CN111019116A - Preparation method of high molecular weight block polyether, silicon ether mixed type defoaming agent and preparation method thereof - Google Patents
Preparation method of high molecular weight block polyether, silicon ether mixed type defoaming agent and preparation method thereof Download PDFInfo
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- CN111019116A CN111019116A CN201911342529.0A CN201911342529A CN111019116A CN 111019116 A CN111019116 A CN 111019116A CN 201911342529 A CN201911342529 A CN 201911342529A CN 111019116 A CN111019116 A CN 111019116A
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- high molecular
- molecular weight
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- 229920000570 polyether Polymers 0.000 title claims abstract description 140
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 138
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 40
- 239000010703 silicon Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 17
- -1 polysiloxane Polymers 0.000 claims abstract description 76
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 64
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 16
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 16
- 239000006184 cosolvent Substances 0.000 claims abstract description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 35
- 239000002904 solvent Substances 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 27
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 20
- 150000005846 sugar alcohols Polymers 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 6
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 6
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 6
- 239000006260 foam Substances 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 18
- 230000005764 inhibitory process Effects 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000004939 coking Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 230000003111 delayed effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 231100000956 nontoxicity Toxicity 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241001391944 Commicarpus scandens Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011261 inert gas Substances 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
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
-
- 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)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention provides a silicon ether mixed defoaming agent, which comprises the following components: 24-40 parts by weight of high molecular weight block polyether; 20-30 parts of high-molecular polyether modified polysiloxane; 10-30 parts by weight of fatty alcohol; 15-35 parts by weight of a cosolvent; the high molecular weight block polyether is obtained by polymerizing polyol and alkylene oxide; the high molecular weight siloxane modified polysiloxane is obtained by modifying polysiloxane with high molecular weight block polyether. Compared with the prior art, the polyether chain segment with hydrophilicity is grafted to the polysiloxane chain segment with hydrophobicity, and the formed silicon ether copolymer has the advantages of two defoaming agents of silicon and ether; the high molecular weight polyether modified polysiloxane and the high molecular weight block polyether are used in a composite mode, so that the good defoaming effect of the high molecular weight polyether modified polysiloxane and the good foam inhibition effect of the high molecular weight block polyether have a synergistic effect, the reduction of the foam amount is effectively guaranteed, and the improvement of the defoaming efficiency is promoted by matching the high surface active fatty alcohol.
Description
Technical Field
The invention belongs to the technical field of defoaming agents, and particularly relates to a preparation method of high molecular weight block polyether, a silicon ether mixed defoaming agent and a preparation method thereof.
Background
The delayed coking is an oil refining device for preparing light oil by thermally destroying and processing heavy residue oil, and is rapidly developed in China due to the advantages of low requirement on raw material quality, low processing cost, low investment and the like. On a delayed coking device, oil gas generated by cracking of raw materials and natural surfactant contained in the raw materials are easy to generate a foam layer in a coking tower, so that the treatment capacity of the coking tower is reduced, and the utilization rate of equipment is low.
In view of the hazards of foam in delayed coking production, it is common to treat with an overhead injection of an anti-foaming agent. The first generation of antifoaming agents mainly comprises fatty acids and organic substances such as fatty acid esters, mineral oil and lower alcohols; the second-generation defoaming agent is a polyether defoaming agent, and mainly comprises a polyoxypropylene-polyoxyethylene block copolymer with relatively low molecular weight; the third generation defoaming agent is a silicone defoaming agent; the fourth generation defoaming agent is polyether modified polysiloxane defoaming agent, which is a novel high-efficiency defoaming agent with the advantages of polyether and polysiloxane, and has the characteristics of strong defoaming efficiency, reverse solubility, no toxicity, self-emulsibility, stability and the like.
The defoaming agent applied to the delayed coking unit at present mainly comprises an organic silicon defoaming agent and a non-silicon defoaming agent, the organic silicon defoaming agent has high silicon content and can influence the activity and the service life of a downstream hydrogenation unit catalyst, and the non-silicon defoaming agent is difficult to replace the organic silicon defoaming agent in a short time due to the defects of poor high-temperature stability, poor defoaming capability, high production cost and the like.
At present, the silicon content and the performance in the defoaming agent are generally positively correlated, when the silicon content is reduced, the defoaming effect is obviously reduced, the coking time of a coke tower is short, the switching time is short, and the waste of energy and personnel is caused. Therefore, the silicon content of the defoaming agent is reduced, the defoaming effect is improved, the addition amount of the defoaming agent is reduced, and the defoaming agent product with low silicon content, high defoaming performance and foam inhibition performance and low addition amount is required by the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a high molecular weight block polyether, a silyl ether mixed defoaming agent and a preparation method thereof, wherein the silyl ether mixed defoaming agent has low silicon content, high defoaming rate and small addition amount.
