CN115286800A - Preparation method of hyperbranched organic silicon emulsifier - Google Patents
Preparation method of hyperbranched organic silicon emulsifier Download PDFInfo
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- 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
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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
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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
- 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 relates to a preparation method of hyperbranched organic silicon emulsifier, which comprises the steps of firstly synthesizing polyether modified trialkoxysilane (I) by trialkoxysilane and allyl polyether, and then carrying out dealcoholization copolymerization on the trialkoxysilane and vinyl trialkoxysilane under an acidic condition to form polyether-polysiloxane copolymer (II); and finally, the polyether-polysiloxane copolymer (II) reacts with silicon polyether under the action of a platinum catalyst to obtain the hyperbranched organosilicon emulsifier. The emulsifying efficiency of the hyperbranched organosilicon emulsifier is obviously improved compared with the efficiency of comb-type polyether modified polysiloxane, end-group polyether modified polysiloxane and trapezoidal polyether modified polysiloxane, and the hyperbranched organosilicon emulsifier can be used for preparing organosilicon emulsions such as defoaming agents, release agents, wetting agents, waterproofing agents and the like.
Description
Technical Field
The invention relates to a preparation method of a hyperbranched organic silicon emulsifier, in particular to a preparation method of a polyether modified hyperbranched polysiloxane emulsifier, namely a hyperbranched organic silicon emulsifier.
Background
At present, the organic silicon emulsion is widely applied to the industries of buildings, electronics and electrics, textile printing and dyeing, automobile industry, mechanical manufacturing, leather papermaking, medical treatment and the like, and the main performances are reflected in the aspects of water resistance, demoulding, wear resistance, scratch resistance, defoaming and the like. With the continuous development of economic construction, the use system of the organic silicon emulsion is gradually complicated and diversified, and therefore, higher requirements are put forward on the performance of the organic silicon emulsion. However, in some high-end fields, most of the used products are imported products, while most of the domestic products are simulated products, and most of the products can only be applied to industry fields with lower requirements.
When the organosilicon emulsion is used in the defoaming agent industry, the defoaming performance of domestic defoaming agent emulsion is generally better than that of foreign products, but the compatibility and the foam inhibition performance in an application system cannot be met, and the reason is that particles are easy to separate out and aggregate in the long-time use process of effective components in the domestic defoaming agent emulsion, so that the compatibility and the foam inhibition performance of the domestic defoaming agent emulsion are poor. Therefore, the stability of silicone emulsions is of great importance for the application of the properties of the emulsions.
The patent US4853474 improves the low temperature resistance of the emulsion by the crosslinked silicon polyether, but the method is difficult to control the crosslinking degree of the silicon polyether, so that the performance stability of the product is difficult to keep consistent; US6512015B1 prepared crosslinked polyether modified polysiloxanes with hydrogen containing polysiloxanes, vinyl terminated polysiloxanes and allyl alcohol polyether, which were used to prepare emulsions; CN113069796A polyether end-capped polysiloxane improves the stability of the prepared emulsion; CN109929120A uses a combination of comb-type polyether modified polysiloxane and ladder-type polyether modified polysiloxane to co-emulsify and disperse high viscosity silicone composition, thereby improving the stability and compatibility of the emulsion. CN101203579A high viscosity silicone oil emulsion is prepared, and emulsion with required particle size is prepared under pressure of 2 to 15MPa. This method has problems that firstly, the requirement for equipment is high, and secondly, only the time for emulsion aggregation is delayed, and the problem of poor stability is not fundamentally solved.
The preparation method comprises the steps of firstly synthesizing polyether modified trialkoxysilane (I), and then carrying out dealcoholization copolymerization on the modified trialkoxysilane and vinyl trialkoxysilane under an acidic condition to form a polyether-polysiloxane copolymer (II); then the polyether-polysiloxane copolymer (II) reacts with silicon polyether under the action of a platinum catalyst to obtain the hyperbranched organosilicon emulsifier. When the prepared hyperbranched organosilicon emulsifier is used for preparing emulsion, the emulsion efficiency is obviously higher than that of side chain polyether modified polysiloxane, end group polyether modified polysiloxane and trapezoidal polyether modified polysiloxane, and the hyperbranched organosilicon emulsifier has wide application prospect.
