CN113150261A - Acetylenic diol polyether surfactant, and preparation method and application thereof - Google Patents
Acetylenic diol polyether surfactant, and preparation method and application thereof Download PDFInfo
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- CN113150261A CN113150261A CN202110352866.9A CN202110352866A CN113150261A CN 113150261 A CN113150261 A CN 113150261A CN 202110352866 A CN202110352866 A CN 202110352866A CN 113150261 A CN113150261 A CN 113150261A
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- ethylene oxide
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 106
- 229920000570 polyether Polymers 0.000 title claims abstract description 93
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000002009 diols Chemical class 0.000 title claims description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 208
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 238000007599 discharging Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 claims description 23
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims description 15
- -1 defoamers Substances 0.000 claims description 15
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 5
- RHRRUYIZUBAQTQ-UHFFFAOYSA-N 2,5,8,11-tetramethyldodec-6-yne-5,8-diol Chemical compound CC(C)CCC(C)(O)C#CC(C)(O)CCC(C)C RHRRUYIZUBAQTQ-UHFFFAOYSA-N 0.000 claims description 4
- HCKFFIBKYQSDRD-UHFFFAOYSA-N 4,7-dimethyldec-5-yne-4,7-diol Chemical compound CCCC(C)(O)C#CC(C)(O)CCC HCKFFIBKYQSDRD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000001804 emulsifying effect Effects 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- 238000004321 preservation Methods 0.000 description 15
- 239000002131 composite material Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000003472 neutralizing effect Effects 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
Abstract
The application relates to the technical field of polymer synthesis, and particularly discloses an alkynediol polyether surfactant, and a preparation method and application thereof. An alkynediol polyether surfactant is prepared from alkynediol, methyl oxirane and epoxyethane through ring-opening polymerization. The preparation method comprises the following steps: adding alkynediol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle, adding a catalyst a, opening a vacuum pump, reducing pressure and removing water, introducing methyl ethylene oxide and/or ethylene oxide, and heating for reaction; adding the catalyst b into the reaction kettle, opening a vacuum pump, reducing pressure and removing water, introducing methyl ethylene oxide and ethylene oxide, heating for reaction, cooling and discharging. The preparation method is used for synthesizing the alkynediol polyether, the yield is high, and the alkynediol polyether surfactant synthesized by the method has small molecular weight and good washing effect, emulsifying effect and dispersing effect.
Description
Technical Field
The application relates to the technical field of polymer synthesis, in particular to an alkynediol polyether surfactant, and a preparation method and application thereof.
Background
The surfactant is a substance which can obviously reduce the surface tension of a target solution, has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution. The surfactant has a series of physical and chemical effects of wetting or anti-sticking, emulsifying or demulsifying, foaming or defoaming, solubilizing, dispersing, washing, corrosion prevention, antistatic and the like and corresponding practical application, so that the surfactant becomes a flexible and diversified fine chemical product with wide application. Besides being used as detergents in daily life, surfactants can cover almost all areas of fine chemistry.
Typical surfactants have a relative molecular mass of about several hundred and carbon numbers in the range of C10-C18 and are referred to as low molecular weight surfactants. When the relative molecular mass is increased to 2000 or more, it is conventionally called a high molecular surfactant, and the high molecular surfactant is widely used because it has a better washing action, emulsifying action, and dispersing action than a low molecular surfactant. The synthetic macromolecular surfactant can be prepared by homopolymerization of an amphiphilic monomer or copolymerization of a hydrophilic monomer and a lipophilic monomer and introduction of the amphiphilic monomer on macromolecular substances with better water solubility, and the variety selection and the composition change range of the monomers are wider. The alkynediol polyether high-molecular surfactant is a widely used high-molecular surfactant.
Aiming at the related technologies, when the alkynediol polyether polymer surfactant is prepared by synthesis, the yield is low, and the production cost is greatly increased.
Disclosure of Invention
In order to improve the yield of the alkynediol polyether surfactant and reduce the production cost, the application provides the alkynediol polyether surfactant, and a preparation method and application thereof.
