CN111072994A - Long-chain alkyl silicone oil waterproof emulsion and preparation method thereof - Google Patents
Long-chain alkyl silicone oil waterproof emulsion and preparation method thereof Download PDFInfo
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- 239000000839 emulsion Substances 0.000 title claims abstract description 102
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 63
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 46
- 238000004945 emulsification Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 12
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 8
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000004530 micro-emulsion Substances 0.000 claims description 8
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 229940069096 dodecene Drugs 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 34
- 229910052697 platinum Inorganic materials 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000004806 packaging method and process Methods 0.000 description 9
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 240000002853 Nelumbo nucifera Species 0.000 description 5
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 5
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Abstract
The invention discloses a long-chain alkyl silicone oil waterproof emulsion and a preparation method thereof. The long-chain alkyl silicone oil waterproof emulsion comprises the following components: 37.5-62.5 parts of tetramethyl tetrahydrocyclotetrasiloxane, 187.5-212.5 parts of octamethylcyclotetrasiloxane, 5-7.5 parts of emulsifier, 30-45 parts of dodecylbenzene sulfonic acid, 750 parts of water and 105-277 parts of long-chain olefin. The preparation method comprises the following steps of S1, preparing mixed liquor; s2, dispersing and phase inversion to obtain a pre-emulsified emulsion; s3, heating and stirring to completely dissolve the materials; s4, dropwise adding for reaction; s5, cooling and stirring to carry out emulsion polymerization; s6, carrying out catalytic reaction; s7, dropwise adding for reaction; and S8, preserving heat and cooling to obtain the long-chain alkyl silicone oil emulsion. The invention synthesizes the hydrogen-containing silicone oil emulsion in an emulsion polymerization mode, and then the hydrogen-containing silicone oil emulsion is added with olefin, and compared with a product obtained by adding the hydrogen-containing silicone oil emulsion by a mechanical emulsification method, the product has better stability, difficult demulsification and good waterproof effect. Compared with the long-chain alkyl silicone oil emulsion obtained by a mechanical emulsification method, the long-chain alkyl silicone oil emulsion has the advantages of good stability, good waterproof effect and strong hydrophobic property.
Description
Technical Field
The invention relates to the technical field of synthesis of organic silicon emulsion, and particularly relates to a preparation method of long-chain alkyl silicone oil waterproof emulsion.
Background
The long-chain alkyl silicone oil is an organic silicon compound with partial methyl substituted by long-chain alkyl in the molecular structure of the dimethyl silicone oil, and the long-chain alkyl belongs to a hydrophobic group, so the long-chain alkyl silicone oil can be used as a waterproof agent, can be used as a waterproof agent for materials such as ceramics, paper, leather, cement, gypsum, marble and the like, and is particularly widely applied to the waterproof aspect of concrete, real stone paint, rock wool and wood.
Usually, long-chain alkyl silicone oil needs to be diluted by a solvent for use according to use requirements, and the solvent pollutes the environment, so that the application is limited and is gradually prohibited; the emulsion can be emulsified into emulsion for use, the emulsion takes water as a diluent, and the emulsion is safe, environment-friendly and convenient to use, can not form oil spots, gradually replaces a solvent type and is widely applied. However, in application, the long-chain alkyl silicone oil emulsion obtained by a mechanical emulsification method has a hydrophobic effect far lower than that of solvent-type long-chain alkyl silicone oil, even has no waterproof effect, and the contact angle does not reach a hydrophobic angle of more than 90 degrees, because the long-chain alkyl has too strong hydrophobicity, a large amount of emulsifier needs to be added to obtain a stable emulsion, and the increase of the emulsifier inevitably causes the reduction of the waterproof property, even has no waterproof property. For example, the patent publication No. CN108753161A discloses a Chinese invention patent with the subject of a preparation method of a special organosilicon waterproofing agent for wood, and the technical scheme is that 20-30 parts of octamethylcyclotetrasiloxane, 20-30 parts of tetravinyltetramethylcyclotetrasiloxane and other raw materials are stirred, heated and stirred for emulsion reaction, then the temperature is raised, a catalyst is added, the heat preservation reaction is carried out, the pH is adjusted, and the material is discharged, so that a pretreatment emulsion is obtained; and stirring and mixing 8-10 parts of isomeric tridecanol polyoxyethylene ether emulsifier and other raw materials, adjusting the pH, and stirring and mixing with distilled water to obtain the special organic silicon waterproof agent for wood. Wherein, the emulsifier accounts for 7.94-10.53% of the total component weight, the water resistance is reduced due to the increase of a large amount of the emulsifier, and the technical proposal still needs to be further improved in the aspect of water resistance.
