CN111116863B - Polyurethane modified organic silicon defoaming agent, preparation method and application - Google Patents
Polyurethane modified organic silicon defoaming agent, preparation method and application Download PDFInfo
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- CN111116863B CN111116863B CN201911402403.8A CN201911402403A CN111116863B CN 111116863 B CN111116863 B CN 111116863B CN 201911402403 A CN201911402403 A CN 201911402403A CN 111116863 B CN111116863 B CN 111116863B
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- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 30
- 239000010703 silicon Substances 0.000 title claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 25
- 239000004814 polyurethane Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 58
- 239000001257 hydrogen Substances 0.000 claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920002545 silicone oil Polymers 0.000 claims abstract description 47
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 42
- 229920000570 polyether Polymers 0.000 claims abstract description 42
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 22
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000013067 intermediate product Substances 0.000 claims abstract description 19
- 239000013530 defoamer Substances 0.000 claims abstract description 17
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 13
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkyne diol Chemical class 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012442 inert solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 claims description 5
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- ZUQAPLKKNAQJAU-UHFFFAOYSA-N acetylenediol Chemical compound OC#CO ZUQAPLKKNAQJAU-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- YDNLNVZZTACNJX-UHFFFAOYSA-N isocyanatomethylbenzene Chemical compound O=C=NCC1=CC=CC=C1 YDNLNVZZTACNJX-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- KZIAXYINKIFPFK-UHFFFAOYSA-N 1,3-diethoxyprop-2-yne-1,1-diol Chemical compound C(C)OC#CC(O)(O)OCC KZIAXYINKIFPFK-UHFFFAOYSA-N 0.000 description 1
- NCEKNYWJCMKNPN-UHFFFAOYSA-N 1,4-diethoxyhex-2-yne-1,1-diol Chemical compound C(C)OC(C#CC(O)(O)OCC)CC NCEKNYWJCMKNPN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- KXUSQYGLNZFMTE-UHFFFAOYSA-N hex-2-yne-1,1-diol Chemical compound CCCC#CC(O)O KXUSQYGLNZFMTE-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
-
- 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
- B01D19/0413—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing N-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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Silicon Polymers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of organic silicon, in particular to a polyurethane modified organic silicon defoaming agent, a preparation method and application thereof. The preparation method of the polyurethane modified organic silicon defoaming agent comprises the following steps: the method comprises the following steps: carrying out hydrosilylation reaction on alkynediol or derivatives thereof, allyl polyether and hydrogen-containing silicone oil under the action of a catalyst at 75-140 ℃ to prepare an intermediate product; step two: the isocyanate group of the alkyl single-end isocyanate reacts with the hydroxyl group of the intermediate product at the temperature of 40-85 ℃ to prepare the polyurethane modified organic silicon defoaming agent; the molecular structural formula of the hydrogen-containing silicone oil contains at least two Si-H bonds. The polyurethane modified organic silicon defoamer prepared by the invention has good defoaming capability and hydrolysis resistance, almost does not change in properties after long-term storage, and can be well used as a defoamer.
Description
Technical Field
The invention relates to the technical field of organic silicon, in particular to a polyurethane modified organic silicon defoaming agent, a preparation method and application thereof.
Background
At present, in the industries of aqueous system coating, printing ink, papermaking, leather and the like, common defoaming agents mainly comprise mineral oil, polyether (without organic silicon) and polyether modified organic silicon. Compared with mineral oil and polyether defoaming agents, the polyether modified silicone defoaming agent is widely applied because the polyether modified silicone defoaming agent can quickly eliminate foam in a system, is less in addition amount, enables surface flaws of a coating film to be less and enables production to be more efficient.