In a first aspect, the present application provides a method for preparing an acetylenic diol polyether surfactant, which adopts the following technical scheme:
a preparation method of an alkynediol polyether surfactant comprises the following steps:
s1, adding alkynediol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle, adding a catalyst a, opening a vacuum pump, reducing pressure and removing water, introducing methyl ethylene oxide and/or ethylene oxide, and heating for reaction to obtain an intermediate product;
s2, adding the catalyst b into the reaction kettle, opening a vacuum pump, reducing pressure and removing water, introducing methyl ethylene oxide and ethylene oxide, heating for reaction, cooling and discharging.
By adopting the technical scheme, the alkynediol is used as an initiator, methyl ethylene oxide and/or ethylene oxide are/is added, and ring-opening polymerization is carried out under the action of a catalyst to obtain the alkynediol polyether surfactant. The preparation method has the advantages that the alkyne diol polyether surfactant is obtained through two-step reaction polymerization, the operation is simple, the reaction condition is controllable, meanwhile, the alkyne diol polyether surfactant is synthesized through the preparation method, the yield is good, the molecular weight of the prepared alkyne diol polyether surfactant is relatively low, and therefore the prepared alkyne diol polyether surfactant has good washing effect, emulsifying effect and dispersing effect.
Preferably, the alkynediol is selected from any one of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 4, 7-dimethyl-5-decyne-4, 7-diol, and 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol.
By adopting the technical scheme, the alkyne diol is used as an initiator, has two polar hydroxyl groups, and can be polymerized with ethylene oxide and methyl ethylene oxide to generate the alkyne diol polyether surfactant.
Preferably, in the S1 and S2, the vacuum pumping is carried out, the pressure is reduced to-0.060 to-0,099 MPa, and the water is removed for 30-60 min.
By adopting the technical scheme, oxygen and water in the air play a role in inhibiting polymerization in the ring opening polymerization reaction, and the water and air content in the reaction system is effectively reduced through the vacuumizing, depressurizing and dewatering process, so that the normal operation of the polymerization reaction is ensured.
Preferably, in the S1 and S2, the reaction temperature is 120-180 ℃, the reaction pressure is 0.1-0.4MPa, and the reaction time is 1-2 h.
By adopting the technical scheme, the reaction temperature range is controlled in the range, when the reaction temperature is lower than 120 ℃, the reaction time can be prolonged, the yield is reduced, and when the reaction temperature is higher than 180 ℃, the synthesized alkynediol polyether surfactant has higher chroma; within the above pressure range, the synthesized alkynediol polyether surfactant has high yield and narrow molecular weight distribution.
Preferably, the catalyst a is selected from any one of potassium hydroxide, calcium oxide and sodium methoxide.
Preferably, the catalyst b is selected from any one of ammonium hydroxide, sodium ethoxide and N-methylmorpholine.
By adopting the technical scheme, a small amount of the catalyst is added into the reaction system, so that the polymerization reaction rate can be obviously accelerated, and the catalyst does not react with each raw material component, and the reaction time is effectively shortened on the premise of not influencing the quantity and quality of the product.
Preferably, the catalyst a and the catalyst b are used in an amount of 0.01 to 0.2 percent of the usage amount of the alkyne diol.
By adopting the technical scheme, the use amount of the catalyst is reduced on the premise of ensuring that the catalyst has certain catalytic activity in the whole reaction process and preventing the synthesis period from being overlong, meanwhile, the post-treatment process of neutralizing or vacuum removing the catalyst is omitted, the production efficiency is improved, and the acetylene glycol polyether surfactant with lower molecular weight and narrower molecular weight distribution can be synthesized.
In a second aspect, the present application provides an acetylenic diol polyether surfactant, which adopts the following technical scheme:
the alkynediol polyether surfactant is prepared by the preparation method of the alkynediol polyether surfactant, and has a structural formula as follows:
R1、R2: h or C1-C10Alkyl groups of (a);
R3、R4、R5、R6: h or methyl;
x: represents the number of ethylene oxides, ranging from 0 to 40;
y: represents the number of methyl oxiranes, and ranges from 0 to 10.