To obtain a good water-proof effect, it is necessary to use as few emulsifiers as possible for the long-chain alkyl silicone oil emulsion, but the use of a small amount of emulsifiers leads to instability of the emulsion, which is a conflicting problem.
The long-chain alkyl silicone oil emulsion can be obtained by an emulsion addition method, namely, hydrogen-containing silicone oil emulsion and long-chain olefin are added, but the hydrogen-containing silicone oil emulsion obtained by a conventional mechanical emulsification method has larger grain diameter and poorer stability of a product obtained by adding the long-chain olefin, and if the content of the required emulsifier is more for obtaining more stable emulsion, the demulsification failure is easily caused and the waterproofness is reduced.
Disclosure of Invention
The invention aims at overcoming the defects and shortcomings and provides the long-chain alkyl silicone oil emulsion with good stability, good waterproof effect and strong hydrophobicity.
Another object of the present invention is to provide a method for preparing the above emulsion.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
the long-chain alkyl silicone oil waterproof emulsion comprises the following components: tetramethyltetrahydrocyclotetrasiloxane, octamethylcyclotetrasiloxane, emulsifier, dodecylbenzenesulfonic acid, water, and long-chain olefin; wherein the components are 37.5-62.5 parts of tetramethyl tetrahydrocyclotetrasiloxane, 187.5-212.5 parts of octamethylcyclotetrasiloxane, 5-7.5 parts of emulsifier, 30-45 parts of dodecylbenzene sulfonic acid, 750 parts of water and 105-277 parts of long-chain olefin in sequence by weight.
According to a further technical scheme, the components comprise 47.5-52.5 parts of tetramethyl tetrahydrocyclotetrasiloxane, 197.5-202.5 parts of octamethylcyclotetrasiloxane, 5.5-6.5 parts of emulsifier, 35-40 parts of dodecylbenzene sulfonic acid, 720-760 parts of water and 150-220 parts of long-chain olefin in sequence by weight.
As a further technical scheme of the invention, the long-chain olefin is 1-dodecene, 1-tetradecene, 1-hexadecene or 1-octadecene.
As a further technical scheme of the invention, the emulsifier is OP-4, OP-7, OP-10, OP-15 or OP-20 type emulsifier. In the present invention, it is preferable that the emulsifier is OP-10 emulsifier.
The preparation method of the long-chain alkyl silicone oil waterproof emulsion comprises the following steps:
A. preparing hydrogen-containing silicone oil microemulsion:
s1, adding tetramethyltetrahydrocyclotetrasiloxane, octamethylcyclotetrasiloxane and an emulsifier into a reaction container to obtain a mixed solution;
s2, dispersing the mixed solution at a high speed for 5-10 minutes, then slowly adding deionized water, and emulsifying for 30-60 minutes to obtain a pre-emulsified emulsion;
s3, adding dodecylbenzene sulfonic acid into a container filled with deionized water, heating to 80-85 ℃, and stirring to completely dissolve the dodecylbenzene sulfonic acid;
s4, transferring the pre-emulsified emulsion into a dripping container, adjusting the dripping speed to continuously drip, and controlling the dripping time to be 2-5 hours;
wherein, with the dropping, blue light is gradually generated in the system, and after the dropping is finished, the heating is stopped to obtain the emulsion after the dropping;
s5, cooling the dropwise added emulsion to room temperature, continuing stirring for emulsion polymerization, adding a small amount of 10-30% sodium silicate aqueous solution after 5-8 hours, and adjusting the pH value to 6-7 to obtain the hydrogen-containing silicone oil microemulsion;
wherein the system is in a blue light transparent state;
B. preparation of long-chain alkyl silicone oil emulsion
S6, adding the hydrogen-containing silicone oil into a reactor, adding a catalyst 1, 3-divinyl tetramethyl disiloxane platinum complex, and heating to 80-90 ℃;
s7, transferring the long-chain olefin into a dripping container, and adjusting the dripping speed to continuously drip;
and S8, after the dropwise addition is finished, continuously preserving the heat for 2-4 hours, stopping the reaction, and cooling to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
As a further technical scheme of the invention, the mass of the deionized water added in the step S2 and the mass of the deionized water added in the step S3 are equal.