However, the application of the polyether modified silicone defoaming agent brings a headache problem, namely, the defoaming capability is reduced after storage, so that the problem of shrinkage cavity is often caused after storage, at the moment, a large amount of wetting agent has to be added to reduce the surface tension and reduce the generation of shrinkage cavity, the problems are difficult to completely solve on site, the problem of difficult defoaming is caused after the surface tension is reduced by adding the wetting agent, and the problems are difficult to defoam in cycles, the more the formula is, the more the problem is complicated, the cost is increased, and the stability of the product is difficult to ensure.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a polyurethane-modified silicone defoamer which hardly decreases in defoaming ability after long-term storage, a preparation method and use thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a polyurethane modified organic silicon defoaming agent comprises the following steps:
the method comprises the following steps: carrying out hydrosilylation reaction on alkynediol or derivatives thereof, allyl polyether and hydrogen-containing silicone oil under the action of a catalyst at 75-140 ℃ to prepare an intermediate product;
step two: the isocyanate group of the alkyl single-end isocyanate reacts with the hydroxyl group of the intermediate product at the temperature of 40-85 ℃ to prepare the polyurethane modified organic silicon defoaming agent;
the molecular structural formula of the hydrogen-containing silicone oil contains at least two Si-H bonds.
The term "reacting" as used herein generally refers to a sufficient reaction.
The alkyne diol or the derivative thereof, the allyl polyether and the hydrogen-containing silicone oil are mixed for carrying out hydrosilylation reaction, the alkyne diol or the derivative thereof and the allyl polyether are grafted to the hydrogen-containing silicone oil through multiple bonds contained in the alkyne diol or the derivative thereof and at least two Si-H bonds contained in the molecular structural formula of the hydrogen-containing silicone oil to obtain an intermediate product, and the intermediate product is reacted with alkyl single-end-group isocyanate through alcoholic hydroxyl contained in the intermediate product to prepare the organic silicon defoaming agent containing carbamate functional groups (NHCOO) in the molecule, wherein the organic silicon defoaming agent can be an organic silicon defoaming agent containing more than 2 carbamate functional groups (NHCOO) in a single molecule.
Wherein, the multiple bond refers to a bond which can carry out silicon hydrogen addition reaction with a Si-H bond of hydrogen-containing silicone oil, and can be a carbon-carbon double bond or a carbon-carbon triple bond.
Through reaction, the obtained polyurethane modified organic silicon defoaming agent has strong defoaming capability and can be stored for a long time.
Since one hydrogen-containing silicone oil molecule contains at least two Si-H bonds, in the reaction of the step one, the reaction can be as follows: at least one Si-H bond in the hydrogen-containing silicone oil molecule and one alkyne diol or derivative molecule thereof are subjected to hydrosilylation reaction, so that the alkyne diol or derivative thereof is grafted to the hydrogen-containing silicone oil molecule; and (3) carrying out hydrosilylation reaction on at least one Si-H bond in the rest of the hydrogen-containing silicone oil molecule and one allyl polyether molecule, so that the allyl polyether is grafted to the hydrogen-containing silicone oil molecule.
The alkyl single-ended isocyanate in the present invention means a substance having an isocyanate group at one end of an alkyl group.
As a further improvement, the molecular structural formula (first formula) of the alkynediol is:
wherein z and g are integers, z is more than or equal to 0 and less than or equal to 4, and g is more than or equal to 0 and less than or equal to 4; r' is C0-C12Alkyl groups of (a);1r' is C0-C12Alkyl group of (1).
The molecular structural formula (second general formula) of the allyl polyether is as follows:
wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 12; y is more than or equal to 0 and less than or equal to 14, and when one of x and y is 0, the other is more than zero; r' is any one of hydrogen radical, methyl, ethyl or butyl;
the molecular structural formula (third general formula) of the hydrogen-containing silicone oil is as follows:
wherein, 1) a is more than or equal to 0, b is more than or equal to 2, and a and b are integers.
As a further improvement, the ratio of the amount of the substance with multiple bonds in the alkyne diol or derivative thereof and the allyl polyether to the amount of the substance with Si-H bonds in the hydrogen-containing silicone oil is as follows: (0.8-1.1):1, and the amount of the substance of the acetylenic diol or derivative thereof and the alkyl single-ended isocyanate is (0.5-1.9): 1; the mass ratio of the acetylenic diol or derivative thereof to the allyl polyether is (0.4-4.5): 1.