By adopting the technical scheme, compared with a commercial high-molecular surfactant, the alkynediol polyether surfactant has a smaller molecular weight, can be rapidly dispersed in the whole using system, and reduces the occurrence of aggregation and migration phenomena on the surface of the using system, and meanwhile, has lower static and dynamic surface tension, is more suitable for high-speed spraying or rapid roller coating construction, and can rapidly reduce the surface tension when being applied to a dispersing agent of a water-based coating; compared with other commercial polymer surfactants, the alkynediol polyether surfactant has a strong eliminating effect on tiny foams; the alkynediol polyether surfactant has small molecular weight, can not be scattered and damaged in the process of fast dispersion in a use system, and has better stability.
Preferably, x is in the range of 2 to 20; the range of y is 1-5.
By adopting the technical scheme, the alkynediol polyether surfactant has lower molecular weight, and the phenomena of aggregation and migration of the alkynediol polyether surfactant on the surface of a system are further reduced, so that the alkynediol polyether surfactant is rapidly and uniformly dispersed in the whole system.
In a third aspect, the application provides an application of an acetylenic diol polyether surfactant, which adopts the following technical scheme: the application of the alkynediol polyether surfactant in an aqueous coating wetting agent, a defoaming agent, a dispersing agent, a leveling agent and an aqueous ink adhesive.
By adopting the technical scheme, the alkynediol polyether surfactant is applied to the water-based paint defoamer, so that the elimination effect on micro-foam is remarkably improved, and the problems of shrinkage and the like are avoided; the alkynediol polyether surfactant is applied to the water-based paint leveling agent, so that the surface tension of the water-based paint can be effectively reduced; the alkyne diol polyether surfactant is applied to the water-based paint dispersing agent, so that solid and liquid particles of inorganic and organic pigments which are difficult to dissolve in liquid can be uniformly dispersed, and the particles are prevented from settling and coagulating; and the alkynediol polyether surfactant can be rapidly and uniformly dispersed in the whole system, the phenomena of surface migration and the like can not occur, and the influence on later-stage use is reduced.
In summary, the present application has the following beneficial effects:
1. the preparation method disclosed by the application is used for obtaining the alkynediol polyether surfactant through two-step reaction polymerization, the operation is simple, the yield is high, and the prepared alkynediol polyether surfactant has low relative molecular weight and narrow molecular weight distribution;
2. according to the preparation method, by controlling the using amount of the catalyst, the adding amount of the catalyst is reduced on the premise of ensuring that the catalyst has certain catalytic activity in the whole reaction process, so that the step of removing the catalyst by post-treatment can be omitted, and the production efficiency is improved;
3. the alkynediol polyether surfactant synthesized by the application has smaller molecular weight and narrower molecular weight distribution, has stronger eliminating effect on tiny foam, has lower static and dynamic surface tension, is suitable for high-speed spraying or quick roller coating construction, can be quickly and uniformly dispersed in the whole system, and can not be scattered or damaged in the dispersing process.
Detailed Description
The present application will be described in further detail with reference to examples.
The reaction kettle in the embodiment of the application is obtained from Shanghai Europe river mechanical equipment Co., Ltd, and is in the model of AIR-10L;
2,4,7, 9-tetramethyl-5-decyne-4, 7-diol is obtained from Alfa Angsa (China) chemical Co., Ltd., and is not less than 98%;
the 4, 7-dimethyl-5-decyne-4, 7-diol is obtained from Afaha chemical company Limited and is more than or equal to 98 percent;
the 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol is collected from Shanghai Qiao chemical technology Co., Ltd;
methyl oxirane was obtained from Sigma-Aldrich Sigma Aldrich trade, Inc. > 99.5%;
ethylene oxide Sigma-Aldrich Sigma Aldrich trade ltd;
sodium methoxide was obtained from Shanghai Aladdin Biotechnology, Inc., 97%, technical grade;
sodium ethoxide is collected from Shanghai Aladdin Biotechnology, Inc., 98%, Industrial grade;
n-methylmorpholine is collected from Shanghai Aladdin Biotechnology GmbH and is more than or equal to 99%.
Examples
Example 1: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, and carrying out heat preservation reaction for 1 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1h, cooling to 50 ℃ and discharging.
Example 2: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of calcium oxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, and carrying out heat preservation reaction for 1 h;
s2, adding 0.452g of sodium ethoxide into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1h, cooling to 50 ℃ and discharging.
Example 3: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of sodium methoxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, and carrying out heat preservation reaction for 1 h;
s2, adding 0.452g of N-methylmorpholine into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃, the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1h, cooling to 50 ℃ and discharging.
