A kind of silicon composition
?
Technical field
The present invention relates to a kind of silicon composition that can be used for organic silicon emulsion.Therefore, the invention belongs to technical field of fine chemical preparations.
Background technology
Foam is common phenomena in the live and work.But foam can bring great harm sometimes in industrial production, for example reduce machine working efficiency, incur loss through delay working time, influence the quality of product etc.The method of eliminating harmful foam mainly contains physical method and chemical process, and the defoamer froth breaking is one of chemical process.Along with the significantly raising of industrial enterprise's industrial scale and production efficiency, the defoamer froth breaking is more widely used.At present, defoamer has been widely used in the industries such as papermaking, textile printing and dyeing, oil production and refining, coating, letex polymerization, sewage disposal, metal cleaning, and defoamer has become indispensable functional aid in the production process.
According to the difference of defoaming composition, defoamer is divided into mineral oil origin, polyether-type and several main types such as silicone based.Compare with other defoamers, poly organo siloxane defoamer stable chemical performance, side effect is little, and good froth breaking ability and the lasting bubble ability that presses down are also arranged under the very low situation of consumption simultaneously, thereby, favored very much.
Defoaming composition is the core of defoamer, and its antifoaming speed and suds suppressing properties directly influence the performance of the finished product.For silicone based defoamer, the improvement of the antifoaming performance of its actives is the improvement direction of silicone antifoam agent.The most original polysiloxane defoamers actives is handled through specific process technology by polydimethylsiloxane and silicon-dioxide and is obtained, and the defoaming agent composition of introducing as US3383327 comes to this.But because it can not press down bubble lastingly, namely suds suppressing properties is poor, and therefore, domestic and international research personnel have carried out large-scale expansion research to its performance.US4338217A1 replaces common polysiloxane and silicon dioxide granule combination treatment to make defoaming composition with the alkoxyl group polysiloxane; US5824739 introducing amino-polysiloxane or carboxyl polysiloxane obtain defoaming composition as the main body of defoaming composition with the silicon-dioxide combination treatment; EP163541B1 introduces with the polysiloxane that contains terminal hydroxyl and form the side chain organopolysiloxane with the organopolysiloxane reaction that contains other active function groups under the effect of catalyzer, and replace common polysiloxane and hydrophilic silicon dioxide combination treatment with this, prepared defoamer has very high viscosity, is difficult to this emulsification is dispersed in the water.US5153258 introduces in system and introduces the antifoaming performance that lightly crosslinked organopolysiloxane can improve composition, for example contain vinyl organopolysiloxane and hydrogeneous organopolysiloxane, hydroxyl organopolysiloxane and alkyl silicate and under the effect of catalyzer, crosslinking reaction takes place, but crosslinking degree is difficult to control.US5486306 introduced the hydrogeneous organopolysiloxane of a kind of direct usefulness and α-
The synthetic defoamer of olefine reaction is used for washing powder, and this technology is synthetic simple, but the defoamer antifoam performance that obtains is poor, contacts with fabric and easily produces the silicon spot; After having introduced the reaction of hydrogeneous organopolysiloxane and vinyl organopolysiloxane among the WO2007137948A1, the polydimethylsiloxane dilution that adds the trimethylsiloxy group end-blocking, when hydrogeneous organopolysiloxane and vinyl organopolysiloxane react in the above-mentioned patent, viscosity is big, wayward, the defoaming agent composition antifoaming performance that obtains is poor.CN1931417A discloses a kind of defoaming agent composition of high temperature resistant anti-highly basic, it is obtained by polysiloxane and silicone resin crosslinking reaction, actives is prepared into test performance after the emulsion, it has suds suppressing properties preferably, but antifoaming speed remains further to be improved, and, because defoaming composition viscosity is bigger, be dispersed in the water it quite difficult.
The silicone antifoam agent of EP-A341952 introduction use branching and the composition of polyethers-polysiloxane copolymer are used for pulp production as defoamer.US5523019 introduces the composition of mineral oil and polyethers-polysiloxane copolymer as defoamer, it is said to have positive effect.According to WO 98/000216, the siloxanes that contains dimethyl-3-hydroxypropyl-polyoxyethylene polyoxypropylene group is specially suitable tensio-active agent in the defoamer formulation.The more difficult greatly emulsification of defoaming agent composition suds suppressing properties difference in the above-mentioned patent or viscosity.
