CN1253492C - Preparation of carboxy silicon oil emulsion - Google Patents
Preparation of carboxy silicon oil emulsion Download PDFInfo
- Publication number
- CN1253492C CN1253492C CN 200410041395 CN200410041395A CN1253492C CN 1253492 C CN1253492 C CN 1253492C CN 200410041395 CN200410041395 CN 200410041395 CN 200410041395 A CN200410041395 A CN 200410041395A CN 1253492 C CN1253492 C CN 1253492C
- Authority
- CN
- China
- Prior art keywords
- emulsion
- silicone oil
- carboxyl
- oil emulsion
- siloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a preparation method of carboxy silicon oil emulsion, which comprises: ester group modified silicon oil, small molecule siloxane, an emulsifying agent, dodecylbenzene sulfonic acid as a catalyst and water react at the temperature of 70 to 95DEG C for 5 to 15 hours, the total consumption of the ester group modified silicon oil and the small molecule siloxane makes carboxylic organosilicon chain links in carboxy silicon oil as the final product account for 0.5 to 30% of the total organosilicon chain links, the consumption of the emulsifying agent accounts for 0.1 to 10% of the total mass of the emulsion, and the consumption of the dodecylbenzene sulfonic acid as the catalyst accounts for 3 to 30% of the total mass of the emulsion; a water solution of sodium bicarbonate is added after reactants are cooled, and the reactants are neutralized to obtain the carboxy silicon oil emulsion. In the method of the present invention, ester group hydrolysis and siloxane polymerization are simultaneously carried out through a single step of simple operation, and simultaneously, the granule diameter of the generated carboxy silicon oil emulsion can be changed by means of the regulation of the consumption of the dodecylbenzene sulfonic acid and the consumption of the nonionic emulsifying agent, etc., and the carboxy silicon oil emulsion even can be made into microemulsion.
Description
Technical Field
The invention relates to modified silicone oil, in particular to a preparation method of carboxyl modified silicone oil emulsion.
Background
The carboxyl modified silicone oil is one of carbon functional modified silicone oil, which means that two ends or side chains of an organic silicon molecular chain contain carboxyl groups, wherein the carboxyl groups are connected with polysiloxane through Si-C bonds, and the chemical structure is as follows:
R1R2 2SiO(SiR2 2O)n(SiR2R3O)mSiR2 2R1
wherein R is1＝R2、R3or-OH, R2An organic aliphatic or aromatic substituent of C1-C6, R3＝-(CH2)a-COOH，n＝10～10000，m＝1～1000，n/m＝1～1000，a＝1～30。
Carboxyl silicone oil has the general characteristics of silicone and reactivity of carboxyl group, and can be used as a lubricant for fabrics such as sewing thread, a finishing agent for chemical fiber, silk and wool cloth, a brightening additive for paint, a mold release agent, a chemical modifier for polymer, and the like (see: US 6313335; EP 6147157). In many cases, silicone oils are sold and used in the form of environmentally friendly aqueous emulsions.
There are several methods available for introducing carboxyl groups into silicone chains, or groups that can be converted to carboxyl groups by chemical reaction, such as ester groups, nitrile groups, and the like. Some reports have been made on the production of carboxyl-modified silicone oils and emulsions thereof:
kojima et al describe a process for preparing carboxyl-modified silicone oils by copolymerizing octamethylcyclotetrasiloxane with silicone oils of high carboxyl content (cf. Kojima K, Gore CR, Marvel CS. J Polym SciA-1, 1966, 4: 2325). Silicone oils with high carboxyl content (or per-carboxyl silicone oils) can be obtained by hydrosilylation of hydrogen-containing siloxanes with unsaturated fatty acids, before hydrosilylation, trimethyl silicon must be used to block and protect the carboxyl groups that can react with the active hydrogen in hydrogen-containing silicone oils, and strict water-proof protection measures are required in the preparation process, which is complicated and requires multiple reactions to complete (see: EP 196169; JP 61-223031).