Disclosure of Invention
The hyperbranched organosilicon emulsifier is prepared by synthesizing polyether modified alkoxy silane, vinyl trialkoxy silane and silicon polyether under the action of a catalyst, and has obviously improved emulsifying efficiency compared with comb type polyether modified polysiloxane, end group polyether modified polysiloxane and trapezoidal polyether modified polysiloxane, and is not influenced by the difference of the viscosities of emulsified substances. Therefore, the stability, temperature resistance and shearing resistance of the organic silicon emulsion are obviously improved. The multi-branched polyether modified polysiloxane can be used for preparing organic silicon emulsions such as defoaming agents, release agents, wetting agents, waterproofing agents and the like.
When preparing the allyl polyether modified trialkoxysilane (I), the mass percent of the used raw materials is as follows:
15 to 40 percent of allyl polyether
Trialkoxysilane 15 to 40 percent
40 to 60 percent of solvent
Platinum catalyst 5 to 15ppm
The preparation method of the allyl polyether modified trialkoxysilane (I) comprises the following steps:
adding a solvent, allyl polyether and a platinum catalyst into a container, starting stirring, heating to 50-80 ℃, slowly adding trialkoxysilane, controlling the temperature of materials in the container to be 90-120 ℃, reacting for 1-5 h, and then removing the solvent under reduced pressure to obtain a viscous liquid polyether modified trialkoxysilane (I).
The allyl polyether has the following structural formula:
CH 2 =CHCH 2 (EO) a (PO) b R 1
in the formula, subscriptaAndbsubscripts for degree of polymerization of ethylene oxide EO and propylene oxide POaThe numerical value is 5 to 100, and the subscriptbThe numerical value is 5 to 100; r 1 Is a blocking group selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group;
the trialkoxysilane is selected from trimethoxy silane, triethoxy silane, tripropoxy silane and tributoxy silane;
the solvent is selected from isopropanol, benzene, toluene and xylene; the platinum catalyst is platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution or platinum-vinyl complex.
When the polyether-polysiloxane copolymer (II) is prepared, the following raw materials are used in percentage by mass:
30 to 50 percent of polyether modified trialkoxysilane (I)
Vinyl trialkoxysilane 15 to 45 percent
10 to 30 percent of water
Ethanol: 10 to 20 percent
Hydrochloric acid: 5 to 10 percent
The total content is 100%
The preparation method of the polyether-polysiloxane copolymer comprises the following steps:
adding water, ethanol, hydrochloric acid, polyether modified trialkoxysilane (I) and vinyl trialkoxysilane into a flask, starting stirring, heating to 50-80 ℃ for reaction for 5-10h, then neutralizing the hydrochloric acid, filtering to remove salt, and removing the solvent under reduced pressure to obtain the polyether-polysiloxane copolymer (II).
The vinyl trialkoxysilane is selected from vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane and vinyl tributoxy silane.