The inventor finds to form in the process of silicon composition in hydrogeneous organopolysiloxane, silicone resin and the reaction of hydroxyl organopolysiloxane, if hydrogeneous organopolysiloxane is direct and the reaction of hydroxyl organopolysiloxane, do not react with silicone resin, the silicon composition crosslinking degree that obtains is excessive, and viscosity is difficult to control.If but hydrogeneous organopolysiloxane, hydroxyl organopolysiloxane and silicone resin are reacted jointly, the silicon composition suds suppressing properties that obtains is poor.
Summary of the invention
The present invention adds the hydroxyl organopolysiloxane by a kind of again based on hydrogeneous organopolysiloxane and silicone resin reaction, through the hydrophobic particles combination treatment, obtains silicon composition.Because the hydroxyl in hydrogeneous organopolysiloxane and the silicone resin reacts, make silicon composition have the siloxanes space structure of long-chain branch, improve the bonding force of silicon composition and organic materials, in being rich in the system of anion surfactant, foam has been had good inhibition effect after the synthesizing organo-silicon emulsion.
Technical scheme
A kind of silicon composition is characterized in that it is made up of following material:
A. modified polyorganosiloxanes
Modified polyorganosiloxanes of the present invention is that hydrogeneous organopolysiloxane, silicone resin and the reaction of hydroxyl organopolysiloxane obtain.
A1. hydrogeneous organopolysiloxane
At least a general structure is following hydrogeneous organopolysiloxane:
H
c Me 3-
cSiO(
MeHSiO)
a (
Me 2SiO)
b Si
Me 3-
c H
c
MeBe methyl, subscript
cBe 0,1 or 2,
aBe 2 ~ 100 integer,
bBe 20 ~ 300 integer, each molecule has at least 2 silicon bonded hydrogen atom.The consumption of described hydrogeneous organopolysiloxane is 45 ~ 70% of silicon composition total mass.
A2. silicone resin
Silicone resin commonly used is a kind of silicone resin of space structure, preferably contains the siloxanes unit R
aSiO
4-a/2, wherein R is hydroxyl, alkyl or-oxyl, a is 0.5 ~ 2.4; More preferably contain the R of M functional group
0 3SiO
1/2With the SiO of Q functional group
4/2, R wherein
0Be univalence hydrocarbyl, the mol ratio of M:Q is (0.4 ~ 1.2): 1.0, be preferably (0.5 ~ 0.8): 1.0.Most preferred silicone resin is only formed by M base and Q are basic as defined above, comprises M base, trivalent R but also can use
0SiO
3/2(T) resin of base and Q base.Silicone resin also can contain divalent unit R
0SiO
2/2, preferably its be no more than all existence siloxane unit 20%.Described radicals R (and R
0) identical or different, be preferably the alkyl with 1 ~ 6 carbon atom, most preferable, ethyl or phenyl.Also can there be other alkyl, for example the alkenyl with 1 ~ 6 carbon atom that exists with dimethyl vinyl silyl.Also can exist and silicon bonded alkoxy group, for example methoxyl group.Also can there be hydrogen base, hydroxyl with the silicon bonding.Silicone resin can be by some silane material of hydrolysis, in solvent or produced in situ.Under the existence particularly preferably in solvent (for example dimethylbenzene), make the precursor of tetravalence siloxy groups (for example four ortho-silicates, tetraethylorthosilicise, poly-ethyl silicon ester or water glass) and precursor hydrolysis and the condensation of monovalence trialkylsiloxy unit (for example, trimethylchlorosilane, trimethylethoxysilane, hexamethyldisiloxane or hexamethyldisilazane).The present invention selects to contain the silicone resin of oh group, and the consumption of silicone resin is 1 ~ 10% of silicon composition total mass.
A3. hydroxyl organopolysiloxane
The general structure of described hydroxyl organopolysiloxane is as follows:
HO(SiR
1 2O)
m H
R in the formula
1Base is identical or different, is the alkyl of carbonatoms 1 ~ 30, comprises methyl, ethyl, propyl group, n-propyl, butyl, isobutyl-, and preferred carbonatoms is 1 ~ 10; Or carbonatoms is 6 ~ 20 aryl, comprises phenyl, phenmethyl; Or carbonatoms is 7 ~ 20 aralkyl; Subscript m is 500 ~ 3000 integer; The consumption of described hydroxyl organopolysiloxane is 15 ~ 45% of silicon composition total mass.