The invention provides a silicon ether mixed defoaming agent, which comprises the following components:
the high molecular weight block polyether is obtained by polymerizing polyol and alkylene oxide;
the high molecular weight polyether modified polysiloxane is obtained by high molecular weight block polyether modified polysiloxane.
Preferably, the polyol is selected from one or more of glucose, fructose, pentaerythritol and glycerol; the alkylene oxide is two or more selected from ethylene oxide, propylene oxide and butylene oxide; the acid anhydride substance is selected from acetic anhydride and/or maleic anhydride.
Preferably, the high molecular weight block polyether comprises the following segments:
wherein m, n and p are polymerization degrees, and m is 20-40; n is 10 to 3, and p is 20 to 40.
Preferably, the polysiloxane is of formula (I):
wherein x is the polymerization degree, and x is 20-150.
Preferably, the fatty alcohol is selected from one or more of isooctanol, isoamyl alcohol, n-heptanol, dodecanol and tetradecanol;
the cosolvent is one or more selected from 120# solvent oil, 200# solvent oil, dearomatized solvent oil D40 and dearomatized solvent oil D60.
Preferably, the high molecular weight polyether modified polysiloxane is obtained by modifying polysiloxane after the high molecular weight block polyether is terminated by an anhydride compound.
Preferably, the method comprises the following steps:
and mixing fatty alcohol and a cosolvent, then sequentially adding high-molecular-weight block polyether and high-molecular-weight polyether modified polysiloxane, and uniformly mixing to obtain the silicon ether mixed defoaming agent.
The invention also provides a preparation method of the high molecular weight block polyether, which comprises the following steps:
taking polyhydric alcohol as an initiator, and carrying out ring-opening polymerization reaction with alkylene oxide under the action of a catalyst to obtain high molecular weight block polyether; the catalyst is an alkali metal catalyst and/or a high molecular weight block polyether.
Preferably, the method comprises the following steps:
s1) mixing polyalcohol and aliphatic hydrocarbon solvent of C6-C16 with a catalyst, heating and pressurizing in a protective atmosphere, and then adding propylene oxide for reaction to obtain a first intermediate product;
s2) cooling the first intermediate product, adding ethylene oxide, heating and reacting to obtain a second intermediate product;
s3) cooling the second intermediate product, adding propylene oxide, heating and reacting to obtain the high molecular weight block polyether.
Preferably, the molar ratio of the polyol, the catalyst and the propylene oxide in the step S1) is 1: (0.01-0.2): (100-200); the reaction temperature is 110-140 ℃; the reaction time is 2-4 h; the reaction pressure is 1.2-1.8 MPa;
the molar ratio of the ethylene oxide to the polyhydric alcohol added in the step S2) is (50-150): 1; the reaction temperature is 80-110 ℃; the reaction time is 1.5-3 h; the reaction pressure is 1.2-1.8 MPa;
the molar ratio of the propylene oxide to the polyhydric alcohol added in the step S3) is (100-200): 1; the reaction temperature is 110-140 ℃; the reaction time is 2-4 h; the reaction pressure is 1.2-1.8 MPa.