When the hyperbranched organosilicon emulsifier is prepared, the mass percent of the used raw materials is as follows:
5 to 40 percent of polyether-polysiloxane copolymer (II)
Silicon polyether 60 to 95 percent
Platinum catalyst 5 to 15ppm
The structural formula of the silicon polyether is as follows:
in the formula R 2 And R 3 Is methyl or-CH 2 CH 2 CH 2 O(EO) c (PO) d R 4 ，R 2 And R 3 The same or different from allyl alcohol polyether used in synthesizing polyether modified trialkoxysilane, and R 2 And R 3 The same or different; r 4 Is a blocking group selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group;canddis the degree of polymerization of ethylene oxide and propylene oxide,cis 0 or an integer of 1 to 50,dis 0 or an integer of 1 to 50, andcanddcannot be 0 at the same time;
in the formulam、nAndtis the degree of polymerization of the three segments,m、nandtthe value of (A) ensures that the hydrogen content of the hydrogen-containing silicone oil used for synthesizing the silicon polyether is 0.05 to 0.75 percent,t1~3, dynamic viscosity at 25 ℃ of 100 to 1,000mPa · s;
the dynamic viscosity of the silicon polyether at 25 ℃ is 600 to 5, 000mPa.s;
the platinum catalyst is a platinum-alcohol complex, a platinum-olefin complex, a platinum-alkoxide complex, a platinum-ether complex, a platinum-ketone complex, a chloroplatinic acid isopropanol solution or a platinum-vinyl complex; the dosage of the catalyst calculated by platinum is 5 to 15ppm of the total mass of the multi-branched polyether modified polysiloxane emulsifier;
the preparation method of the hyperbranched polyether modified polysiloxane emulsifier comprises the following steps:
adding silicon polyether and polyether-polysiloxane copolymer (II) into a flask, heating to 60-90 ℃, adding a platinum catalyst, continuously heating to 120-150 ℃, keeping the temperature for 0.5-3 hours to ensure that the mixture becomes transparent and the viscosity becomes 2~5 times of the original viscosity, and then cooling to room temperature to obtain the hyperbranched polyether modified polysiloxane emulsifier.
Detailed Description
Example 1:
synthesis of polyether modified trialkoxysilane I-A:
the flask is charged with 60 part of isopropanol, 15 parts of allyl polyether (subscript)a= 5, subscriptb = 98；R 1 Hydrogen atom) and 10ppm of chloroplatinic acid in terms of platinum, starting stirring, heating to 60 ℃, slowly adding 25 parts of trimethoxy silane, controlling the temperature of materials in a flask to be 90-95 ℃ for reaction for 3 hours, and then removing isopropanol under reduced pressure to obtain viscous liquid which is polyether modified trialkoxy silane I-A.
Example 2:
synthesis of polyether modified trialkoxysilane I-B:
a flask was charged with 40 parts toluene, 20 parts allyl polyether (subscript)aIndex = 100b = 5；R 1 Methyl) and 6ppm of platinum-divinyl tetramethyl disiloxane complex calculated by platinum, starting stirring, heating to 80 ℃, slowly adding 20 parts of tripropoxysilane, controlling the temperature of materials in a flask to be 102-105 ℃, reacting for 1 hour, and then removing toluene under reduced pressure to obtain viscous liquid which is polyether modified trialkoxysilane I-B.
Example 3:
synthesis of polyether modified trialkoxysilane I-C:
the flask was charged with 40 parts xylene, 40 parts allyl polyether (subscript)a= 20, subscriptb = 40；R 1 Butyl) and 15ppm platinum-divinyl tetramethyl disiloxane complex calculated by platinum, starting stirring, heating to 80 ℃, slowly adding 20 parts of triethoxysilane, controlling the temperature of materials in the flask to be 115-120 ℃ for reaction for 1 hour, and then removing xylene under reduced pressure to obtain viscous liquid which is polyether modified trialkoxysilane I-C.
Example 4:
synthesis of polyether modified trialkoxysilane I-D:
the flask was charged with 40 parts benzene, 20 parts allyl polyether (subscript)a= 10, subscriptb = 10；R 1 Ethyl) and 8ppm of chloroplatinic acid in terms of platinum, starting stirring, heating to 50 ℃, slowly adding 40 parts of triethoxysilane, controlling the temperature of materials in a flask to be 105-110 ℃ for reaction for 5 hours, and then removing benzene under reduced pressure to obtain viscous liquid which is polyether modified trialkoxysilane I-D.
Example 5:
synthesis of polyether modified trialkoxysilane I-E:
the flask was charged with 45 parts toluene, 30 parts allyl polyether (subscript)a= 20, subscriptb = 30；R 1 Propyl) and an ethanol solution of chloroplatinic acid accounting for 12ppm in terms of platinum, starting stirring, heating to 70 ℃, slowly adding 25 parts of triethoxysilane, controlling the temperature of materials in a flask to be 100-105 ℃ for reaction for 3 hours, and then removing toluene under reduced pressure to obtain viscous liquid which is polyether modified trialkoxysilane I-E.