As a further technical scheme of the invention, a high-speed dispersion machine is used for dispersion in the step S2, the rotating speed is 3000-5000 r/min, and the time is 6-8 minutes.
As a further technical scheme of the invention, the emulsification time in the step S2 is 40-50 minutes; the heating temperature in the step S3 is 82-84 ℃; and the dripping time in the step S4 is 3-4 hours.
As a further technical scheme of the invention, in the step S6, the temperature is raised to 85-88 ℃.
In a further embodiment of the present invention, the reaction vessel in step S1 is an emulsifying cup, the vessel in step S3 is a three-necked flask, the dropping vessel in step S4 is an isopiestic dropping funnel, and the dropping vessel in step S7 is an isopiestic dropping funnel.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention synthesizes the hydrogen-containing silicone oil emulsion in an emulsion polymerization mode, and then the hydrogen-containing silicone oil emulsion is added with olefin, and compared with a product obtained by adding the hydrogen-containing silicone oil emulsion by a mechanical emulsification method, the product has better stability, difficult demulsification and good waterproof effect.
(2) Compared with the long-chain alkyl silicone oil emulsion obtained by a mechanical emulsification method, the long-chain alkyl silicone oil emulsion has the advantages of good stability, good waterproof effect and strong hydrophobic property.
The invention will be further described with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which should be understood as merely explaining the technical solutions of the present invention and not limiting the scope of the claims.
In the specific embodiment of the invention, the tetramethyltetrahydrocyclotetrasiloxane is referred to as D4H for short; octamethylcyclotetrasiloxane is abbreviated as D4; the emulsifier OP-10 is abbreviated as OP-10.
Pre-emulsification 1
37.5 g of D4H, 212.5 g of D4 and 5 g of OP-10 are weighed into an emulsification cup, a high-speed dispersion machine is started to mix for 5 minutes, and 375 g of water is weighed and slowly added to emulsify to obtain a milky liquid. The emulsification time was 30 minutes.
Polymerization emulsion 1
375 g of water is weighed into a 2000 ml three-neck flask, 45 g of dodecylbenzene sulfonic acid is added, the temperature is heated to 80 ℃, and the mixture is stirred to be completely dissolved. And transferring the pre-emulsified emulsion into a 500 ml constant pressure dropping funnel, adjusting the dropping speed to continuously drop the emulsion, and controlling the whole dropping process to be finished within 2 hours. As the dropwise addition proceeded, the system was gradually generated from blue light. After the dropwise addition, the heating is stopped, the mixture is cooled to room temperature and is continuously stirred for emulsion polymerization, and after 6 hours, 10% sodium silicate aqueous solution is added for neutralization until the pH value is 6, and the system is transparent in blue light. Obtaining the hydrogen-containing silicone oil microemulsion with 25 percent of organic silicon content, and the active hydrogen mass fraction is 0.0625 percent.
Pre-emulsification 2
62.5 g of D4H, 187.5 g of D4 and 7.5 g of OP-10 are weighed into an emulsification cup, a high-speed dispersion machine is started, the mixture is mixed for 7 minutes, and 375 g of water is weighed and slowly added to emulsify the mixture to obtain milky liquid. The emulsification time was 40 minutes.
Polymerization emulsion 2
375 g of water is weighed into a 2000 ml three-neck flask, 37.5 g of dodecylbenzene sulfonic acid is added, heated to 83 ℃, and stirred to be completely dissolved. And transferring the pre-emulsified emulsion into a 500 ml constant pressure dropping funnel, adjusting the dropping speed to continuously drop the emulsion, and controlling the whole dropping process to be finished within 4 hours. As the dropwise addition proceeded, the system was gradually generated from blue light. After the dropwise addition, the heating is stopped, the mixture is cooled to room temperature and is continuously stirred for emulsion polymerization, and a small amount of 20% sodium silicate aqueous solution is added after 6 hours to neutralize the mixture until the pH value is 7, so that the system is transparent in blue light. Obtaining the hydrogen-containing silicone oil microemulsion with 25 percent of organic silicon content and 0.1037 percent of active hydrogen mass fraction.
Pre-emulsification 3
62.5 g of D4H, 187.5 g of D4 and 5 g of OP-10 are weighed into an emulsification cup, a high-speed dispersion machine is started to mix for 10 minutes, and 375 g of water is weighed and slowly added to emulsify to obtain a milky liquid. The emulsification time was 50 minutes.