As a further improvement, the hydrogen content of the hydrogen-containing silicone oil is between 0.2 and 0.75 percent; the average molecular weight is between 500 and 3000; the alkyl single-terminal isocyanate is C7-C18The alkyl single-terminal isocyanate of (1).
As a further improvement, the alkyl single-end group isocyanate is one or more of octadecyl isocyanate, dodecyl isocyanate and benzyl isocyanate.
As a further improvement, the concrete preparation method of the polyurethane modified organic silicon defoamer comprises the following steps:
the method comprises the following steps: slowly stirring and mixing the alkynediol or the derivative thereof, the allyl polyether, the catalyst and the hydrogen-containing silicone oil at 75-115 ℃, and then stirring and reacting at 100-140 ℃ for 3-6 hours to obtain an intermediate product;
step two: and then slowly stirring and uniformly mixing the intermediate product and the alkyl single-end isocyanate at the temperature of between 40 and 45 ℃, then heating to between 78 and 85 ℃, preserving the temperature, stirring and reacting for 3 hours to obtain the product.
The term "slow" as used herein means a speed at which the occurrence of gel phenomenon is avoided as much as possible during the reaction and the reaction proceeds smoothly without the occurrence of gel, for example: when 150 g of a mixture of acetylenic diol or derivative thereof, allyl polyether and catalyst is to be added to the hydrogen-containing silicone oil, the addition time may be 2-3 hours.
As a further improvement, the reaction of the first step is a reaction carried out in the presence of a solvent and a catalyst, the solvent being an inert solvent with respect to the reactions of the first and second steps; the inert solvent is xylene or an ester solvent; the catalyst is a Kaster catalyst or chloroplatinic acid; and after the product is obtained in the step two, the product is subjected to a vacuumizing impurity removal process at 120 ℃.
As a further improvement, the concrete preparation method of the polyurethane modified organic silicon defoamer comprises the following steps:
step A), adding an inert solvent into a container, and refluxing to remove water;
step B): adjusting the temperature in the container to 75-115 ℃, adding hydrogen-containing silicone oil into the container, gradually dropwise adding a mixture of allyl polyether, alkynediol or derivatives thereof and a catalyst into the container, uniformly dropwise adding for 6-8 hours, and maintaining the temperature of 100-140 ℃ for reaction for 3-6 hours;
step C): then cooling to 40-45 ℃, dropwise adding the alkyl single-end isocyanate into the container for 2-3 hours (namely, the dropwise adding time is 2-3 hours), then heating to 78-85 ℃, keeping for 3 hours, heating to 120 ℃, vacuumizing and removing the solvent and the unreacted monomer (or removing impurities);
in steps A), B) and C), the addition, reaction and evacuation are carried out under stirring.
The invention also provides a polyurethane modified organic silicon defoaming agent which is prepared by the preparation method.
The polyurethane modified organic silicon defoaming agent can be used as a defoaming agent to be well applied to coating.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the problem that the defoaming agent is easy to precipitate and layer after being stored in the existing water-based system and further the defoaming capability is reduced, the alkyne diol or the derivative thereof, the allyl polyether and the hydrogen-containing silicone oil are subjected to hydrosilylation reaction under the action of a catalyst to graft the alkyne diol or the derivative thereof and the allyl polyether to the hydrogen-containing silicone oil to obtain an intermediate product; then reacting alkyl single end group isocyanate with an intermediate product to prepare an organic silicon defoaming agent containing carbamate functional groups in a single molecule; the defoaming agent not only has strong defoaming capability and good hydrolysis resistance, but also is not easy to separate out or layer after being stored for a long time, still has strong defoaming capability, simultaneously does not bring the problem of film shrinkage, and can well meet the use requirement.
Detailed Description
The present invention will be further described with reference to the following examples.
It should be noted that the raw materials used in the technical scheme provided by the present invention, except for the specific description, are prepared by conventional means or purchased through commercial channels.