Example 6:
synthesis of polyether-polysiloxane copolymer II-A:
adding 10 parts of water, 15 parts of ethanol, 10 parts of hydrochloric acid, 50 parts of polyether modified trialkoxysilane I-C and 15 parts of vinyl trimethoxy silane into a flask, starting stirring, heating to 50 ℃ for reaction for 10 hours, neutralizing the hydrochloric acid, filtering to remove salt, and removing micromolecular volatile matters under a reduced pressure condition to obtain the polyether-polysiloxane copolymer II-A.
Example 7:
synthesis of polyether-polysiloxane copolymer II-B:
adding 30 parts of water, 20 parts of ethanol, 5 parts of hydrochloric acid, 30 parts of polyether modified trialkoxysilane I-A and 15 parts of vinyl tripropoxysilane into a flask, starting stirring, heating to 70 ℃ for reacting for 8 hours, neutralizing the hydrochloric acid, filtering to remove salt, and removing micromolecule volatile matter under the reduced pressure condition to obtain the polyether-polysiloxane copolymer II-B.
Example 8:
synthesis of polyether-polysiloxane copolymer II-C:
adding 20 parts of water, 10 parts of ethanol, 5 parts of hydrochloric acid, 40 parts of polyether modified trialkoxysilane I-B and 25 parts of vinyl triethoxysilane into a flask, starting stirring, heating to 80 ℃ for reaction for 5 hours, neutralizing the hydrochloric acid, filtering to remove salt, and removing micromolecular volatile components under a reduced pressure condition to obtain the polyether-polysiloxane copolymer II-C.
Example 9:
synthesis of polyether-polysiloxane copolymers II-D:
adding 10 parts of water, 10 parts of ethanol, 5 parts of hydrochloric acid, 30 parts of polyether modified trialkoxysilane I-D and 45 parts of vinyltriethoxysilane into a flask, starting stirring, heating to 65 ℃ for reaction for 6 hours, neutralizing the hydrochloric acid, filtering to remove salt, and removing micromolecular volatile matters under a reduced pressure condition to obtain the polyether-polysiloxane copolymer II-D.
Example 10:
synthesis of polyether-polysiloxane copolymers II-E:
adding 10 parts of water, 10 parts of ethanol, 5 parts of hydrochloric acid, 35 parts of polyether modified trialkoxysilane I-E and 40 parts of vinyl triethoxysilane into a flask, starting stirring, heating to 58 ℃ for reacting for 8 hours, neutralizing the hydrochloric acid, filtering to remove salt, and removing micromolecular volatile components under a reduced pressure condition to obtain the polyether-polysiloxane copolymer II-E.
The values in the structural formula of the silicon polyether used for preparing the hyperbranched organic silicon emulsifier are shown in table 1:
example 11:
adding 95 parts of silicon polyether A and 5 parts of polyether-polysiloxane copolymer II-B into a flask, heating to 60 ℃, adding 10ppm of chloroplatinic acid isopropanol solution calculated by platinum, continuously heating to 120 ℃, keeping the temperature for 2 hours to ensure that the mixture becomes transparent and the viscosity becomes 2,300mPa & s, and then cooling to room temperature to obtain the hyperbranched organosilicon emulsifier A.
Example 12:
adding 60 parts of silicon polyether B and 40 parts of polyether-polysiloxane copolymer II-A into a flask, heating to 90 ℃, adding 15ppm of chloroplatinic acid isopropanol solution calculated by platinum, continuously heating to 150 ℃, keeping the temperature for 0.5h to ensure that the mixture becomes transparent and the viscosity becomes 7,700mPa & s, and then cooling to room temperature to obtain the hyperbranched organosilicon emulsifier B.
Example 13:
adding 70 parts of silicon polyether C and 30 parts of polyether-polysiloxane copolymer II-D into a flask, heating to 70 ℃, adding 5ppm of chloroplatinic acid isopropanol solution calculated by platinum, continuously heating to 130 ℃, keeping the temperature for 3 hours to ensure that the mixture becomes transparent and the viscosity becomes 10,250mPa & s, and then cooling to room temperature to obtain the hyperbranched organosilicon emulsifier C.
