CN108341957A - Polyurethane material antifoaming agent and preparation method thereof - Google Patents
Polyurethane material antifoaming agent and preparation method thereof Download PDFInfo
- Publication number
- CN108341957A CN108341957A CN201810002679.6A CN201810002679A CN108341957A CN 108341957 A CN108341957 A CN 108341957A CN 201810002679 A CN201810002679 A CN 201810002679A CN 108341957 A CN108341957 A CN 108341957A
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- CN
- China
- Prior art keywords
- antifoaming agent
- present
- disilazane
- silane
- chlorosilane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
- C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Abstract
The present invention relates to polyurethane material antifoaming agent and preparation method thereof.The antifoaming agent of the present invention comprising following following raw materials by being made：Methanol or hexylene glycol, silane and disilazane.The antifoaming agent of the present invention can effectively improve the intensity and elongation percentage of product, the bubble of interiors of products be eliminated, to improve product quality.
Description
Technical field
The present invention relates to the preparation of antifoaming agent in polyurethane elastomer and use, belong to disappearing used in polyurethane material
Infusion field.
Technical background
Polyurethane is also referred to as polyurethanes, is the macromolecular compound containing repetition carbamate groups on main chain
General designation.It is typically to be polymerized with dihydroxy or polyol by organic diisocyanate or polyisocyanates.It is poly-
The purposes of urethane is very extensive, such as it can replace rubber, plastics and nylon etc., small for school, airport, hotel, house
Area and landscaping etc..In polyurethane process, needs that bubble rate in antifoaming agent reduction process is added, promoted
Product quality.
The isocyanate material for preparing polyurethane is easy to generate unstable carbamic acid with reacting for water, then resolves into
Carbon dioxide and amine.If isocyanates is excessive, can the reaction was continued generate substituted urea.Monocomponent moisture cure type polyurethane adhesive
Exactly cured using above-mentioned reaction, and two component polyurethane jelly is bonded in wet environment, glue-line easy tos produce
Bubble, adhesive strength can reduce 10%-20%.
Antifoaming agent majority belongs to physical defoaming agent, defaoming mechanisms currently on the market：Its molecule is taken a walk in foam surface, soon
Speed is sprawled, and is formed very thin double film layers, is further spread, infiltration, stratiform is fallen asleep, to replace former foam wall, due to its surface
Tension is low, can flow to the liquid for generating foam high surface tension, the defoaming agent molecule of such low surface tension is between gas-liquid interface
Constantly diffusion, infiltration period membranous wall is thinning, and foam is drawn by the strength of the big film layer of circumferential surface tension again simultaneously, causes to steep
Foam ambient stress is unbalance, to achieve the purpose that brokenly bubble.
Current antifoaming agent on the market is based on organic silicon, including polysiloxane solution, modified polyorganosiloxane solution, containing thin
The polysiloxanes of water particle.
CN105400175A discloses a kind of polyurethane antifoaming agent, is made of the raw material of following parts by weight：Dimethyl
3-5 parts of silicone oil, 1.2-1.5 parts of dimethyl sulfoxide (DMSO), 2-3 parts of diphenyl carbazone, 1.5-2 parts of sodium tripolyphosphate, poly- naphthaldehyde
3-5 parts of sulfonate sodium, 4-6 parts of sodium metnylene bis-naphthalene sulfonate, 3-5 parts of polyethylene glycol.The polyurethane antifoaming agent can reduce poly-
Bubble generation rate in the process of urethane product promotes the quality and yield rate of product, reduces the generation of product defect.But
The composition proportion of the antifoaming agent is complicated, and its dimethyl sulfoxide (DMSO) contained has strong water imbibition, is easy to further result in poly-
Urethane generates bubble.
Methyl-silicone oil has low surface tension, low aqueous solubility, high activity, low volatility, chemical inertness, nothing as antifoaming agent
The characteristics such as physiological-toxicity, antifoaming speed is fast, the suds time is long, widely applicable, but heat-resisting quantity is poor, and strong basicity resisting is weak.