The alkyne diol and the derivatives thereof are grafted to hydrogen-containing silicone oil molecules in a matched manner with allyl polyether, so that good compatibility and low dynamic surface can be provided for the polyurethane modified organic silicon defoamer when the polyurethane modified organic silicon defoamer is applied to a coating system, and a hydrophobic section connected with carbamate on the molecules of the polyurethane modified organic silicon defoamer in the coating system is associated with hydrophobic structures such as latex particles, surfactants, pigments and the like to form a three-dimensional network structure, so that the alkyne diol has strong defoaming capability and good hydrolysis resistance, can not be separated out or layered after storage, still has strong defoaming capability, does not bring about the problem of film shrinkage, and generates unexpected technical effects.
The silicone antifoaming agent in the present invention may be a silicone antifoaming agent containing two or more carbamate functional groups in a single molecule.
A preparation method of a polyurethane modified organic silicon defoaming agent comprises the following steps:
the method comprises the following steps: carrying out hydrosilylation reaction on alkynediol or derivatives thereof, allyl polyether and hydrogen-containing silicone oil under the action of a catalyst at 75-140 ℃ to prepare an intermediate product;
step two: reacting isocyanate group of alkyl single-end isocyanate with hydroxyl of an intermediate product at 40-85 ℃ to prepare a polyurethane modified organic silicon defoaming agent;
the molecular structural formula of the hydrogen-containing silicone oil contains at least two Si-H bonds.
Preferably, the molecular structural formula (first formula) of the acetylenic diol is:
wherein z and g are integers, z is more than or equal to 0 and less than or equal to 4, and g is more than or equal to 0 and less than or equal to 4; r' is C0-C12Alkyl of (2)A group;1r' is C0-C12Alkyl group of (1).
The molecular structural formula (second general formula) of the allyl polyether is as follows:
wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 12; y is more than or equal to 0 and less than or equal to 14, and when one of x and y is 0, the other is more than zero; r' is any one of hydrogen radical, methyl, ethyl or butyl;
the molecular structural formula (third general formula) of the hydrogen-containing silicone oil is as follows:
wherein, 1) a is more than or equal to 0, b is more than or equal to 2, and a and b are integers.
Preferably, the ratio of the amount of the substance having multiple bonds in the acetylenic diol or derivative thereof and the allyl polyether to the amount of the substance having Si — H bonds in the hydrogen-containing silicone oil is: (0.8-1.1):1, and the amount of the substance of the acetylenic diol or derivative thereof and the alkyl single-ended isocyanate is (0.5-1.9): 1; the mass ratio of the acetylenic diol or derivative thereof to the allyl polyether is (0.4-4.5): 1. The average molecular weights used for allyl polyether and hydrogen-containing silicone oil were calculated.
Preferably, the hydrogen content of the hydrogen-containing silicone oil is between 0.2 and 0.75 percent; the average molecular weight is between 500 and 3000; the alkyl single-terminal isocyanate is C7-C18The alkyl single-terminal isocyanate of (1).
Preferably, the alkyl single-end isocyanate is one or more of octadecyl isocyanate, dodecyl isocyanate and benzyl isocyanate.
Preferably, the preparation method comprises the following steps:
the method comprises the following steps: slowly stirring and uniformly mixing the alkynediol or the derivative thereof, the allyl polyether and the catalyst with the hydrogen-containing silicone oil at 75-115 ℃ (the mixture of the alkynediol or the derivative thereof, the allyl polyether and the catalyst can be slowly and uniformly mixed with the hydrogen-containing silicone oil), and then carrying out heat preservation and stirring reaction at 100-140 ℃ for 3-6 hours to obtain an intermediate product;
step two: and then slowly stirring and uniformly mixing the intermediate product and the alkyl single-end isocyanate at the temperature of between 40 and 45 ℃, and then heating to between 78 and 85 ℃ (preferably 80 ℃) to carry out heat preservation and stirring reaction for 3 hours to obtain the product.