A4. catalyzer
Catalyzer is used for the hydrogeneous organopolysiloxane of catalyst component and silicone resin, hydroxyl organopolysiloxane generation condensation reaction.Described catalyzer is selected from platinum-alcohol complex, platinum-alkene complex, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complex compound, isopropyl alcohol solution of chloroplatinic acid, platinum-vinyl complex compound, stannous octoate.Preferred platinum content is the isopropyl alcohol solution of chloroplatinic acid of 1 ~ 20ppm.
B. hydrophobic particles
Hydrophobic particles comprises silicon-dioxide, titanium dioxide, silica powder, aluminum oxide, pure aluminium silicate, zinc oxide, magnesium oxide, or the mixture more than both or both.More above-mentioned particles are not hydrophobic in itself, use but can make it hydrophobization yet.For example by making it hydrophobization with fatty acid treatment, but preferably by using methyl substituted organosilicon material to carry out.Suitable hydrophobizing agent comprises polydimethylsiloxane, have silanol or with silicon bonded alkoxy group end-blocking dimethylsiloxane polymer, hexamethyldisilazane and hexamethyldisiloxane.Usually under at least 80 ℃, carry out hydrophobization.The preferred silicon-dioxide of the present invention, its specific surface area are 50 ~ 500 m
2/ g, hydrophobic value are 50 ~ 70%.It is divided into two kinds of precipitated silica and fumed silicas by manufacture method, is divided into two kinds of hydrophilic silicon dioxide and water drain silicas by surface properties.The present invention is preferably hydrophobic precipitated silica and hydrophobic aerosil.The consumption of described hydrophobic particles is 2 ~ 8% of silicon composition total mass.
The kinetic viscosity of described hydrogeneous organopolysiloxane in the time of 25 ℃ is 80 ~ 1,500mPas.
The preparation method of described silicon composition is as follows:
1. hydrogeneous organopolysiloxane A1 and silicone resin A2 are joined in the reaction vessel, and add catalyst A 4, reaction 0.5 ~ 1.5h in the time of 50 ~ 120 ℃;
2. add hydroxyl organopolysiloxane A3 again, reaction 0.5 ~ 3h in the time of 50 ~ 110 ℃;
3. after reaction finishes, add hydrophobic particles B, at 100 ~ 160 ℃ of insulation 1 ~ 5h, cool to room temperature namely gets described silicon composition.
A kind of method that adopts above-mentioned silicon composition to prepare organic silicon emulsion, implementation method is: with silicon composition and emulsifier mix, and progressively add water and thickening material, pass through mechanical means after mixing, as colloidal mill, clarifixator, preparation oil-in-water-type organic silicon emulsion.
Emulsifying agent comprises nonionogenic tenside and anion surfactant.
Described nonionogenic tenside is polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, lauric acid Soxylat A 25-7, oleic acid polyoxyethylene, sorbitan monostearate, sorbitan monooleate, anhydrous sorbitol tristearate, Witconol AL 69-66, anhydrous sorbitol Stearinsaeure polyoxyethylene ether-ester, anhydrous sorbitol list oleic acid polyoxyethylene ester, anhydrous sorbitol three stearic acid polyoxyethylene ether esters, castor oil polyoxyethylene ether.
Described anion surfactant is dodecyl polyethenoxy ether sodium sulfate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium cetanesulfonate, hexadecyl benzene sulfonic acid sodium salt, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate.
Thickening material is xanthan gum, guar gum, polyvinyl alcohol, Xylo-Mucine, Natvosol, polyacrylic acid, polyacrylamide, polyacrylate(s).
Embodiment
Embodiment 1
Adding 200g viscosity in container is that 800mPas, structural formula are
Me 3SiO (
MeHSiO)
36(
Me 2SiO)
290Si
Me 3Hydrogeneous organopolysiloxane, 25g silicone resin (M:Q=0.75:1) and platinum content are the isopropyl alcohol solution of chloroplatinic acid of 7ppm, at 70 ℃ of reaction 1h; Add 100g hydroxyl organopolysiloxane HO[(CH then
2CH
3)
2SiO]
500H, 90 ℃ of reaction 1h; Adding the 15g specific surface area is 90m
2The hydrophobic precipitated silica of/g, 100 ℃ of insulation 4h namely obtain silicon composition S1 after being down to room temperature.