CN107469414A discloses a kind of organosilicon containing the trapezoidal fluorohydrocarbon base silsesquioxane copolymer of dimethyl silicone polymer-and disappears
Infusion and preparation method thereof, the raw material of the organic silicon defoamer form percentage and are：Dimethyl silicone polymer-ladder
Shape fluorohydrocarbon base silsesquioxane copolymer 10~30%, dimethicone 10~30%, hydrophobic silicic aerogels 4~8%, emulsifier 5
~10%, thickener 0.1~0.3%, deionized water 50~70%.CN104722102A is related to efficiently gathering under a kind of harsh environment
The preparation method of ether organic silicon defoamer is big using a kind of acrylic ester monomer or the blocked polyurethane acrylate of list containing double bond
Molecule monomer is modified silicon oil of low hydrogen content with allyl polyether as composite modifier, and whole process is stablized, and is not necessarily to solvent, can be made
Polyether silicones mother liquor, by with the compoundings system such as dimethicone, hydroxy silicon oil, white carbon, nonionic emulsifier, deionized water
At efficient polyether silicones antifoaming agent.
CN106436455A discloses a kind of antifoaming agent of field of papermaking, includes each substance of following composition by weight：Poly- ammonia
50-60 parts of ester elastomer, 3-7 parts of nano phase ag_2 o, 2-6 parts of nano zine oxide, 9-13 parts of 2- methylpropanols, p-methyl benzenesulfonic acid 7-
11 parts, 2-5 parts of acidum nicotinicum magnesium, 1-4 parts of three silver medal of citric acid, crosslinking 6-10 parts of alcohol amine cellulose, 10-13 parts of terpene resin,
9-14 parts of methacrolein, 5-8 parts of N- methyl -3- aminopropyl trimethoxysilanes, 2-6 parts of 4- methyl -5- formyl thiazoles,
7-13 parts of Adenosine cyclic monophosphate ester, 12-16 parts of phentolamine, 4-8 parts of azodicarbonamide.
The above antifoaming agent is to eliminate bubble from physical method or defoamed without being used for polyurethane, and cannot disappear from the root cause
The generation of bubble removing bubble, if moisture is overweight, defoaming effect unobvious, this is if increasing the additive amount of antifoaming agent, virtually
Cost can be increased.
Invention content
In view of the above shortcomings of the prior art, the present invention provides a kind of antifoaming agent for polyurethane material.The present invention's
Antifoaming agent can effectively improve the intensity and elongation percentage of product, eliminate the bubble of interiors of products, to improve product quality.
One aspect of the present invention provides a kind of antifoaming agent, wherein the antifoaming agent is by including following following raw material systems
At：Hexylene glycol or methanol, silane and disilazane.
Specifically, heretofore described hexylene glycol can be 1,6 hexylene glycols or 1,2 hexylene glycols.It is heretofore described
Silane can be chlorosilane, such as a chlorosilane or dichlorosilane.Further, a chlorosilane of the present invention can be
Trim,ethylchlorosilane or the dichlorosilane can be dimethyldichlorosilane.Disilazane of the present invention can be six
Methyl disilazane.
In an embodiment of the invention, be used to prepare antifoaming agent of the present invention material benzenemethanol or oneself two
Mol ratio between alcohol, silane and disilazane is：1-2:1-2:1-2.Specifically, being used to prepare of the present invention disappear
Hexylene glycol described in the raw material of infusion can be 1,6 hexylene glycols or 1,2 hexylene glycols.It is used to prepare antifoaming agent of the present invention
Raw material described in silane can be chlorosilane, such as a chlorosilane or dichlorosilane.Further, it is used to prepare the present invention
A chlorosilane described in the raw material of the antifoaming agent can be trim,ethylchlorosilane or the dichlorosilane can be diformazan
Base dichlorosilane.It can be two silicon nitrogen of hexamethyl to be used to prepare the disilazane described in the raw material of antifoaming agent of the present invention
Alkane.
Preferably, the material benzenemethanol for being used to prepare antifoaming agent of the present invention or hexylene glycol, silane and two silicon nitrogen
Mol ratio between alkane is：1:1:1.Be used to prepare antifoaming agent of the present invention methanol 1,6 hexylene glycols or 1,2 oneself two
Alcohol, the chlorosilane for being used to prepare antifoaming agent of the present invention, such as a chlorosilane (such as trim,ethylchlorosilane) or dichloro silicon
Alkane (such as dimethyldichlorosilane) and disilazane (such as the hexamethyl for being used to prepare antifoaming agent of the present invention
Disilazane) between molar ratio be 1:1:1.It is highly preferred that the raw material for being used to prepare antifoaming agent of the present invention is methanol
Or 1,6 hexylene glycols, dimethyldichlorosilane and hexamethyldisilazane, and the molar ratio between them is 1:1:1.