The invention provides a silicon ether mixed defoaming agent, which comprises the following components: 24-40 parts by weight of high molecular weight block polyether; 20-30 parts of high-molecular polyether modified polysiloxane; 10-30 parts by weight of fatty alcohol; 15-35 parts by weight of a cosolvent; the high molecular weight block polyether is obtained by polymerizing polyol and alkylene oxide; the high molecular weight siloxane modified polysiloxane is obtained by modifying polysiloxane with high molecular weight block polyether. Compared with the prior art, the high molecular block polyether in the defoaming agent provided by the invention adopts multi-branched isomeric polyol as an initiator, the synthesized block polyether has high branching degree and the molecular weight is increased in multiple levels, the high temperature stability of the block polyether is improved, the multi-branched structure is easy to form different surface tensions on the foam surface in different directions, the foam is easy to break, and meanwhile, the defoaming agent is not easy to decompose due to high molecular weight, and the continuity is good; in addition, the polyether chain segment with hydrophilicity is grafted to the polysiloxane chain segment with hydrophobicity, the formed siloxane copolymer has the advantages of silicon and ether defoaming agents, namely the polysiloxane segment has the characteristics of quick defoaming, long foam inhibition time, safety, no toxicity and the like, and the polyether segment has the characteristics of high temperature resistance, strong acid and alkali resistance and the like under severe conditions, so that the defoaming performance is more excellent, and the application field is wider; finally, the high molecular polyether modified polysiloxane and the high molecular weight block polyether are used in a composite mode, so that the good defoaming effect of the high molecular polyether modified polysiloxane and the good foam inhibition effect of the high molecular weight block polyether have a synergistic effect, the reduction of the foam quantity is effectively guaranteed, meanwhile, the high surface active fatty alcohol is matched, the substitution and modification effects of the high molecular polyether modified polysiloxane and the high molecular weight block polyether on the foam surface are promoted, the surface activity of the foam is reduced, and the improvement of the defoaming efficiency is promoted.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of high molecular weight block polyether, which comprises the following steps: taking polyhydric alcohol as an initiator, and carrying out ring-opening polymerization reaction with alkylene oxide under the action of a catalyst to obtain high molecular weight block polyether; the catalyst is an alkali metal catalyst and/or a high molecular weight block polyether.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The invention takes the polyol as an initiator, can increase the esterification degree of the block polyether, increases the molecular weight of the block polyether in multiple order, improves the high-temperature stability of the block polyether, and can improve the foam inhibition performance of the block polyether by virtue of a multi-block structure. In the invention, the polyalcohol is preferably one or more of glucose, fructose, pentaerythritol and glycerol; the alkali metal catalyst is preferably potassium hydroxide or sodium hydroxide; in the present invention, the catalyst is preferably a high molecular weight block polyether, i.e. a self-made high molecular weight block polyether; the high molecular weight block polyether as the catalyst can be prepared by taking an alkali metal catalyst as the catalyst, taking polyol as an initiator, and carrying out ring-opening polymerization reaction with alkylene oxide at the beginning, or taking the polyol as the initiator and carrying out ring-opening polymerization reaction with the alkylene oxide without adding the catalyst, and directly taking the obtained high molecular weight block polyether as the catalyst in the subsequent reaction; the alkylene oxide is preferably two or more of ethylene oxide, propylene oxide and butylene oxide, and more preferably ethylene oxide and propylene oxide; the molar ratio of the polyol, catalyst and alkylene oxide is preferably 1: (0.01-0.2): (250-550), more preferably 1: (0.02-0.1): (250-550).
The invention adopts the high molecular block polyether product as the catalyst directly in the synthesis of the high molecular block polyether, avoids the phenomenon that bimetallic and alkali metal as the catalyst enter metal impurities, and needs to add an acid neutralizing agent for treatment after the reaction is finished, thereby thoroughly eliminating the danger of the neutralization step, simultaneously the product has no metal residue, the metal content of the coking raw oil can not be increased, and the influence on the activity of the catalyst in the subsequent processing section caused by metal introduction can not be ensured.
The invention takes polyol as an initiator to carry out ring-opening polymerization reaction with alkylene oxide under the action of a catalyst, and preferably, the method specifically comprises the following steps: s1) mixing polyalcohol and aliphatic hydrocarbon solvent of C6-C16 with a catalyst, heating and pressurizing in a protective atmosphere, and then adding propylene oxide for reaction to obtain a first intermediate product; s2) cooling the first intermediate product, adding ethylene oxide, heating and reacting to obtain a second intermediate product; s3) cooling the second intermediate product, adding propylene oxide, and heating for reaction to obtain the high molecular weight block polyether.
Mixing polyalcohol, aliphatic hydrocarbon solvent of C6-C16 and catalyst; the aliphatic hydrocarbon solvent of C6-C16 is preferably an aliphatic hydrocarbon solvent of C6-C12, more preferably an aliphatic hydrocarbon solvent of C6-C10, and even more preferably an aliphatic hydrocarbon solvent of C6-C7; the molar ratio of the polyhydric alcohol, the aliphatic hydrocarbon solvent with C6-C16 and the catalyst is preferably 1: (0.5-1): (0.01 to 0.2), more preferably 1: (0.6-0.8): (0.02 to 0.1), and more preferably 1: 0.6: 0.1.
after mixing, heating and pressurizing in a protective atmosphere; preferably, after heating in a protective atmosphere, preferably vacuumizing to remove moisture, and pressurizing; the protective atmosphere is preferably nitrogen; the heating temperature is preferably 110-140 ℃, and more preferably 110-120 ℃; the pressurization is preferably micro positive pressure, more preferably 1.2 to 1.8MPa, more preferably 1.4 to 1.6MPa, and still more preferably 1.5 MPa.