Example 14:
adding 85 parts of silicon polyether D and 15 parts of polyether-polysiloxane copolymer II-E into a flask, heating to 70 ℃, adding 5ppm of chloroplatinic acid isopropanol solution calculated by platinum, continuously heating to 130 ℃, keeping the temperature for 1.5 hours to ensure that the mixture becomes transparent and the viscosity becomes 5,000mPa & s, and then cooling to room temperature to obtain the hyperbranched organosilicon emulsifier D.
Example 15:
adding 77 silicon polyether E and 23 parts of polyether-polysiloxane copolymer II-C into a flask, heating to 80 ℃, adding 8ppm chloroplatinic acid isopropanol solution counted by platinum, continuously heating to 120 ℃, keeping the temperature for 2 hours to ensure that the mixture becomes transparent and the viscosity becomes 9,500mPa & s, and then cooling to room temperature to obtain the hyperbranched organosilicon emulsifier E.
Example 16:
adding 70 parts of silicon polyether F and 30 parts of polyether-polysiloxane copolymer II-D into a flask, heating to 90 ℃, adding 12ppm of chloroplatinic acid isopropanol solution calculated by platinum, continuously heating to 130 ℃, keeping the temperature for 1h to ensure that the mixture becomes transparent and the viscosity becomes 8,500mPa & s, and then cooling to room temperature to obtain the hyperbranched organosilicon emulsifier F.
Comparative example 1:
the end-side chain silicon polyether in "example 12" was used as a silicone emulsifier C1.
Comparative example 2:
the side chain silicon polyether in "example 16" was used as the silicone emulsifier C2.
Comparative example 3:
patent US6512015B1 prepares trapezoidal polyether modified silicone emulsifier C3 with hydrogen-containing polysiloxane, vinyl-terminated polysiloxane and allyl alcohol polyether, and has a viscosity of 11,200mpa · s.
Comparative example 4:
patent CN109929120a uses comb-type polyether modified polysiloxane and ladder-type polyether modified polysiloxane to obtain silicone emulsifier C4 with viscosity of 50,300mpa · s.
Comparative example 5:
adding 70 parts of silicon polyether F and 30 parts of polyether-polysiloxane copolymer II-D into a flask, heating to 90 ℃, adding 15ppm of chloroplatinic acid isopropanol solution calculated by platinum, continuously heating to 150 ℃, keeping the temperature for 3 hours to ensure that the mixture becomes transparent and the viscosity becomes 26,000mPa & s, and then cooling to room temperature to obtain the hyperbranched organosilicon emulsifier C5.
Comparative example 6:
adding 70 parts of silicon polyether F and 30 parts of polyether-polysiloxane copolymer II-D into a flask, heating to 90 ℃, adding 5ppm of chloroplatinic acid isopropanol solution calculated by platinum, continuously heating to 120 ℃, keeping the temperature for 0.5h to ensure that the mixture becomes transparent and the viscosity becomes 3,500mPa & s, and then cooling to room temperature to obtain the hyperbranched organosilicon emulsifier C6.
Preparation of the silicone emulsion:
the silicone compositions were emulsified with the branched silicone emulsifiers a to F prepared in patent methods examples 11 to 16 and the silicone emulsifier of proportion 1~6, respectively, and the emulsion efficiency was determined by comparing the particle diameters of the emulsions.
Silicone composition SC-1 was prepared according to the method of patent US5283004 and had a viscosity of 100,000mPa · s.
Silicone composition SC-2 was prepared according to the method of patent US4639489 and had a viscosity of 5,000mPa · s.
The emulsion preparation method comprises the following steps:
20 parts of oil phase polysiloxane composition, 5 parts of multi-branched organic silicon emulsifier, 1.6 parts of span 60, 1 part of Tween 60, 30 parts of water and 2.4 parts of acrylic thickener are added into a container, and a high-speed dispersion machine is used for dispersing for 10min at the rotating speed of 1500rpm to obtain the organic silicon emulsion.