Preferably, between raw material hexylene glycol, silane and the disilazane for being used to prepare antifoaming agent of the present invention
Mass ratio be：118:129:160；Mass ratio between methanol, silane and disilazane is：32:129:160.It is used to prepare
The 1 of antifoaming agent of the present invention, 6 hexylene glycols or 1,2 hexylene glycols, the chlorosilane for being used to prepare antifoaming agent of the present invention,
Such as one chlorosilane (such as trim,ethylchlorosilane) or dichlorosilane (such as dimethyldichlorosilane) and be used to prepare this hair
Mass ratio between the disilazane (such as hexamethyldisilazane) of the bright antifoaming agent is 118:129:160.It is optional
Ground, the raw material for being used to prepare antifoaming agent of the present invention are two silicon nitrogen of 1,6 hexylene glycols, dimethyldichlorosilane and hexamethyl
Alkane, and the mass ratio between them is
118:129:160。
Another aspect of the present invention provides the method for preparing antifoaming agent comprising by hexylene glycol or methanol, silane and two silicon
Azane is with 1-2:1-2:The mol ratio of 1-2 is reacted.
Further, prepare the method for antifoaming agent in the present invention, hexylene glycol can be 1,6 hexylene glycols or 1,2 oneself two
Alcohol.It is used to prepare in the method for antifoaming agent of the present invention, the silane can be chlorosilane, such as a chlorosilane or two
Chlorosilane.Further, it can be trimethyl to be used to prepare the chlorosilane described in the method for antifoaming agent of the present invention
Chlorosilane or the dichlorosilane can be dimethyldichlorosilane.It is used to prepare in the method for antifoaming agent of the present invention
The disilazane can be hexamethyldisilazane.
Preferably, in the method for preparing antifoaming agent comprising by methanol or hexylene glycol, silane and disilazane with about
1:1:1 mol ratio is reacted, and is used to prepare in the method for antifoaming agent of the present invention, and the silane is chlorine silicon
Alkane, such as a chlorosilane or dichlorosilane；Being used to prepare the chlorosilane described in the method for antifoaming agent of the present invention is
Trim,ethylchlorosilane or the dichlorosilane are dimethyldichlorosilane；With the side for being used to prepare antifoaming agent of the present invention
Disilazane described in method is hexamethyldisilazane.Optionally, the method for preparing antifoaming agent of the invention includes by methanol
Or 1,6 hexylene glycols, dimethyldichlorosilane and hexamethyldisilazane are with 1:1:1 mol ratio is reacted.
Specifically, the method for preparing antifoaming agent of the present invention includes the following steps：
(1) to methanol or 1, dimethyldichlorosilane and hexamethyldisilazane is added dropwise simultaneously and respectively in 6 hexylene glycols, and
Make methanol or 1,6 hexylene glycols, dimethyldichlorosilane and hexamethyldisilazane with 1:1:1 mol ratio is reacted.
Preferably, controlling reaction temperature is no more than 50 degree during dropwise addition, stops that dimethyl dichloro is added dropwise if being more than
Silane and hexamethyldisilazane, until trim,ethylchlorosilane and hexamethyldisilazane are added dropwise.
(2) reaction is warming up to 80-90 degrees Celsius (preferably 85 degrees Celsius) reaction under stirring, preferably reacts 3-
8 hours, more preferable 5 hours.Preferably, pH can be being tested after completion of the reaction, if pH value between 7-9, shows this
Reaction finishes.
(3) reaction system is cooled to 30 degrees Celsius, centrifugation blowing is to get to antifoaming agent.Preferably, it is used in centrifugal process
Nitrogen protection avoids contact with air.
Further aspect, the present invention provides a kind of polyurethane materials, contain the antifoaming agent of the present invention.
Further, the present invention also provides the antifoaming agent of the present invention for eliminating or reduction prepares polyurethane material
The purposes that middle bubble generates.Preferably, during producing or preparing polyurethane material, by the antifoaming agent for adding the present invention
It is generated to reduce or eliminate bubble.
Still further, the present invention provides the methods for producing or preparing polyurethane material comprising use the present invention's
Antifoaming agent.
Preferably, polyurethane material of the present invention can be poly- for one-component polyurethane sealant, mono component wet solidifying
Urethane adhesive (such as PUR Moisture-curable hot melt adhesives), single-component polyurethane water-proof paint or silicon PU monocomponent polyurethane materials.