Heating and pressurizing, and then adding propylene oxide to react to obtain a first intermediate product; the molar ratio of the polyol to propylene oxide is preferably 1: (100-200), more preferably 1: (120-180), and more preferably 1: (140-160), most preferably 1: 150; the reaction temperature is preferably 110-140 ℃, and more preferably 110-120 ℃; the reaction time is preferably 2-4 h, and more preferably 3 h; the pressure of the reaction is preferably 1.2 to 1.8MPa, more preferably 1.4 to 1.6MPa, and still more preferably 1.5 MPa.
Cooling the first intermediate product, preferably to 30-50 ℃, more preferably to 35-45 ℃, and further preferably to 40 ℃, then adding ethylene oxide, and heating for reaction; the molar ratio of the ethylene oxide to the polyol is preferably (50-150): 1, more preferably (80-120): 1, more preferably 100: 1; the reaction temperature is preferably 80-110 ℃, more preferably 90-110 ℃, and further preferably 100 ℃; the reaction time is preferably 1.5-3 h, more preferably 2-3 h, and still more preferably 2.5 h; the reaction pressure is preferably 1.2 to 1.8MPa, more preferably 1.4 to 1.6MPa, and still more preferably 1.5 MPa.
Cooling the second intermediate product, preferably to 30-50 ℃, more preferably to 35-45 ℃, and further preferably to 40 ℃, then adding propylene oxide, and heating for reaction; the mol ratio of the propylene oxide to the polyhydric alcohol is preferably (100-200): 1, more preferably (140 to 200): 1, and preferably (160-200): 1, most preferably (180-200): 1; the reaction temperature is preferably 110-140 ℃, and more preferably 120-130 ℃; the reaction time is preferably 2-4 h; the pressure of the reaction is preferably 1.2 to 1.8MPa, more preferably 1.4 to 1.6MPa, and still more preferably 1.5 MPa.
After the reaction is finished, the temperature is preferably reduced to 30-50 ℃, more preferably to 35-45 ℃, and is further preferably to 40 ℃, and then the product is subjected to reduced pressure suction filtration washing and drying to obtain the high molecular weight block polyether.
The invention also provides the high molecular weight block polyether prepared by the method, which is obtained by polymerizing the polyhydric alcohol and the alkylene oxide.
The high molecular weight block polyether preferably comprises the following segments:
wherein m, n and p are polymerization degrees, and m is 20-40; n is 10 to 3, and p is 20 to 40.
In the case of the polyol being glucose, the high molecular weight block polyether is preferably represented by the following formula:
wherein m, n and p are polymerization degrees, wherein m is preferably 20-40, n is preferably 10-30, and p is preferably 20-40.
The invention also provides a silicon ether mixed defoaming agent, which comprises the following components:
the high molecular weight block polyether is obtained by polymerizing polyol and alkylene oxide;
the high molecular weight polyether modified polysiloxane is obtained by high molecular weight block polyether modified polysiloxane.
Wherein, the high molecular weight block polyether is the same as the above, and is not described again; in some embodiments provided herein, the high molecular weight block polyether is preferably present in an amount of 30 parts by weight; in some embodiments provided herein, the high molecular weight block polyether is preferably present in an amount of 25 parts by weight; in other embodiments provided herein, the high molecular weight block polyether is preferably present in an amount of 40 parts by weight.
The high molecular block polyether adopted by the invention adopts multi-branched isomeric polyalcohol as an initiator, the synthesized block polyether has high branching degree, a multi-branched structure is easy to form different surface tensions on the foam surface in different directions, the foam is easy to break, and meanwhile, the defoaming agent is difficult to decompose due to high molecular weight, and the continuity is good.
The high molecular weight polyether modified polysiloxane is obtained from high molecular weight block polyether modified polysiloxane, and is preferably obtained by modifying polysiloxane after the high molecular weight block polyether is terminated by an anhydride compound in order to reduce side reactions; the acid anhydride compound is preferably acetic anhydride and/or maleic anhydride.
In the present invention, the high molecular polyether-modified polysiloxane is preferably prepared according to the following steps: using an anhydride compound as a blocking agent, and carrying out blocking treatment on the high molecular weight block polyether to obtain a blocked high molecular weight block polyether; and mixing the end-capped high molecular weight block polyether, polysiloxane and an alcohol solvent, and heating for reaction in the presence of a metal catalyst to obtain the high molecular weight polyether modified polysiloxane.