The emulsion sample numbering rules are as follows:
the emulsion prepared by the polysiloxane composition SC-1 and the hyperbranched organosilicon emulsifier A is SC-1A, and so on;
the emulsion prepared by the polysiloxane composition SC-2 and the hyperbranched organosilicon emulsifier A is SC-2A, and so on;
the emulsion prepared by the polysiloxane composition SC-1 and the hyperbranched organosilicon emulsifier C1 is SC-1C1, and so on;
the emulsion prepared with the silicone composition SC-2 and the hyperbranched silicone emulsifier C1 is SC-2C1, and so on.
The performance of silicone emulsions prepared with the hyperbranched silicone emulsifiers of the patented invention was evaluated from several points:
1. dilution stability test
Taking organosilicon emulsions SC-1A to SC-1F, SC-1C1 to SC-1C5 and SC-2A to SC-2F, SC-2C1 to SC-2C5 as research objects, respectively adding 198g of distilled water into a 250ml beaker, then respectively adding 2g of the organosilicon emulsions into the water, stirring and dispersing the mixture uniformly by using a glass rod, standing for 5min, and testing the particle size in a particle size meter, wherein the test results are shown in the following table 2:
as can be seen from the data in Table 2, the particle diameters of the emulsions SC-1A to SC-1F are smaller than those of the emulsions SC-1C1 to SC-1C 5; SC-1B modifies the emulsifier in SC-1C1 by the patented multi-branching technology, and SC-1F modifies the emulsifier in SC-1C2 by the patented multi-branching technology, and the comparison between SC-1B and SC-1C1, SC-1F and SC-1C2 shows that the emulsifying efficiency of the organosilicon emulsifier after multi-branching modification is obviously improved; the emulsification efficiency of SC-1C3 and SC-1C4 is also relatively high; the viscosity of SC-1C5 is 5 times higher than that of the original silicon polyether, the viscosity of SC-1C6 is 2 times lower than that of the original silicon polyether, and the viscosity is not in the 2~5 protection range of the patent, the particle size of the emulsion is large, and the emulsion efficiency is low.
Table 3 shows that the viscosity of the silicone composition having a viscosity of 100,000mPas was changed to that of only 5,000mPas by a factor of 20, as compared with Table 2, but the results of comparison between the data in Table 2 and Table 3 show that the emulsification efficiencies are substantially the same.
Meanwhile, the hyperbranched silicone emulsifier prepared by the patented method is more universal, and has no great difference in emulsion particle size for polysiloxane compositions with 20-fold difference in emulsifying viscosity, but the vinyl-containing or trapezoidal-containing silicone emulsifiers of SC-1C3 and SC-1C4 have high efficiency in emulsifying polysiloxane with high viscosity, but do not perform well when emulsifying polysiloxane compositions with low viscosity due to the spatial configuration of molecules.
Claims (3)
1. A preparation method of a hyperbranched organic silicon emulsifier is characterized in that the hyperbranched organic silicon emulsifier is prepared from the following raw materials: polyether-polysiloxane copolymer A, silicon polyether B and platinum catalyst C;
A. polyether-polysiloxane copolymer
The preparation method of the polyether-polysiloxane copolymer comprises the following steps:
adding water, ethanol, hydrochloric acid, polyether modified trialkoxysilane (I) and vinyl trialkoxysilane into a flask, starting stirring, heating to 50-80 ℃ for reaction for 5-10h, then neutralizing the hydrochloric acid, filtering to remove salt, and removing the solvent under reduced pressure to obtain a polyether-polysiloxane copolymer (II);
the preparation method of the polyether modified trialkoxysilane (I) comprises the following steps:
adding a solvent, allyl polyether and a platinum catalyst into a container, starting stirring, heating to 50-80 ℃, slowly adding trialkoxysilane, controlling the temperature of materials in the container to be 90-120 ℃, reacting for 1-5 h, and then removing the solvent under reduced pressure to obtain a viscous liquid which is polyether modified trialkoxysilane (I);