Polymerization emulsion 3
375 g of water is weighed into a 2000 ml three-neck flask, 45 g of dodecylbenzene sulfonic acid is added, heated to 85 ℃, and stirred to be completely dissolved. And transferring the pre-emulsified emulsion into a 500 ml constant pressure dropping funnel, adjusting the dropping speed to continuously drop the emulsion, and controlling the whole dropping process to be finished within 4 hours. As the dropwise addition proceeded, the system was gradually generated from blue light. After the dropwise addition, the heating is stopped, the mixture is cooled to room temperature and is continuously stirred for emulsion polymerization, and a small amount of 30% sodium silicate aqueous solution is added after 8 hours to neutralize the mixture until the pH value is 6, so that the system is transparent in blue light. Obtaining the hydrogen-containing silicone oil microemulsion with 25 percent of organic silicon content and 0.1037 percent of active hydrogen mass fraction.
Pre-emulsification 4
37.5 g of D4H, 212.5 g of D4 and 5 g of OP-10 are weighed into an emulsification cup, a high-speed dispersion machine is started, the mixture is mixed for 8 minutes, and 375 g of water is weighed and slowly added to emulsify the mixture to obtain milky liquid. The emulsification time was 60 minutes.
Polymerization emulsion 4
375 g of water is weighed into a 2000 ml three-neck flask, 30 g of dodecylbenzene sulfonic acid is added, the temperature is heated to 84 ℃, and the mixture is stirred to be completely dissolved. And transferring the pre-emulsified emulsion into a 500 ml constant pressure dropping funnel, adjusting the dropping speed to continuously drop the emulsion, and controlling the whole dropping process to be finished within 3 hours. As the dropwise addition proceeded, the system was gradually generated from blue light. After the dropwise addition, the heating is stopped, the mixture is cooled to room temperature and is continuously stirred for emulsion polymerization, and a small amount of 20% sodium silicate aqueous solution is added after 7 hours to neutralize the mixture until the pH value is 7, so that the system is transparent in blue light. Obtaining the hydrogen-containing silicone oil microemulsion with 25 percent of organic silicon content, and the active hydrogen mass fraction is 0.0625 percent.
Example 1
100 g of the polymerization emulsion 1 prepared above was weighed into a three-necked flask, 0.02 g of a platinum complex catalyst, 1, 3-divinyltetramethyldisiloxane (platinum mass fraction: 5000ppm), was added thereto, and the temperature was raised to 80 ℃. 10.5 g of 1-dodecene is weighed and transferred into a constant pressure dropping funnel, and the dropping speed is adjusted to continuously drop. And after the dropwise addition is finished, continuously preserving the heat for 3 hours, stopping the reaction, cooling and packaging to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
Example 2
100 g of the polymerization emulsion 1 prepared above was weighed into a three-necked flask, 0.02 g of a platinum complex catalyst, 1, 3-divinyltetramethyldisiloxane (platinum mass fraction: 5000ppm), was added thereto, and the temperature was raised to 85 ℃. 15 g of 1-hexadecene was weighed and transferred to a constant pressure dropping funnel, and the dropping speed was adjusted to continuously drop. And after the dropwise addition is finished, keeping the temperature for 2 hours, stopping the reaction, cooling and packaging to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
Example 3
100 g of the polymerization emulsion 2 prepared above was weighed into a three-necked flask, 0.02 g of a platinum complex catalyst, 1, 3-divinyltetramethyldisiloxane (platinum mass fraction: 5000ppm), was added thereto, and the temperature was raised to 90 ℃. 21.5 g of 1-tetradecene was weighed and transferred to a constant pressure dropping funnel, and the dropping speed was adjusted to continuously drop. And after the dropwise addition is finished, keeping the temperature for 2 hours, stopping the reaction, cooling and packaging to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
Example 4
100 g of the polymerization emulsion 2 prepared above was weighed into a three-necked flask, 0.02 g of a platinum complex catalyst, 1, 3-divinyltetramethyldisiloxane (platinum mass fraction: 5000ppm), was added thereto, and the temperature was raised to 80 ℃. 27.7 g of 1-octadecene was weighed out and transferred to a constant pressure dropping funnel, and the dropping speed was adjusted to continuously drop. And after the dropwise addition is finished, keeping the temperature for 4 hours, stopping the reaction, cooling and packaging to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
Example 5
100 g of the polymerization emulsion 3 prepared above was weighed into a three-necked flask, and 0.02 g of a platinum complex catalyst, 1, 3-divinyltetramethyldisiloxane (platinum mass fraction: 5000ppm), was added thereto, and the temperature was raised to 88 ℃. 18.5 g of 1-dodecene is weighed and transferred into a constant pressure dropping funnel, and the dropping speed is adjusted to continuously drop. And after the dropwise addition is finished, continuously preserving the heat for 3 hours, stopping the reaction, cooling and packaging to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