Using anhydride compounds as end capping agents, and carrying out end capping treatment on high molecular weight block polyether; the acid anhydride compound is preferably acetic anhydride and/or maleic anhydride; the preferred molar ratio of the anhydride compound to the high molecular weight block polyether is (3-6): 1, and preferably (4-6): 1; the end-capping treatment is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen and/or argon; the temperature of the end-capping treatment is preferably 130-160 ℃; the end-capping time is preferably 2-4 h.
After the end capping treatment, preferably using inert gas to vacuumize and purge, and removing unreacted anhydride compounds to obtain end capped high molecular weight block polyether; the inert gas is preferably nitrogen and/or argon; in the case of the capping agent being acetic anhydride, the resulting capped high molecular weight block polyether is preferably as follows:
mixing the end-capped high molecular weight block polyether, polysiloxane and an alcohol solvent, and heating for reaction in the presence of a metal catalyst; the molar ratio of the end-capped high molecular weight block polyether to polysiloxane is preferably 1: (1.05 to 1.30), more preferably 1: (1.1-1.20); the polysiloxane is preferably represented by the formula (I); the alcohol solvent is preferably isoamyl alcohol and/or isooctyl alcohol; the metal catalyst is preferably a chloroplatinic acid catalyst; the mass of the metal catalyst is preferably 0.05-0.1%, and the temperature for heating and reacting is preferably 110-130 ℃, and more preferably 120 ℃; the heating reaction time is preferably 4-6 h, and more preferably 5 h.
Wherein x is the polymerization degree, and x is preferably 20-150.
After the reaction is finished, preferably cooling, more preferably cooling to 60-90 ℃, and then preferably cooling to 70-80 ℃; and then, removing the solvent and micromolecular impurities by vacuum filtration at the temperature to obtain the macromolecular polyether modified polysiloxane.
In the present invention, taking the end-capping reagent as acetic anhydride as an example, the polymer polyether modified polysiloxane is preferably as follows:
in the silicone ether mixed defoaming agent provided by the invention, the content of the high-molecular polyether modified polysiloxane is preferably 25 parts by weight, 30 parts by weight or 20 parts by weight.
The synthesis of the high molecular polyether modified polysiloxane is that a polyether chain segment with hydrophilicity is grafted to a polysiloxane chain segment with hydrophobicity, and the formed siloxane copolymer has the advantages of two defoamers of silicon and ether, namely the polysiloxane segment has the characteristics of quick defoaming, long foam inhibition time, safety, no toxicity and the like, and the polyether segment has the characteristics of high temperature resistance, strong acid and alkali resistance and the like under severe conditions, so that the defoaming performance is more excellent, and the application field is wider.
The content of the fatty alcohol in the silicon ether mixed type defoaming agent is preferably 15-30 parts by weight; in some embodiments provided herein, the fatty alcohol is preferably present in an amount of 20 parts by weight; in some embodiments provided herein, the fatty alcohol is preferably present in an amount of 30 parts by weight; in other embodiments provided herein, the fatty alcohol is preferably present in an amount of 15 parts by weight; the fatty alcohol is preferably one or more of isooctanol, isoamyl alcohol, n-heptanol, dodecanol and tetradecanol.
The content of the cosolvent is preferably 15-30 parts by weight, and more preferably 15-20 parts by weight; the cosolvent is preferably one or more of 120# solvent oil, 200# solvent oil, dearomatized solvent oil D40 and dearomatized solvent oil D60.
The high molecular block polyether in the defoaming agent provided by the invention adopts multi-branched isomeric polyol as an initiator, the synthesized block polyether has high branching degree, the molecular weight is increased in multiple levels, the high-temperature stability of the block polyether is improved, the multi-branched structure is easy to form different surface tensions in different directions on the foam surface, the foam is easy to break, and meanwhile, the defoaming agent is not easy to decompose due to high molecular weight, and the continuity is good; in addition, the polyether chain segment with hydrophilicity is grafted to the polysiloxane chain segment with hydrophobicity, the formed siloxane copolymer has the advantages of silicon and ether defoaming agents, namely the polysiloxane segment has the characteristics of quick defoaming, long foam inhibition time, safety, no toxicity and the like, and the polyether segment has the characteristics of high temperature resistance, strong acid and alkali resistance and the like under severe conditions, so that the defoaming performance is more excellent, and the application field is wider; finally, the high molecular polyether modified polysiloxane and the high molecular weight block polyether are used in a composite mode, so that the good defoaming effect of the high molecular polyether modified polysiloxane and the good foam inhibition effect of the high molecular weight block polyether have a synergistic effect, the reduction of the foam quantity is effectively guaranteed, meanwhile, the high surface active fatty alcohol is matched, the substitution and modification effects of the high molecular polyether modified polysiloxane and the high molecular weight block polyether on the foam surface are promoted, the surface activity of the foam is reduced, and the improvement of the defoaming efficiency is promoted.