Embodiment 2
Adding 250g viscosity in container is that 600mPas, structural formula are H
Me 2SiO (
MeHSiO)
70(
Me 2SiO)
250Si
Me 2(M:Q=0.75:1) and platinum content are the isopropyl alcohol solution of chloroplatinic acid of 3ppm, at 100 ℃ of reaction 1.2h for the hydrogeneous organopolysiloxane of H, 25g silicone resin; Add 100g hydroxyl organopolysiloxane HO[(CH then
3)
2SiO]
1000H, 90 ℃ of reaction 1.5h; Adding the 15g specific surface area is 150m
2The hydrophobic precipitated silica of/g, 100 ℃ of insulation 2h namely obtain silicon composition S2 after being down to room temperature.
Embodiment 3
Adding 200g viscosity in container is that 450mPas, structural formula are
Me 3SiO (
MeHSiO)
26(
Me 2SiO)
200Si
Me 3Hydrogeneous organopolysiloxane, 25g silicone resin (M:Q=0.75:1) and platinum content are the isopropyl alcohol solution of chloroplatinic acid of 11ppm, at 110 ℃ of reaction 1.5h; Add 50g hydroxyl organopolysiloxane HO[(CH then
3)
2SiO]
1500H, 100 ℃ of reaction 2h; Adding the 18g specific surface area is 220m
2The hydrophobic aerosil of/g is cooled to 100 ℃ of insulation 4h, namely obtains silicon composition S3 after being down to room temperature.
Embodiment 4
Adding 250g viscosity in container is that 1000mPas, structural formula are
Me 3SiO (
MeHSiO)
90(
Me 2SiO)
280Si
Me 3Hydrogeneous organopolysiloxane, 25g silicone resin (M:Q=0.75:1) and platinum content are the isopropyl alcohol solution of chloroplatinic acid of 14ppm, at 60 ℃ of reaction 0.5h; Add 180g hydroxyl organopolysiloxane HO[(CH then
3) (C
6H
5) SiO]
2000H, 80 ℃ of reaction 3h; Adding the 18g specific surface area is 300m
2The hydrophobic precipitated silica of/g, 150 ℃ of insulation 3h namely obtain silicon composition S4 after being down to room temperature.
Embodiment 5
Adding 250g viscosity in container is that 100mPas, structural formula are H
Me 2SiO (
MeHSiO)
26(
Me 2SiO)
50Si
Me 2(M:Q=0.75:1) and platinum content are the isopropyl alcohol solution of chloroplatinic acid of 19ppm, at 70 ℃ of reaction 0.5h for the hydrogeneous organopolysiloxane of H, 25g silicone resin; Add 120g hydroxyl organopolysiloxane HO[(CH then
3) (CH
2CH
3) SiO]
800H, 110 ℃ of reaction 0.5h; Adding the 20g specific surface area is 100m
2The hydrophobic precipitated silica of/g, 140 ℃ of insulation 5h namely obtain silicon composition S5 after being down to room temperature.
Embodiment 6
Adding 200g viscosity in container is that 100mPas, structural formula are
Me 3SiO (
MeHSiO)
26(
Me 2SiO)
50Si
Me 3Hydrogeneous organopolysiloxane, 30g silicone resin (M:Q=0.75:1) and platinum content are the isopropyl alcohol solution of chloroplatinic acid of 15ppm, at 100 ℃ of reaction 1h; Add 180g hydroxyl organopolysiloxane HO[(CH then
3)
2SiO]
2900H, 70 ℃ of reaction 1.5h; Adding the 20g specific surface area is 50m
2The hydrophobic aerosil of/g, 100 ℃ of insulation 4h namely obtain silicon composition S6 after being down to room temperature.
Comparative Examples 1
Adding 200g viscosity in container is that 800mPas, structural formula are
Me 3SiO (
MeHSiO)
36(
Me 2SiO)
290Si
Me 3Hydrogeneous organopolysiloxane, 100g hydroxyl organopolysiloxane HO[(CH
3)
2SiO]
500H and platinum content are the isopropyl alcohol solution of chloroplatinic acid of 10ppm, and behind 70 ℃ of reaction 0.5h, (M:Q=0.75:1), be warming up to 150 ℃ of reaction 2h, adding the 15g specific surface area then is 90m to add the 25g silicone resin
2The hydrophobic precipitated silica of/g is cooled to 100 ℃ of insulation 4h, namely obtains silicon composition D1 after being down to room temperature.