Description of the drawings
Fig. 1 is the polyurethane products for being not added with antifoaming agent of the present invention.
Fig. 2 is the polyurethane products for adding antifoaming agent of the present invention.
It below will be by the way that the present invention be described in more detail by following embodiment.Following embodiment is merely illustrative,
It should be understood that the present invention is not limited by following embodiments.
Embodiment 1
Production equipment：1000L enamel reaction stills, 500L stainless steel surge tanks.Nitrogen.
Factory formula：
Table 1：Raw material and formula of the present invention
Product Process：
(1) 1,6 hexylene glycol of liquid or methanol are added in reaction kettle, while by dimethyldichlorosilane and hexamethyl two
Silazane is separately added into two stainless steel surge tanks；Dimethyldichlorosilane, hexamethyldisilazane, the two drop are added dropwise simultaneously
It is 129 to add ratio:160；
(2) reactor temperature is controlled by cooling system and is no more than 50 degrees Celsius, stop that dimethyl is added dropwise if being more than
Dichlorosilane and hexamethyldisilazane, until dimethyldichlorosilane and hexamethyldisilazane are added dropwise；
(3) so that reaction kettle is warming up to 80-90 degrees Celsius under stirring, react 5 hours；
(4) pH is tested after completion of the reaction, and pH value indicates that reaction finishes between 7-9, and cools to 30 degrees Celsius, in nitrogen
The lower centrifugation blowing of protection obtains antifoaming agent.
The character of prepared antifoaming agent is as shown in table 2 below.
Table 2：Gained antifoaming agent character
Embodiment 2：
Polyurethane elastomer is prepared by proportioning shown in the following table 3.
Table 3：Application example of this product in polyurethane moisture curing coating
After organic silicon defoamer in the antifoaming agent that compared the addition present invention and on the market, measured data such as the following table 4：
Table 4：Polyurethane moisture curing coating performance comparison
The concrete structure of the said goods also can be found in Fig. 1 and Fig. 2 (for the antifoaming agent of formula 2).From Fig. 1 and Fig. 2 and
Table 4 can be seen that the intensity and elongation percentage of product can be effectively improved by adding product of the present invention, the main reason is that the defoaming of the present invention
Agent can more preferably eliminate the bubble of interiors of products, to improve product quality.
Although with above embodiments describe the present invention, it should be appreciated that before the spirit without departing substantially from the present invention
It puts, the present invention further can be modified and be changed, and these modifications and variation all belong to the scope of protection of the present invention it
It is interior.
Claims (10)
1. a kind of antifoaming agent, wherein by being made comprising following following raw materials：Methanol or hexylene glycol, silane and disilazane.
2. antifoaming agent according to claim 1, wherein the hexylene glycol can be 1,6 hexylene glycols or 1,2 hexylene glycols；Institute
The silane stated is chlorosilane；And/or the disilazane can be hexamethyldisilazane.
3. antifoaming agent according to claim 2, wherein the chlorosilane is a chlorosilane or dichlorosilane.
4. antifoaming agent according to claim 3 a, wherein chlorosilane is trim,ethylchlorosilane or the dichloro silicon
Alkane is dimethyldichlorosilane.
5. antifoaming agent according to claim 3, wherein the mol ratio between the hexylene glycol, silane and disilazane
For：1-2:1-2:1-2.
6. antifoaming agent according to claim 5, wherein mole between the methanol or hexylene glycol, silane and disilazane
Proportioning is：1:1:1.
7. antifoaming agent according to claim 6, wherein the hexylene glycol is 1,6 hexylene glycols, the silane is dimethyl two
Chlorosilane, the disilazane is hexamethyldisilazane, and the molar ratio between them is 1:1:1.
8. the method for preparing antifoaming agent comprising by methanol or hexylene glycol, silane and disilazane with 1-2:1-2:Mole of 1-2
Proportioning is reacted.
9. a kind of polyurethane material, be by using described in any one of claim 1-7 antifoaming agent or claim 8 institute
Prepared by the antifoaming agent of preparation.
10. the antifoaming agent prepared by antifoaming agent or claim 8 described in any one of claim 1-7 is preparing polyurethane material
Purposes in material.
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| CN201810002679.6A CN108341957A (en) | 2018-01-02 | 2018-01-02 | Polyurethane material antifoaming agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810002679.6A CN108341957A (en) | 2018-01-02 | 2018-01-02 | Polyurethane material antifoaming agent and preparation method thereof |
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