The invention also provides a preparation method of the silicon ether mixed defoaming agent, which comprises the following steps: and mixing fatty alcohol and a cosolvent, then sequentially adding high-molecular-weight block polyether and high-molecular-weight polyether modified polysiloxane, and uniformly mixing to obtain the silicon ether mixed defoaming agent.
The invention also provides the application of the silicon ether mixed defoaming agent as a delayed coking defoaming agent.
In order to further illustrate the present invention, the following will describe in detail the preparation method of high molecular weight block polyether, the silicon ether mixed type defoaming agent and the preparation method thereof provided by the present invention with reference to the examples.
The reagents used in the following examples are all commercially available; in the examples of the present invention, unless otherwise specified, the parts are all referred to as molar parts.
Example 1
Adding 1 part by mass of glucose, 0.6 part by mass of 120# solvent oil and 0.1 part by mass of a self-made polymer block polyether product (the preparation method and the process are the same as the embodiment, except that potassium hydroxide alkali metal is used as a catalyst) into a dry high-pressure kettle as a catalyst, filling the high-pressure kettle, replacing air in the kettle with nitrogen for 3 times, starting heating, vacuumizing to remove water when the temperature is increased to 110 ℃, filling nitrogen into the kettle to a micro positive pressure, controlling the temperature in the kettle to be 110 ℃ and the pressure to be 1.5MPa, adding 150 parts by mass of propylene oxide through a feed valve, closing the feed valve, reacting for 3 hours, cooling to 40 ℃ after the reaction is finished, adding 100 parts by mass of ethylene oxide, closing the feed valve, heating to 100 ℃, reacting for 2.5 hours, cooling to 40 ℃ after the reaction is finished, adding 200 parts by mass of propylene oxide, closing the feed valve, heating to 120 ℃, reacting for 2 hours, cooling to 40 ℃ after the reaction, discharging, and carrying out reduced pressure filtration, washing and drying on the product for 3 times to obtain the high molecular weight block polyether.
The hydroxyl value of the product in example 1 is detected to be 10-15mgKOH/g, which represents that the reaction is finished, and the high molecular weight block polyether is obtained.
The product of example 1 was analysed by infrared analysis at 3512cm-1The peak appears as a strong stretching vibration peak of-OH, and is 1211cm-1The strong stretching vibration peak of C-O-C appears, which indicates that polyether molecules are formed, and the number average molecular weight is 5120 by adopting an Agilent liquid mass instrument, which indicates that the product is the expected high molecular block polyether; performing elemental analysis on the product, wherein C: 60%, H: 10%, O: 30%, further indicating the synthesis of high molecular weight block polyethers.
Example 2
2.1 end capping of the high molecular weight block polyethers
The high molecular weight block polyether obtained in example 1 and the end-capping reagent acetic anhydride were mixed in a molar ratio of 1: 6, adding the mixture into a reaction kettle, raising the temperature to 140 ℃ under the protection of nitrogen, reacting for 3 hours, vacuumizing and blowing the nitrogen after the reaction is finished, and blowing out the residual acetic anhydride to obtain the end-sealed high molecular weight block polyether.
2.1 preparation of high-molecular polyether-modified polysiloxanes
Adding the end-sealed high molecular weight block polyether and the polymethylsiloxane oil (with the polymerization degree of 80) prepared in 2.1 into a 250mL three-neck flask provided with a reflux condenser pipe, a thermometer and a stirrer, wherein the molar ratio of the high molecular weight block polyether to the polymethylsiloxane oil is 1:1.1, adding isoamyl alcohol accounting for 10% of the total mass of the end-sealed high molecular weight block polyether and the polymethylsiloxane oil as a solvent, uniformly stirring, observing that the substance in the flask is turbid liquid, raising the reaction temperature to 40 ℃, adding a chloroplatinic acid catalyst accounting for 0.5% of the total mass of the end-sealed high molecular weight block polyether and the polymethylsiloxane oil, continuously raising the reaction temperature to 120 ℃, reacting for 5 hours, cooling to 80 ℃ when the reactant is changed into a light yellow transparent liquid, decompressing and filtering to remove the solvent and micromolecular impurities, and finally obtaining the light yellow viscous liquid, namely the high molecular polyether.