Preferably, the preparation method comprises the following steps: the reaction in the first step is carried out in the presence of a solvent and a catalyst, wherein the solvent is an inert solvent (i.e. does not react with other substances in the system) relative to the reactions in the first step and the second step; the inert solvent is xylene or an ester solvent; the catalyst is a Kaster catalyst or chloroplatinic acid; and after the product is obtained in the step two, the product is subjected to a vacuumizing impurity removal process at 120 ℃. After vacuumizing and impurity removal, the obtained product can be filtered to obtain filtrate, and impurity removal is further performed.
The amount of the Kanst catalyst or chloroplatinic acid is an amount such that the reaction proceeds normally, and for example, the amount of the Kanst catalyst and the amount of the chloroplatinic acid solution (the chloroplatinic acid is added to the system in the form of the chloroplatinic acid solution) are both 0.005 to 0.01% by mass of the total mass of the acetylenediol or its derivative, the allyl polyether and the hydrogen-containing silicone oil.
In examples 1 to 4, unless otherwise specified, the molecular structural formula of the alkynediol is the first general formula; the molecular structural formula of the allyl polyether is a second general formula; the molecular structural formula of the hydrogen-containing silicone oil is a third general formula.
In examples 1 to 4, the hydrogen content of the hydrogen-containing silicone oil means the content of hydrogen in the silicon-hydrogen bond of the hydrogen-containing silicone oil in percentage by mass to the hydrogen-containing silicone oil.
In examples 1 to 4, the molecular weight of allyl polyether is the average molecular weight, which is determined by the product supplier at the time of purchase of the product, since there are some impurities (some values of x and y are deviated (very few x and y are fluctuated)) except for the main portion in the second formula. The molecular weight of the hydrogen-containing silicone oil is also an average molecular weight, which may be given by the product supplier at the time of purchase of the product. The chloroplatinic acid solution isAn aqueous chloroplatinic acid solution having a chloroplatinic acid content of 8%.1R 'is a branched or branched alkyl group and R' is a branched or branched alkyl group.
In the second formula of the present invention, x and y refer to x and y of the main part.
The molecular weight of the present invention is the number average molecular weight.
Example 1
Step 1): adding 200 g of dimethylbenzene into a four-neck flask, and refluxing for 2 hours at 140 ℃ to remove water;
step 2): the temperature in the four-necked flask was lowered to 75 ℃, 220 g (0.11mol) of hydrogen-containing silicone oil (hydrogen content: 0.2%, average molecular weight: 2000) was added to the four-necked flask, and 195 g (0.30mol) of allyl polyether (i.e., x is 0; y is about 14; R' is methyl, average molecular weight: 650; also called allyl polyethylene glycol monomethyl ether), 40.2 g of acetylenediol (z is 2; g is 2 in the first formula),1r' is C4R' is C4The alkyl group is also called tetraethoxydecynediol, the molecular weight is 346,0.12mol) and 0.0414g of chloroplatinic acid solution, after the dropwise addition is completed for 6 hours, the temperature is gradually increased to 110 ℃, and the reaction is maintained at 100 ℃ and 120 ℃ for 6 hours;
step 3): then the temperature is reduced to 40 ℃, 68.5 g (molecular weight is 295.5, 0.23mol) of octadecyl isocyanate is dripped into the container for 2 hours, the temperature is increased to 80 ℃ and kept for 3 hours, then the temperature is increased to 120 ℃, and the container is vacuumized for 1 hour (the vacuum degree is more than-0.09) to remove the solvent and the unreacted monomer. Sample 1 was prepared.
Example 2
Step 1): adding 200 g of dimethylbenzene into a four-neck flask, and refluxing at 140 ℃ for 2 hours to remove water;
step 2): the temperature in the four-necked flask was lowered to 95 ℃ and 110 g of hydrogen-containing silicone oil (hydrogen content 0.4%, average molecular weight 1500, 0.07mol) was added to the four-necked flask, and then 110 g of allyl polyethylene glycol polypropylene glycol monobutyl ether (i.e., in the second formula: x is about 12; y is about 9; R' is butyl; average molecular weight 1100,0.10mol) and 29.8 g of hexynediol (i.e., in the first formula: z and g are both 0,1r' is-CH2-CH2-, R' is-CH2-CH2114,0.26mol) and 0.0139g of a Karsted catalyst, dropping at a constant speed, gradually raising the temperature to 120 ℃ after 8 hours of dropping, and maintaining the temperature between 120 ℃ and 130 ℃ for 3 hours;
step 3): then the temperature is reduced to 40 ℃, 31.8 g (0.15mol) of dodecyl isocyanate is dripped into the container for 3 hours, then the temperature is increased to 80 ℃ and kept for 3 hours, and then the temperature is increased to 120 ℃ and the vacuum is pumped for 1 hour (the vacuum degree is more than-0.09) to remove the solvent and the unreacted monomer. Sample 2 was prepared.