Comparative Examples 2
Adding 300g viscosity in container is that 450mPas, structural formula are
Me 3SiO (
MeHSiO)
26(
Me 2SiO)
200Si
Me 3Hydrogeneous organopolysiloxane, 80g hydroxyl organopolysiloxane HO[(CH
3)
2SiO]
1500(M:Q=0.75:1) and platinum content are the isopropyl alcohol solution of chloroplatinic acid of 14ppm, are warming up to 150 ℃ of reaction 2h, and adding the 18g specific surface area then is 90m for H, 25g silicone resin
2The hydrophobic aerosil of/g is cooled to 100 ℃ of insulation 4h, namely obtains silicon composition D2 after being down to room temperature.
Embodiment 7 ~ 15
According to prior art, adopt the silicon composition of above-mentioned S1 ~ S6, D1 and D2 to prepare organic silicon emulsion:
Under the room temperature, 40g silicon composition, 8g Witconol AL 69-66 and 12g oleic acid polyoxyethylene (4) ether are under agitation fully mixed 40min, temperature with above-mentioned system after finishing is increased to 80 ℃, then, keep system temperature, add 40g water lentamente, improving stirring velocity makes it become emulsion oil-in-water by water-in-oil emulsion, continuing to add 20g water to mass concentration is 50%, cross the further emulsification of colloidal mill, being diluted to solid content with the acrylic thickener aqueous solution at last is 30%, gets organosilicon emulsion defoaming agents M1 ~ 8.
The organic silicon emulsion performance test
(1) sodium dodecyl benzene sulfonate aqueous solution testing method: with the 0.5%(mass percent) is the foaming medium, in 100mL tool plug graduated cylinder, add above-mentioned foaming medium 50mL, the organosilicon emulsion defoaming agents that adds 0.010g then, leave standstill behind the shake 50 times in vertical direction, the record foam disappears to the liquid level time occurring, is foam time
T 50 , shake records foam time 50 times again
T 100 , every jolting is just recorded foam time 50 times, reaches till 400 times until always shaking a bottle number of times, and under the identical jolting number of times, foam time is more short, and it is more good to represent that disappearing of organic silicon emulsion pressed down the bubble effect.Test result sees Table 1:
The antifoam performance contrast of table 1 organic silicon emulsion
Foam time/s |
M1 |
M2 |
M3 |
M4 |
M5 |
M6 |
M7 |
M8 |
T
50
|
5 |
4 |
3 |
6 |
5 |
6 |
6 |
6 |
T
100
|
4 |
5 |
3 |
7 |
6 |
5 |
7 |
5 |
T
150
|
7 |
5 |
5 |
6 |
8 |
7 |
9 |
7 |
T
200
|
8 |
6 |
6 |
6 |
9 |
7 |
9 |
8 |
T
250
|
9 |
7 |
8 |
7 |
9 |
9 |
11 |
9 |
T
300
|
9 |
7 |
9 |
8 |
10 |
9 |
14 |
15 |
T
350
|
11 |
6 |
9 |
9 |
10 |
11 |
17 |
19 |
T
400
|
11 |
7 |
10 |
10 |
11 |
10 |
23 |
23 |
From last table result as can be seen, be better than 7,8 synthetic organosilicon emulsion defoaming agents M7 ~ 8 of silicon composition D1, D2 of Comparative Examples with the performance of synthetic organosilicon emulsion defoaming agents M1 ~ 6, silicon composition S1 ~ 6 of embodiment 1 ~ 6, this illustrates that silicon composition of the present invention has stronger froth breaking ability in the negatively charged ion system.
(2) in washing composition, carry out the antifoam performance test
Testing apparatus: portable circulation bubbling instrument
Probe temperature: 75 ℃
Test traffic: 7L/min
Defoamer consumption: 0.4g
The foaming medium: commercially available white cat washing composition, mass concentration is 0.5%
Testing method: clean the plant and instrument that uses.Add 600mL foaming medium and defoamer, be heated to 75 ℃; Under the flow of 7L/min, the bubbling that circulates, record lather volume V is along with the Changing Pattern of time.The height of scale foam is more low at one time, illustrates that then the suds suppressing properties of defoamer is more good.Test result sees Table 2:
Antifoam performance test in table 2 washing composition
From last table result as can be seen, be better than 7,8 synthetic organic silicon emulsion M7 ~ 8 of silicon composition D1, D2 of Comparative Examples with synthetic organic silicon emulsion M1 ~ 6 performances in silicon composition S1 ~ 6 of embodiment 1 ~ 6, this illustrates that defoaming composition of the present invention has stronger disappearing and presses down the bubble ability in detergent system.