In the formula (I), x is the degree of polymerization, and x is preferably 80.
The product of example 2 was subjected to elemental analysis using atomic absorption to determine the silicon content of 0.53%, where C: 59.46%, H: 9.73%, O: 30.28 percent, which shows the synthesis of the macromolecular polyether modified polysiloxane.
The defoaming rate of the product is 77 percent under the conditions of 300 ℃ and 30mg/kg of dosage, which shows that the qualified high molecular polyether modified polysiloxane is obtained.
Example 3
Calculated by mass portion
The preparation method of the silicon ether mixed defoaming agent comprises the following steps:
adding isoamylol into No. 120 solvent oil, and mixing to obtain a mixed solution a; adding high molecular weight block polyether into the mixed solution a, and mixing to obtain a mixed solution b; and adding the high-molecular silicon ether modified polysiloxane into the mixed solution b, and uniformly mixing to obtain the silicon ether mixed defoaming agent.
Example 4
The preparation method of the silicon ether mixed defoaming agent comprises the following steps:
adding dodecanol into dearomatized solvent oil D60, and mixing to obtain a mixed solution a; adding high molecular weight block polyether into the mixed solution a, and mixing to obtain a mixed solution b; and adding the high-molecular silicon ether modified polysiloxane into the mixed solution b, and uniformly mixing to obtain the silicon ether mixed defoaming agent.
Example 5
The preparation method of the silicon ether mixed defoaming agent comprises the following steps:
adding isooctyl alcohol into 200# solvent oil, and mixing to obtain a mixed solution a; adding high molecular weight block polyether into the mixed solution a, and mixing to obtain a mixed solution b; and adding the high-molecular silicon ether modified polysiloxane into the mixed solution b, and uniformly mixing to obtain the silicon ether mixed defoaming agent.
The application properties of the defoaming agent of the present invention were evaluated by the following experimental data, and comparative example 1 is the high molecular weight polyether-modified polysiloxane obtained in example 2, and comparative example 2 is the high molecular weight block polyether obtained in example 1.
1. Evaluation of defoaming Properties
Adding 200mL of foaming liquid (10% of vacuum residue oil and 90% of coking gas oil in mass ratio) into a 1000mL measuring cylinder, covering the measuring cylinder with a rubber plug, heating to 300 ℃, stabilizing for 10min, then opening an air inlet valve, introducing nitrogen into the system according to 500mL/min, blowing the nitrogen through a gas diffusion head, recording the highest height of a foam layer after the foaming liquid is stable in foaming, namely static foam is unchanged at a certain height for one minute, and recording as H1In mm, quickly adding a defoaming agent solution (the addition ratio of the defoaming agent is 30mg/kg) while recording, and recording the lowest height of a foam layer and recording the lowest height as H2The defoaming ratio η in mm is calculated as follows, and the results of the defoaming property evaluation test are shown in Table 1.
TABLE 1 defoaming Property evaluation test results
| Defoaming rate/%) | |
| Example 3 | 97 |
| Example 4 | 95 |
| Example 5 | 98 |
| Comparative example 1 | 34 |
| Comparative example 2 | 77 |
Under the same conditions and the same dosage, the defoaming performance of the examples 3 to 5 is obviously superior to that of the comparative examples 1 to 2.
2. Dosage evaluation
According to the method of evaluation 1, the dosage of each of examples 3 to 5 was 10, 20 and 30mg/kg, and the dosage of each of comparative examples 1 to 2 was 30, 40 and 50mg/kg, and the results of the tests for obtaining the defoaming ratio are shown in Table 2.
TABLE 2 defoaming Property evaluation test results under different dosing conditions
Under the same test conditions, the addition amount of 10mg/kg in the examples 3-5 is equal to the addition amount of 30mg/kg in the comparative example 2 and is 50mg/kg higher than the addition amount of 50mg/kg in the comparative example 1; the addition amount of 20mg/kg in examples 3-5 is equivalent to the addition amount of 40mg/kg in comparative example 2, the addition amount of 30mg/kg in examples 3-5 is equivalent to the addition amount of 50mg/kg in comparative example 2, and the compound scheme in the invention is obviously superior to the single application effect of the high molecular weight block polyether and polysiloxane in examples 1 and 2.