Example 3
Step 1): adding 200 g of dimethylbenzene into a four-neck flask, and refluxing for 2 hours at 140 ℃ to remove water;
step 2): the temperature in the four-necked flask was lowered to 115 ℃ and 200 g of hydrogen-containing silicone oil (hydrogen content: 0.5%, molecular weight: 500, 0.4mol) was added to the four-necked flask, and 150 g of allyl polypropylene glycol monomethyl ether (molecular weight: about 750, i.e., x: about 12, y: 0, R' is methyl; 0.20mol), 181.8 g of diethoxy hexynediol (i.e., in the first formula,2r' is-CH2-CH2-, R' is-CH2-CH2-z and g are both 1; a molecular weight of 202; 0.90mol) and 0.0367g of chloroplatinic acid solution, gradually raising the temperature to 130 ℃ after the dropwise addition of the chloroplatinic acid solution at a constant speed for 8 hours, and maintaining the temperature between 120 ℃ and 140 ℃ for 3 hours;
step 3): and cooling to 40 ℃, dropwise adding 181.8 g (0.86mol) of dodecyl isocyanate into the container for 3 hours, heating to 80 ℃, keeping for 3 hours, then maintaining at 120 ℃, and vacuumizing for 1 hour (the vacuum degree is more than-0.09) to remove the solvent and unreacted monomers, thus obtaining a sample 3.
Example 4
Step 1): adding 200 g of dimethylbenzene into a four-neck flask, and refluxing at 140 ℃ for 2 hours to remove water;
step 2): the temperature in the four-necked flask was lowered to 75 ℃ and 160 g of hydrogen-containing silicone oil (hydrogen content 0.75%, average molecular weight 3000; 0.05mol) was added to the four-necked flask, and 160 g of allyl polyethylene glycol monobutyl ether (average molecular weight 400, i.e., the second one) was gradually added dropwise to the four-necked flaskIn the three general formula, y is 6 and 7, and R' is butyl; 0.40mol), 131.2 g diethoxypropynediol (i.e. in the first formula,1r' is-CH2-, R "is not taken or R" is-CH2-,1R' is not taken, and z and g are both 1; molecular weight 160,0.82mol) and 0.0415g of Kaster catalyst, gradually raising the temperature to 130 ℃ after the uniform dropping for 6 hours, and maintaining the temperature between 130 ℃ and 140 ℃ for 6 hours.
Step 3): then, the temperature was decreased to 45 ℃, 130.7 g (about 0.44mol) of octadecyl isocyanate was added dropwise for 2 hours, the temperature was increased to 80 ℃ and maintained for 3 hours, then the temperature was maintained at about 120 ℃, and the vacuum was applied for 1 hour (vacuum degree-0.09 or more) to remove the solvent and unreacted monomer, thereby obtaining sample 4.
In examples 1 to 4, the dropwise addition, the reaction and the evacuation were all performed under stirring, that is, the reactions of steps 1), 2) and 3) in the four-necked flask were all performed under stirring, and the dropwise addition process of steps 2 and 3) was performed under stirring, so that the various substances were uniformly mixed during and after the dropwise addition; the speed of the stirring paddle can be 100-300r/min during stirring.
And (4) testing results:
preparation of samples
Step 1): 680 g of water-soluble acrylic resin (DSM; model: Neocryl XK14) and 120 g of deionized water were added to a 1000 ml vessel A and uniformly dispersed to obtain a mixture;
step 2): the mixture prepared in step one is divided into 8 equal parts on average, each part is placed into a 200ml container B, and 0.2 g of each of 1 to 4 samples and 4 commercially available antifoaming agents is taken and added into each container B to obtain 8 samples.
