following feeding procedure, with the total feeding amount of alkylene oxide being 100% in the maintenance of the constant total feeding amount of alkylene oxide in the unit:
initially, PO or BO: EO is 100wt%:0wt%;
in the middle of the reaction, PO or BO: EO is 100wt%:0wt% to 0wt%:100wt%;
end of reaction, PO or BO: EO is 0wt%:100wt%.
3. The method for producing allyl polyether according to claim 2, wherein in the feeding procedure, the initial stage of the reaction comprises 1/15 to 1/10 stage of the total reaction time from the start of the reaction to the total time of the whole feeding process, the middle stage of the reaction comprises 9/10 to 14/15 stage of the total reaction time from the 1/15 to 1/10 stage of the total reaction time to the total time of the whole reaction, and the final stage of the reaction comprises 9/10 to 14/15 stage of the total reaction time to the end of the reaction.
4. A process for the preparation of allyl polyethers according to claim 3 in which the total time of the dosing process is 8 to 10 hours.
5. The method for producing allyl polyether according to any one of claims 1 to 4, wherein in the step (1):
the mass ratio of the allyl alcohol to the total amount of the alkylene oxide is 1:7-100;
in the step (1), the mass ratio of the PO or the BO to the EO is 4:6-6:4.
6. the method according to any one of claims 1 to 4, wherein in the step (2), the alkyl capping step comprises a step of reacting the hydroxyl-terminated PO/BO-EO tapered polyallylate in the presence of tetrabutylammonium and sodium methoxide, and a step of reacting by introducing a halogenated alkane.
7. The method for producing allyl polyether according to claim 6, wherein:
the mol ratio of the hydroxyl-terminated PO/BO-EO graded hybrid polyallylpolyether to the tetrabutylammonium and sodium methoxide is 1: (0.01-0.03): (1.1-1.3);
the molar ratio of the hydroxyl-terminated PO/BO-EO tapered heteropoly allyl polyether to the halogenated alkane is 1: (1.1-1.3).
8. An alkyl-capped PO/BO-EO tapered polyallylpolyether prepared by the process of any one of claims 1 to 7.
9. Use of the alkyl-capped PO/BO-EO tapered polyallylpolyether of claim 8 for preparing a silicone foam stabilizer and/or a polyurethane foam.
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| JP2013035832A (en) * | 2011-07-14 | 2013-02-21 | Matsumoto Yushi Seiyaku Co Ltd | Alkylene oxide adduct and production method therefor |
| CN103347912A (en) * | 2011-01-30 | 2013-10-09 | 戴纳索尔伊莱斯托米罗斯公司 | Tapered triblock copolymers |
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