the dosage of the polyether-polysiloxane copolymer is 5 to 40 percent of the total mass of the hyperbranched organosilicon emulsifier;
B. silicon polyether
The structural formula of the silicon polyether is as follows:
in the formula R 2 And R 3 Is methyl or-CH 2 CH 2 CH 2 O(EO) c (PO) d R 4 ，R 2 And R 3 The same or different from allyl alcohol polyether used in synthesizing polyether modified trialkoxysilane, and R 2 And R 3 The same or different; r 4 Is a blocking group selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group;canddis the degree of polymerization of ethylene oxide and propylene oxide,cis 0 or an integer of 1 to 50,dis 0 or an integer of 1 to 50, andcanddcannot be 0 at the same time;
in the formulam、nAndtis the degree of polymerization of the three segments,m、nandtthe value of (A) ensures that the hydrogen content of the hydrogen-containing silicone oil used for synthesizing the silicon polyether is 0.05 to 0.75 percent,t1~3, dynamic viscosity at 25 ℃ of 100 to 1,000mPa · s;
the dynamic viscosity of the silicon polyether at 25 ℃ is 600 to 5,000mPa & s;
the dosage of the silicon polyether is 60 to 95 percent of the total mass of the hyperbranched organosilicon emulsifier;
C. platinum catalyst
The platinum catalyst is a platinum-alcohol complex, a platinum-olefin complex, a platinum-alkoxide complex, a platinum-ether complex, a platinum-ketone complex, a chloroplatinic acid isopropanol solution or a platinum-vinyl complex; the dosage of the catalyst calculated by platinum is 5 to 15ppm of the total mass of the hyperbranched organosilicon emulsifier;
the preparation method of the hyperbranched polyether modified polysiloxane emulsifier comprises the following steps:
adding silicon polyether and polyether-polysiloxane copolymer (II) into a flask, heating to 60-90 ℃, adding a platinum catalyst, continuously heating to 120-150 ℃, keeping the temperature for 0.5-3 hours to ensure that the mixture becomes transparent and the viscosity becomes 2~5 times of the original viscosity, and then cooling to room temperature to obtain the hyperbranched polyether modified polysiloxane emulsifier.
2. The preparation method of the hyperbranched organosilicon emulsifier according to claim 1, wherein the polyether-polysiloxane copolymer is prepared from the following raw materials in percentage by mass:
30 to 50 percent of polyether modified trialkoxysilane (I)
Vinyl trialkoxysilane 15 to 45 percent
10 to 30 percent of water
10 to 20 percent of ethanol
Hydrochloric acid 5 to 10%
The sum of the mass percentages of the substances is 100 percent;
the vinyl trialkoxysilane is selected from vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane and vinyl tributoxy silane.
3. The method for preparing the hyperbranched organosilicon emulsifier according to claim 2, wherein the polyether modified trialkoxysilane (i) in the polyether-polysiloxane copolymer is prepared from the following raw materials in percentage by mass:
15 to 40 percent of allyl polyether
Trialkoxysilane 15 to 40 percent
40 to 60 percent of solvent
Platinum catalyst 5 to 15ppm
The allyl polyether has the following structural formula:
CH 2 =CHCH 2 (EO) a (PO) b R 1
in the formula, subscriptaAndbsubscripts for degree of polymerization of ethylene oxide EO and propylene oxide POaThe numerical value is 5 to 100, and the subscriptbThe numerical value is 5 to 100; r 1 Is a blocking group selected from a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group;
the trialkoxysilane is selected from trimethoxy silane, triethoxy silane, tripropoxy silane and tributoxy silane;
the solvent is selected from isopropanol, benzene, toluene and xylene;
the platinum catalyst is platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution or platinum-vinyl complex.
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| CN107090084A (en) * | 2017-04-21 | 2017-08-25 | 苏州博纳化学科技有限公司 | Defoamer of polyethers scion grafting polysiloxanes and preparation method thereof |
| CN109929120A (en) * | 2019-01-03 | 2019-06-25 | 南京瑞思化学技术有限公司 | A kind of organic silicon emulsion |
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| US4631208A (en) * | 1984-11-09 | 1986-12-23 | Dow Corning, Ltd. | Organosiloxane-oxyalkylene copolymers |
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