Step 3): the substances in each container B were mixed uniformly, and after standing for 2 hours, the foam suppressing ability and appearance of the sample in each container B were tested.
Of these, 4 commercially available defoamers were sample 5 (100% mineral oil type defoamer), sample 6 (100% polyether type defoamer), sample 7 (100% polyether modified silicone) and sample 8 (100% polyether modified silicone);
the 8 samples were: sample 1 (sample added to container B is sample 1), sample 2 (sample added to container B is sample 2), sample 3 (sample added to container B is sample 3), sample 4 (sample added to container B is sample 4), sample 5 (sample added to container B is commodity 1), sample 6 (sample added to container B is commodity 2), sample 7 (sample added to container B is commodity 3), and sample 8 (sample added to container B is commodity 4).
Defoaming capability test:
1. samples 1-8 were shaken in a shaker for 10 minutes, then poured into 8 graduated bottles (bottles are cylindrical; volume 200mL, height 20cm), respectively, and the initial bubble bath height was noted, followed by recording the foam height for 2 hours and 24 hours in sequence.
2. After the samples 1-8 were stored at 50 ℃ for 14 days, they were put into a shaker and shaken for 10 minutes, and then poured into 8 bottles with scales (the bottles were cylindrical; volume was 100mL, height was 6cm), and the initial bubble bath height was recorded, and then the foam heights were recorded for 2 hours and 24 hours in order.
The oscillator is purchased from Shanghai modern instruments Co., Ltd, the reciprocating frequency during oscillation is 680 times/min, and the swing angle is 15 degrees multiplied by 2 degrees to 30 degrees. The results are shown in Table 1.
3. The defoaming condition of the sample can be tested after 3 parts of each sample is prepared, the defoaming condition of the sample is tested after another 3 parts of the sample is stored for 14 days, and the data is averaged.
TABLE 1
The data in Table 1 show that the polyurethane modified defoamer prepared according to the invention has strong defoaming property, and the foam of the sample added with the product of the invention is much lower than that of the product on the market.
In addition, after the 50 ℃ heat storage (namely 50 ℃ storage) for 14 days, the defoaming capability of the defoaming agent prepared by the invention is hardly reduced, the defoaming capability of the defoaming agent sold on the market is greatly reduced, and the initial foam height is increased from 130mm to 140mm from 120 mm; the foam height after 2 hours was also significantly higher than the product of the invention, indicating a significant improvement in the product of the invention.
Paint film compatibility and gloss
Preparation of the scraper: each sample was coated on a flat plate, the sample was pressed with a film maker (the film maker is a hollow object having left and right side faces and a top face), then the film maker was pulled up so that the thickness of the coated film (paint film) was 100 μm, and after the coated film was dried, various properties of the coated film (in this case, a dry film) were measured, and this process for preparing a dry film was also called a process of a squeegee.
The state of the dry film was observed, compatibility was judged, and then gloss was measured. The results are shown in Table 2. Wherein, the compatibility judgment standard is that the permeability of the coating film is gradually increased from 1-5 grades, 5 grades are the most permeable, 1 grade is the least permeable, and the more permeable shows that the compatibility is better.
The glossiness is tested by a specular gloss meter with an incidence angle of 60 degrees, and the higher the glossiness is, the fewer the shrinkage holes are, and the better the compatibility of the coating film is.
TABLE 2
The data in Table 2 show that the polyurethane modified defoamer prepared by the invention has good compatibility, and the transparency of the polyurethane modified defoamer is much better than that of the product on the market.
The compatibility of the prepared defoaming agent is not reduced after the defoaming agent is stored for 14 days at 50 ℃, and the compatibility of samples on the market is reduced after the samples are stored for 14 days at 50 ℃.
In the present invention, C0Is meant to be free of carbon groups.
The allyl polyether in the invention can be purchased from Nantong morning-moisturizing chemical industry Co., Ltd, Hangzhou Danwei technology Co., Ltd, or from other companies.