Example 4: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide within 1.5h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, and keeping the temperature and reacting for 1 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 880g of ethylene oxide within 4h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1h, cooling to 50 ℃ and discharging.
Example 5: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 440g of ethylene oxide within 1.5h, controlling the reaction temperature to be 120 ℃, controlling the reaction pressure to be 0.1MPa, and carrying out heat preservation reaction for 1 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 580g of methyl ethylene oxide and 440g of ethylene oxide within 4h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1h, cooling to 50 ℃ and discharging.
Example 6: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 254g of 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.025g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃, the reaction pressure to be 0.1MPa, and carrying out heat preservation reaction for 1 h;
s2, adding 0.508g of ammonium hydroxide into the reaction kettle, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1h, cooling to 50 ℃ and discharging.
Example 7: an acetylenic diol polyether surfactant prepared by the steps of:
s1, melting 198g of 4, 7-dimethyl-5-decyne-4, 7-diol at 70 ℃, adding the melted diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.020g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃, the reaction pressure to be 0.1MPa, and carrying out heat preservation reaction for 1 h;
s2, adding 0.396g of ammonium hydroxide into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1h, cooling to 50 ℃ and discharging.
Example 8: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.080 MPa, removing water for 45min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 150 ℃, controlling the reaction pressure to be 0.3MPa, and carrying out heat preservation reaction for 1.5 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, opening a vacuum pump, reducing the pressure to-0.080 MPa, removing water for 45min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature at 150 ℃ and the reaction pressure at 0.3MPa, preserving the temperature for reaction for 1.5h, cooling to 50 ℃ and discharging.
Example 9: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.099 MPa, dehydrating for 60min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 180 ℃ and the reaction pressure to be 0.4MPa, and carrying out heat preservation reaction for 2 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, opening a vacuum pump, reducing the pressure to-0.099 MPa, removing water for 60min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 180 ℃ and the reaction pressure to be 0.4MPa, keeping the temperature for reaction for 2h, cooling to 50 ℃ and discharging.
Example 10: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.226g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.080 MPa, removing water for 45min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 150 ℃, controlling the reaction pressure to be 0.3MPa, and carrying out heat preservation reaction for 1.5 h;
s2, adding 0.226g of ammonium hydroxide into the reaction kettle, opening a vacuum pump, reducing the pressure to-0.080 MPa, removing water for 45min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 150 ℃ and the reaction pressure to be 0.3MPa, preserving the temperature for reaction for 1.5h, cooling to 50 ℃ and discharging.
Example 11: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.452g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.080 MPa, removing water for 45min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 150 ℃, controlling the reaction pressure to be 0.3MPa, and carrying out heat preservation reaction for 1.5 h;
s2, adding 0.023g of ammonium hydroxide into the reaction kettle, opening a vacuum pump, reducing the pressure to-0.080 MPa, removing water for 45min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature at 150 ℃ and the reaction pressure at 0.3MPa, preserving the temperature for reaction for 1.5h, cooling to 50 ℃ and discharging.
Comparative example
Comparative example 1: an acetylenic diol polyether surfactant prepared by the steps of:
226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol was melted at 65 ℃ and then put into a 2L stirred tank after drying, stirring was started at 300rpm, and nitrogen was substituted three times, at which time the gauge pressure on the tank was-0.098 MPa, 7.4g of triethylamine was sucked in under this pressure, and the final gauge pressure was-0.096 MPa. After 0.5h of catalyst activation, a mixture of ethylene oxide and methyl ethylene oxide (880 g for ethylene oxide and 580g for methyl ethylene oxide) was passed through at 80 ℃ and 0.3MPa gauge. After the heat preservation and curing are finished for 3h, the vacuum pump is started and then the vacuum is carried out, the pressure on the kettle is maintained at-0.098 MPa for 15min, and the temperature is reduced to 50 ℃ for discharging.