Example 6
100 g of the polymerization emulsion 3 prepared above was weighed into a three-necked flask, and 0.02 g of a platinum complex catalyst, 1, 3-divinyltetramethyldisiloxane (platinum mass fraction: 5000ppm), was added thereto, and the temperature was raised to 84 ℃. 21.5 g of 1-tetradecene was weighed and transferred to a constant pressure dropping funnel, and the dropping speed was adjusted to continuously drop. And after the dropwise addition is finished, continuously preserving the heat for 2.5 hours, stopping the reaction, cooling and packaging to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
Example 7
100 g of the polymerization emulsion 4 prepared above was weighed into a three-necked flask, 0.02 g of a platinum complex catalyst, 1, 3-divinyltetramethyldisiloxane (platinum mass fraction: 5000ppm), was added thereto, and the temperature was raised to 90 ℃. 15 g of 1-hexadecene was weighed and transferred to a constant pressure dropping funnel, and the dropping speed was adjusted to continuously drop. And after the dropwise addition is finished, keeping the temperature for 2 hours, stopping the reaction, cooling and packaging to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
Example 8
100 g of the polymerization emulsion 4 prepared above was weighed into a three-necked flask, and 0.02 g of a platinum complex catalyst, 1, 3-divinyltetramethyldisiloxane (platinum mass fraction: 5000ppm), was added thereto, and the temperature was raised to 83 ℃. 17.3 g of 1-octadecene is weighed and transferred into a constant pressure dropping funnel, and the dropping speed is adjusted to continuously drop. And after the dropwise addition is finished, continuously preserving the heat for 3.5 hours, stopping the reaction, cooling and packaging to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
Comparative example 1
100 g of hydrogen-containing silicone oil emulsion prepared by a mechanical emulsification method (the content of organic silicon is 25 percent, the mass fraction of active hydrogen is 0.1037 percent) is weighed into a three-neck flask, 0.02 g of catalyst 1, 3-divinyl tetramethyl disiloxane platinum complex (the mass fraction of platinum is 5000ppm) is added, and the temperature is raised to 90 ℃. 15 g of 1-hexadecene was weighed and transferred to a constant pressure dropping funnel, and the dropping speed was adjusted to continuously drop. And after the dropwise addition, keeping the temperature for 3 hours, stopping the reaction, cooling and packaging.
Comparative example 2
30 g of commercially available long-chain alkyl silicone oil and 5 g of OP-10 are weighed in an emulsification cup, a high-speed dispersion machine is started to mix for 10 minutes, and then 65 g of water is weighed and slowly added to emulsify to obtain milky liquid. The emulsification time is 50 minutes
In the embodiments 1 to 8, the emulsifier accounts for 1.56 to 2.37 mass percent of the total components, and compared with the prior art, the emulsifier dosage is greatly reduced, and the waterproof effect is significant. The following are comparisons of emulsion stability and water-repellent effect:
comparison of emulsion stability
The emulsions of examples 1 to 8 and comparative examples 1 to 2 were filled in a sealed plastic bottle, and placed in a constant temperature oven at 50 ℃ to check whether or not delamination occurred after one month. The results are given in table 1 below:
comparison of Water-proofing effects of emulsions
The emulsions of examples 1 to 8 and comparative examples 1 to 2 were diluted to a mass content of 10%, applied to a concrete block of C30 designation, a square of 300 g, and water-repellent test for water drop effect after curing for 48 hours, with the results as shown in table 1 below:
TABLE 1 comparison table of stability and water-proof effect of examples 1 to 8 and comparative example 1
The lotus leaf has the water-proof effect, namely the lotus effect and the self-cleaning effect, is mainly applied to the surface of an object, and can achieve the water-proof and oil-proof effects. Can keep the surface of an object clean, reduces the pollution of the detergent to the environment, and is safe and labor-saving.
Judging the waterproof effect indexes of the lotus leaves: the water drops can roll on the surface of the base material, and the water drops do not adhere to the surface of the base material like the effect of rolling on the surface of the lotus leaves, so that the lotus leaf waterproof effect is achieved.
While the present invention has been described by way of examples, and not by way of limitation, other variations of the disclosed embodiments, as would be readily apparent to one of skill in the art, are intended to be within the scope of the present invention, as defined by the claims.