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the embodiments are only used to help understanding the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, there may be variations in the specific implementation manners and application ranges, and in summary, the content of the present description should not be construed as a limitation to the present invention.
Claims (9)
1. A preparation method of a polyurethane modified organic silicon defoaming agent is characterized by comprising the following steps:
the method comprises the following steps: carrying out hydrosilylation reaction on alkynediol or derivatives thereof, allyl polyether and hydrogen-containing silicone oil under the action of a catalyst at 75-140 ℃ to prepare an intermediate product;
step two: the isocyanate group of the alkyl single-end isocyanate reacts with the hydroxyl group of the intermediate product at the temperature of 40-85 ℃ to prepare the polyurethane modified organic silicon defoaming agent;
the molecular structural formula of the hydrogen-containing silicone oil contains at least two Si-H bonds.
2. The method of claim 1, wherein the method comprises: the ratio of the quantity of the multiple bonds in the alkyne diol or the derivative thereof and the allyl polyether to the quantity of the Si-H bonds in the hydrogen-containing silicone oil is as follows: (0.8-1.1):1, and the amount of the substance of the acetylenic diol or derivative thereof and the alkyl single-ended isocyanate is (0.5-1.9): 1; the mass ratio of the acetylenic diol or derivative thereof to the allyl polyether is (0.4-4.5): 1.
3. The method for producing the urethane-modified silicone antifoaming agent according to claim 1, wherein the hydrogen content of the hydrogen-containing silicone oil is between 0.2 and 0.75%; the average molecular weight is between 500 and 3000.
4. The method for preparing the polyurethane modified silicone defoamer according to claim 3, wherein the alkyl single-end isocyanate is one or more of octadecyl isocyanate and dodecyl isocyanate.
5. The method of claim 1, wherein the method comprises:
the method comprises the following steps: slowly stirring and uniformly mixing the alkynediol or the derivatives thereof, the allyl polyether, the catalyst and the hydrogen-containing silicone oil at 75-115 ℃, and then stirring and reacting at 100-140 ℃ for 3-6 hours to obtain an intermediate product;
step two: and then slowly and uniformly mixing the intermediate product and the alkyl single-end isocyanate at the temperature of between 40 and 45 ℃, and then heating to between 78 and 85 ℃ and carrying out heat preservation and stirring reaction for 3 hours to obtain the product.
6. The method of claim 5, wherein the method comprises: the reaction in the first step is carried out in the presence of a solvent and a catalyst, wherein the solvent is an inert solvent relative to the reaction in the first step and the reaction in the second step; the inert solvent is xylene or an ester solvent; the catalyst is a Kaster catalyst or chloroplatinic acid; and after the product is obtained in the step two, the product is subjected to a vacuumizing impurity removal process at 120 ℃.
7. The method of claim 5, wherein step A) comprises adding an inert solvent to a vessel, and refluxing to remove water;
step B): adjusting the temperature in the container to 75-115 ℃, adding hydrogen-containing silicone oil into the container, gradually dropwise adding a mixture of allyl polyether, alkynediol or derivatives thereof and a catalyst into the container, uniformly dropwise adding for 6-8 hours, and maintaining the temperature of 100-140 ℃ for reaction for 3-6 hours;
step C): then cooling to 40-45 ℃, dropwise adding alkyl single-end isocyanate into the container for 2-3 hours, heating to 78-85 ℃ for 3 hours, heating to 120 ℃, and vacuumizing to remove the solvent and unreacted monomers;
the dripping, the reaction and the vacuum pumping are all carried out under the stirring condition; the mass of the catalyst is 0.005-0.01% of the total mass of the alkynediol or the derivative thereof, the allyl polyether and the hydrogen-containing silicone oil.
8. A polyurethane-modified silicone defoaming agent characterized by being produced by the production method according to any one of claims 1 to 7.
9. The use of the polyurethane-modified silicone defoamer of claim 8, wherein the polyurethane-modified silicone defoamer is used as a defoamer in a coating film.
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