Comparative example 2: an acetylenic diol polyether surfactant prepared by the steps of:
226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 5g of potassium hydroxide are added into a reaction kettle, nitrogen is used for replacing air in the reaction kettle for 3 times, then the reaction kettle is vacuumized for 30min at 60 ℃ and under the pressure of minus 0.05MPa, ethylene oxide is introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.2MPa until the total amount of the ethylene oxide is 880g, then the introduction of the ethylene oxide is stopped, and the temperature of the reaction kettle is maintained to be 120 ℃ until the pressure of the reaction kettle does not drop any more, which indicates that the curing reaction is finished. Cooling to 80 ℃, neutralizing with citric acid, dehydrating in vacuum, and filtering to obtain the product of the alkynediol polyether surfactant.
Comparative example 3: an acetylenic diol polyether surfactant prepared by the steps of:
226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 5g N-methylmorpholine are added into a reaction kettle, nitrogen is used for replacing air in the reaction kettle for 3 times, then vacuum pumping is carried out for 30min at the temperature of 60 ℃ and the pressure of-0.05 MPa, ethylene oxide is introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.2MPa until the total amount of the ethylene oxide is 880g, then the introduction of the ethylene oxide is stopped, and the temperature of the reaction kettle is maintained to be 120 ℃ until the pressure of the reaction kettle does not drop any more, which indicates that the curing reaction is finished. Cooling to 80 ℃, neutralizing with citric acid, dehydrating in vacuum, and filtering to obtain the alkynediol polyether surfactant.
Comparative example 4: an acetylenic diol polyether surfactant prepared by the steps of:
226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 5g of composite catalyst are added into a reaction kettle, the composite catalyst is formed by mixing 3g N-methylmorpholine and 2g of potassium hydroxide, air in the reaction kettle is replaced by nitrogen for 3 times, then the reaction kettle is vacuumized for 30min at the temperature of 60 ℃ and the pressure of-0.05 MPa, then ethylene oxide is introduced into the reaction kettle, the reaction temperature is controlled to be 120 ℃ and the reaction pressure is controlled to be 0.2MPa until the total amount of the introduced ethylene oxide is 880g, then the introduction of the ethylene oxide is stopped, the temperature of the reaction kettle is maintained to be 120 ℃ until the pressure of the reaction kettle does not drop any more, and the curing reaction is finished. Cooling to 80 ℃, neutralizing with citric acid, dehydrating in vacuum, and filtering to obtain the product of the alkynediol polyether surfactant.
Comparative example 5: an acetylenic diol polyether surfactant prepared by the steps of:
adding 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 0.113g of composite catalyst into a reaction kettle, wherein the composite catalyst is formed by mixing AlEt3 and dimethylamine according to the weight ratio of 1:3, replacing gas in the kettle for 3 times by nitrogen, heating to 110 ℃, carrying out vacuum dehydration for 1h, controlling the temperature to be 100 ℃, slowly dripping 396g of ethylene oxide within 3h, controlling the pressure to be 0.35Mpa, and curing for 0.5h until the reaction pressure is basically unchanged; then controlling the reaction temperature at 65 ℃, slowly dripping 58g of methyl ethylene oxide within 0.5h, controlling the pressure at 0.35Mpa, and curing for 3h until the reaction pressure is basically unchanged; after the reaction is finished, controlling the temperature at 100 ℃, and degassing for 1h in vacuum to remove unreacted ethylene oxide and methyl ethylene oxide; and reducing the temperature to 65 ℃, neutralizing with citric acid, and cooling to obtain the alkynediol polyether surfactant.
Comparative example 6: an acetylenic diol polyether surfactant prepared by the steps of:
adding 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 0.113g of composite catalyst into a reaction kettle, wherein the composite catalyst is formed by mixing AlEt3 and dimethylamine according to the weight ratio of 1:3, replacing gas in the kettle for 3 times by nitrogen, heating to 110 ℃, carrying out vacuum dehydration for 1h, controlling the temperature to be 100 ℃, slowly dripping 58g of methyl ethylene oxide within 0.5h, controlling the pressure to be 0.35MPa, and curing for 0.5h until the reaction pressure is basically unchanged; then controlling the reaction temperature at 65 ℃, slowly dripping 396g of ethylene oxide within 3h, controlling the pressure at 0.35Mpa, and curing for 3h until the reaction pressure is basically unchanged; after the reaction is finished, controlling the temperature at 100 ℃, and degassing for 1h in vacuum to remove unreacted ethylene oxide and methyl ethylene oxide; and reducing the temperature to 65 ℃, neutralizing with citric acid, and cooling to obtain the alkynediol polyether surfactant.