3. Evaluation of high temperature stability
The test results of the defoaming rates obtained in examples 3 to 5 and comparative examples 1 to 2 were shown in Table 3, which were evaluated by raising the test temperature to 330 ℃ and 360 ℃ according to the method of evaluation 1.
TABLE 3 defoaming Properties evaluation test results under different test temperature conditions
The defoaming rate of the examples 3 to 5 is slightly reduced along with the temperature rise, but the defoaming rate can reach more than 85 percent, the defoaming rate of the comparative example 1 is obviously reduced along with the temperature rise, the defoaming rate of the comparative example 2 is reduced along with the temperature rise, and the defoaming rate is reduced to about 60 percent.
Therefore, the effect of the single application of the high molecular polyether modified polysiloxane and the high molecular block polyether is poor, the defoaming effect is obviously improved after the high molecular polyether modified polysiloxane and the high molecular block polyether are compounded with the fatty alcohol and the cosolvent according to the scheme of the invention, and the addition proportion is obviously reduced. The compound effect is superior to the theoretical effect addition performance of the two.
Claims (10)
1. A silyl ether hybrid defoamer, comprising:
the high molecular weight block polyether is obtained by polymerizing polyol and alkylene oxide;
the high molecular weight polyether modified polysiloxane is obtained by high molecular weight block polyether modified polysiloxane.
2. The silicone ether hybrid defoamer as claimed in claim 1, wherein said polyol is selected from one or more of glucose, fructose, pentaerythritol and glycerol; the alkylene oxide is two or more selected from ethylene oxide, propylene oxide and butylene oxide; the acid anhydride substance is selected from acetic anhydride and/or maleic anhydride.
3. The silicone ether hybrid defoamer as claimed in claim 1, wherein the high molecular weight block polyether comprises the following segments:
wherein m, n and p are polymerization degrees, and m is 20-40; n is 10 to 3, and p is 20 to 40.
4. The silicone ether hybrid defoamer of claim 1, wherein the polysiloxane is according to formula (I):
wherein x is the polymerization degree, and x is 20-150.
5. The silicone ether hybrid defoamer as claimed in claim 1, wherein the fatty alcohol is selected from one or more of isooctanol, isoamyl alcohol, n-heptanol, dodecanol and tetradecanol;
the cosolvent is one or more selected from 120# solvent oil, 200# solvent oil, dearomatized solvent oil D40 and dearomatized solvent oil D60.
6. The silicone ether mixed type defoaming agent according to claim 1, wherein the high molecular weight polyether modified polysiloxane is obtained by modifying polysiloxane after the high molecular weight block polyether is terminated with an anhydride compound.
7. The method of claim 1 for preparing the silyl ether mixed defoamer, comprising:
and mixing fatty alcohol and a cosolvent, then sequentially adding high-molecular-weight block polyether and high-molecular-weight polyether modified polysiloxane, and uniformly mixing to obtain the silicon ether mixed defoaming agent.
8. A method for preparing high molecular weight block polyether is characterized by comprising the following steps:
taking polyhydric alcohol as an initiator, and carrying out ring-opening polymerization reaction with alkylene oxide under the action of a catalyst to obtain high molecular weight block polyether; the catalyst is an alkali metal catalyst and/or a high molecular weight block polyether.
9. The method of claim 8, comprising:
s1) mixing polyalcohol and aliphatic hydrocarbon solvent of C6-C16 with a catalyst, heating and pressurizing in a protective atmosphere, and then adding propylene oxide for reaction to obtain a first intermediate product;
s2) cooling the first intermediate product, adding ethylene oxide, heating and reacting to obtain a second intermediate product;
s3) cooling the second intermediate product, adding propylene oxide, heating and reacting to obtain the high molecular weight block polyether.
10. The method as claimed in claim 9, wherein the molar ratio of the polyol, the catalyst and the propylene oxide in step S1) is 1: (0.01-0.2): (100-200); the reaction temperature is 110-140 ℃; the reaction time is 2-4 h; the reaction pressure is 1.2-1.8 MPa;
the molar ratio of the ethylene oxide to the polyhydric alcohol added in the step S2) is (50-150): 1; the reaction temperature is 80-110 ℃; the reaction time is 1.5-3 h; the reaction pressure is 1.2-1.8 MPa;
the molar ratio of the propylene oxide to the polyhydric alcohol added in the step S3) is (100-200): 1; the reaction temperature is 110-140 ℃; the reaction time is 2-4 h; the reaction pressure is 1.2-1.8 MPa.
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