Claims (10)
1. A long-chain alkyl silicone oil waterproof emulsion is characterized in that:
comprises the following components: tetramethyltetrahydrocyclotetrasiloxane, octamethylcyclotetrasiloxane, emulsifier, dodecylbenzenesulfonic acid, water, and long-chain olefin;
the components comprise, by mass, 37.5-62.5 parts of tetramethyltetrahydrocyclotetrasiloxane, 187.5-212.5 parts of octamethylcyclotetrasiloxane, 5-7.5 parts of an emulsifier, 30-45 parts of dodecylbenzene sulfonic acid, 650-850 parts of water and 105-277 parts of long-chain olefin.
2. The long-chain alkyl silicone oil waterproof emulsion according to claim 1, characterized in that: the components are 47.5-52.5 parts of tetramethyl tetrahydrocyclotetrasiloxane, 197.5-202.5 parts of octamethylcyclotetrasiloxane, 5.5-6.5 parts of emulsifier, 35-40 parts of dodecylbenzene sulfonic acid, 720-760 parts of water and 150-220 parts of long-chain olefin in sequence by weight.
3. The long-chain alkyl silicone oil waterproof emulsion according to claim 1, characterized in that: the long-chain olefin is 1-dodecene, 1-tetradecene, 1-hexadecene or 1-octadecene.
4. The long-chain alkyl silicone oil waterproof emulsion according to claim 1, characterized in that: the emulsifier is OP-4, OP-7, OP-10, OP-15 or OP-20 type emulsifier.
5. A preparation method of the long-chain alkyl silicone oil waterproof emulsion as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps:
A. preparing hydrogen-containing silicone oil microemulsion:
s1, adding tetramethyltetrahydrocyclotetrasiloxane, octamethylcyclotetrasiloxane and an emulsifier into a reaction container to obtain a mixed solution;
s2, dispersing the mixed solution at a high speed for 5-10 minutes, then slowly adding deionized water, and emulsifying for 30-60 minutes to obtain a pre-emulsified emulsion;
s3, adding dodecylbenzene sulfonic acid into a container filled with deionized water, heating to 80-85 ℃, and stirring to completely dissolve the dodecylbenzene sulfonic acid;
s4, transferring the pre-emulsified emulsion into a dripping container, adjusting the dripping speed to continuously drip, and controlling the dripping time to be 2-5 hours;
s5, cooling the dropwise added emulsion to room temperature, continuing stirring for emulsion polymerization, adding a small amount of 10-30% sodium silicate aqueous solution after 5-8 hours, and adjusting the pH value to 6-7 to obtain the hydrogen-containing silicone oil microemulsion;
B. preparation of long-chain alkyl silicone oil emulsion
S6, adding the hydrogen-containing silicone oil into a reactor, adding a catalyst 1, 3-divinyl tetramethyl disiloxane platinum complex, and heating to 80-90 ℃;
s7, transferring the long-chain olefin into a dripping container, and adjusting the dripping speed to continuously drip;
and S8, after the dropwise addition is finished, continuously preserving the heat for 2-4 hours, stopping the reaction, and cooling to obtain the long-chain alkyl silicone oil emulsion obtained by the emulsion addition method.
6. The method for preparing the long-chain alkyl silicone oil waterproof emulsion according to claim 5, characterized in that: the mass of the deionized water added in the step S2 and the step S3 is equal.
7. The method for preparing the long-chain alkyl silicone oil waterproof emulsion according to claim 5, characterized in that: and in the step S2, a high-speed dispersion machine is used for dispersion, the rotating speed is 3000-5000 r/min, and the time is 6-8 minutes.
8. The method for preparing the long-chain alkyl silicone oil waterproof emulsion according to claim 5, characterized in that: the emulsification time in the step S2 is 40-50 minutes; the heating temperature in the step S3 is 82-84 ℃; and the dripping time in the step S4 is 3-4 hours.
9. The method for preparing the long-chain alkyl silicone oil waterproof emulsion according to claim 5, characterized in that: and in the step S6, heating to 85-88 ℃.
10. The method for preparing the long-chain alkyl silicone oil waterproof emulsion according to claim 5, characterized in that: the reaction vessel in the step S1 is an emulsifying cup, the vessel in the step S3 is a three-neck flask, the dropping vessel in the step S4 is an isopiestic dropping funnel, and the dropping vessel in the step S7 is an isopiestic dropping funnel.
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