Comparative example 7: an acetylenic diol polyether surfactant prepared by the steps of:
adding 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol and 0.113g of composite catalyst into a reaction kettle, wherein the composite catalyst is formed by mixing AlEt3 and dimethylamine according to a weight ratio of 1:3, replacing gas in the kettle for 3 times by nitrogen, heating to 110 ℃, carrying out vacuum dehydration for 1h, controlling the temperature to be 100 ℃, slowly dripping 58g of methyl ethylene oxide and 396g of ethylene oxide within 4h, controlling the reaction pressure to be 0.35MPa, curing for 3h until the reaction pressure is basically unchanged, after the reaction is finished, controlling the temperature to be 100 ℃, carrying out vacuum degassing for 1h, removing unreacted ethylene oxide and methyl ethylene oxide, reducing the temperature to 65 ℃, neutralizing by citric acid, and cooling to obtain the alkynediol polyether surfactant.
Comparative example 8: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, and carrying out heat preservation reaction for 1 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃, the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1h, cooling to 50 ℃, neutralizing with citric acid, filtering and discharging.
Comparative example 9: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, and carrying out heat preservation reaction for 1.5 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 120 ℃ and the reaction pressure to be 0.1MPa, keeping the temperature for reaction for 1.5h, cooling to 50 ℃, and discharging.
Comparative example 10: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 80 ℃ and the reaction pressure to be 0.05MPa, and carrying out heat preservation reaction for 1.5 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to 80 ℃ and the reaction pressure to 0.05MPa, keeping the temperature for reaction for 1.5h, cooling to 50 ℃ and discharging.
Comparative example 11: an acetylenic diol polyether surfactant prepared by the steps of:
s1, dissolving 226g of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol at 70 ℃, adding the dissolved diol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle for 5 times, adding 0.023g of potassium hydroxide, opening a vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 190 ℃ and the reaction pressure to be 0.6MPa, and carrying out heat preservation reaction for 1.5 h;
s2, adding 0.452g of ammonium hydroxide into the reaction kettle, opening the vacuum pump, reducing the pressure to-0.060 MPa, removing water for 30min, slowly introducing 290g of methyl ethylene oxide and 440g of ethylene oxide within 3h, controlling the reaction temperature to be 190 ℃ and the reaction pressure to be 0.6MPa, keeping the temperature for reaction for 1.5h, cooling to 50 ℃ and discharging.
Performance test
Taking the acetylene glycol polyether surfactants prepared in examples 1 to 11 and comparative examples 1 to 11 as test objects, respectively, weighing the test objects, and calculating the yield;
the static surface tension of the acetylenic diol polyether surfactants obtained in examples 1 to 11 and comparative examples 1 to 11 was measured according to the cyclics method in GB/T22237-2008 "determination of surface tension of surfactants";
the hydroxyl value of the acetylenic diol polyether surfactants obtained in examples 1 to 11 and comparative examples 1 to 11 was measured according to the phthalic anhydride method in GB T7383-2007 determination of hydroxyl value of nonionic surfactant, and the results are shown in the following Table 1.
As can be seen from the test data in table 1: the hydroxyl value of the alkyne diol polyether surfactants prepared in the embodiments 1-11 of the application is more than 157mgKOH/g, the static surface tension is lower than 30mN/m, and the yield is higher than 83%.
Combining examples 1-11 and comparative examples 1-7, and table 1, it can be seen that the acetylene glycol polyether surfactants prepared in examples 1-11 all have hydroxyl numbers above 157mg KOH/g, while the acetylene glycol polyether surfactants prepared in comparative examples 1-7 all have hydroxyl numbers below 147mg KOH/g, indicating that the acetylene glycol polyether surfactants synthesized by the process of the present application have relatively low molecular weights and possess relatively low static surface tensions. Meanwhile, the yield of the alkynediol polyether surfactant in the examples 1 to 11 is obviously higher than that of the alkynediol polyether surfactant in the comparative examples 1 to 7, which shows that the alkynediol polyether surfactant prepared by the method has higher yield, and the synthesized alkynediol polyether surfactant has lower static surface tension and better washing action, emulsifying action and dispersing action.
By combining example 1 and comparative example 8, and table 1, it can be seen that the hydroxyl value and static surface tension of the acetylenic diol polyether surfactant prepared in example 1 and comparative example 8 are not significantly different, and the yield of the acetylenic diol polyether surfactant prepared by the method of example 1 and comparative example 8 is 84%, which indicates that the preparation steps of the examples of the present application omit the post-treatment process of neutralization or vacuum removal of the catalyst, the product yield and quality are not significantly changed, and the production efficiency is improved.
Combining example 1 and comparative example 9, and table 1, it can be seen that the preparation process of comparative example 9 does not carry out the vacuum water removal process, which results in the presence of water and air in the reaction system, which hinders the normal proceeding of the polymerization reaction, which results in the early termination of the polymerization reaction, and the yield and hydroxyl value of the product are significantly reduced.
As can be seen from the combination of examples 1, 8 and 9 and comparative examples 10 and 11 and Table 1, the preferred reaction temperature in the examples of the present application is 180 ℃ and the preferred reaction pressure is 0.1 to 0.4 MPa. Wherein the optimal reaction dimension is 150 ℃, and the optimal reaction pressure is 0.3 MPa. Within this condition, the reaction has better yield, and the synthesized alkynediol polyether surfactant has lower molecular weight and lower static surface tension. Outside this temperature and pressure range, the reaction time is significantly prolonged while the yield is reduced.
Table 1 results of performance testing
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A preparation method of an alkynediol polyether surfactant is characterized by comprising the following steps:
s1, adding alkynediol into a reaction kettle, introducing nitrogen to replace air in the reaction kettle, adding a catalyst a, opening a vacuum pump, reducing pressure and removing water, introducing methyl ethylene oxide and/or ethylene oxide, and heating for reaction;
s2, adding the catalyst b into the reaction kettle, opening a vacuum pump, reducing pressure and removing water, introducing methyl ethylene oxide and ethylene oxide, heating for reaction, cooling and discharging.
2. The method for producing an alkynediol polyether surfactant according to claim 1, wherein the alkynediol is selected from any one of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 4, 7-dimethyl-5-decyne-4, 7-diol, and 2,5,8, 11-tetramethyl-6-dodecyne-5, 8-diol.
3. The method for preparing the alkynediol polyether surfactant as claimed in claim 1, wherein in S1 and S2, the pressure is reduced to-0.060-0.099 MPa, and the water is removed for 30-60 min.
4. The method for preparing the alkynediol polyether surfactant as recited in claim 1, wherein the reaction temperature in S1 and S2 is 120-.
5. The method for producing an acetylenic diol polyether surfactant according to claim 1, wherein said catalyst a is selected from any one of potassium hydroxide, calcium oxide and sodium methoxide.
6. The method for preparing an acetylenic diol polyether surfactant according to claim 1 wherein said catalyst b is selected from any one of ammonium hydroxide, sodium ethoxide and N-methylmorpholine.
7. The method for preparing an acetylenic diol polyether surfactant according to claim 1 wherein the amount of catalyst a and catalyst b used is 0.01-0.2% of the amount of acetylenic diol used.
8. An acetylenic diol polyether surfactant prepared by the method of any one of claims 1 to 6 and having the formula:
R1、R2: h or C1-C10Alkyl groups of (a);
R3、R4、R5、R6: h or methyl;
x: represents the number of ethylene oxides, ranging from 0 to 40;
y: represents the number of methyl oxiranes, and ranges from 0 to 10.
9. The acetylenic diol polyether surfactant of claim 8 wherein x is in the range of 2-20; the range of y is 1-5.
10. Use of an acetylenic diol polyether surfactant according to any of the claims 8-9 characterised in that the acetylenic diol polyether surfactant is used in aqueous paint wetting agents, defoamers, dispersants, levelling agents and aqueous ink adhesives.
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| US20020055660A1 (en) * | 1999-05-04 | 2002-05-09 | Lassila Kevin Rodney | Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture |
| CN103965461A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Method for synthesizing acetylene alcohol polyoxyethylene ether |
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| US20020055660A1 (en) * | 1999-05-04 | 2002-05-09 | Lassila Kevin Rodney | Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture |
| CN103965461A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Method for synthesizing acetylene alcohol polyoxyethylene ether |
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