Hydrolysis of ester-or nitrile-modified silicone oils (see: Ohyanagi M et al, poly M commun, 1985, 26: 249) produces carboxyl-modified silicone oils, which are synthesized by hydrosilylation of acrylate or methacrylate with hydrogen-containing monomers (methyldichlorosilane, etc.) in nova et al (see: nova, butyl, Linxu, et al, J.Boscholaris, 1986, 3 (4): 349) to produce small molecule silanes containing ester groups, which can be further reacted to produce ester-or carboxyl-modified silicone oils (see: Zhang Ming, Severlon, organosilicon materials 1999, 6: 7), but under these hydrosilylation conditions, reaction of acrylate or methacrylate with methyldichlorosilane produces both α -and β -site addition (see: nova, butyl, forest et al, Polisbee, 1986, 3 (4): 349; Zhang Ming, Villolon, Severron, Var, et al, Miq. J.7, which can be easily separated from the nitrile-containing silicone oils by hydrolysis of vinyl chloride, carboxyl-containing groups, which can be easily separated from the subsequent hydrolysis of acrylonitrile-containing cyanoethyl chlorosilane, which can be easily converted to the product of carboxyl-containing chlorosilane, which is easily accessible by hydrolysis of the nitrile group-containing cyanoethyl chlorosilane, which can be easily handled by hydrolysis of the subsequent hydrolysis of the silanol, which can be easily accessible by hydrolysis of the silanol-containing cyanogroup-containing cyanoethyl chlorosilane, which can be easily handled by the silanol-containing cyanogroup, which is easily accessible to produce the silanol-modified silicone oils (see: 7, which can be easily accessible to produce the silanol-modified silicone oils, which can be easily handled by hydrolysis of the silanol-containing cyanogroup-modified silicone oils, which can be easily handled by the silanol-modified silicone oils, which can be easily handled by hydrolysis of the silanol-modified silicone oils, which can be easily accessible to produce the silanol-free from the silanol-containing cyanoethyl-modified silicone oils, which can be easily handled.
The carboxyl modified silicone oil, emulsifier, water and the like are emulsified by emulsification and dispersion equipment to prepare emulsion, the stability of the emulsion is greatly related to the formula of the emulsion, the emulsification process, the equipment and the like, and generally, the particle size of emulsion particles obtained by the method is difficult to control and the distribution is wide.
Disclosure of Invention
The invention aims to provide a simple and convenient preparation method of stable carboxyl modified silicone oil emulsion.
The basic idea of the invention is: and carrying out hydrosilylation reaction on the high-hydrogen-content silicone oil and unsaturated olefine acid ester to obtain the ester-based modified silicone oil with high ester group content. The ester group modified silicone oil, the organosilicon ring body, the alkyl benzene sulfonic acid, the emulsifier and other raw materials are added into a reaction kettle, the hydrolysis of ester groups and the copolymerization of siloxane are carried out simultaneously, and the stable side chain carboxyl modified silicone oil emulsion can be obtained through one-step reaction, wherein the alkyl benzene sulfonic acid is used as a catalyst for the hydrolysis of the ester group and a catalyst for the polymerization of the siloxane and is also one of the emulsifiers of the emulsion.
The ester-based modified silicone oil is obtained by carrying out hydrosilylation on hydrogen-containing silicone oil and fatty acid ester, and the reaction equation is as follows:
in the formula 1, the ≡ Si-H represents hydrogen-containing silicone oil, generally trimethyl-terminated high-hydrogen-containing silicone oil, or a ring body of methyl hydrogen siloxane, such as a cohydrolysis material of dimethylchlorosilane, dimethyldichlorosilane and trimethylchlorosilane, or a product obtained by hydrolyzing the cohydrolysis material and then performing acid equilibrium reaction. The viscosity is generally 1 to 500cp, preferably 10 to 100 cp. Meanwhile, in order to improve the production efficiency, high hydrogen-containing siloxane is generally adopted, and the hydrogen content is in the range of 0.2-1.66%, preferably 1.0-1.6%. The aliphatic olefinic acid ester is methyl ester or ethyl ester of acid containing double bond of three or more carbon atoms, and the double bond may be at the end of carbon chain, or in the middle of chain, preferably at the end, such as methyl acrylate, ethyl acrylate, methyl 10-undecylenate, ethyl 10-undecylenate, etc. The catalyst for the hydrosilylation reaction may be a transition metal compound such as platinum or rhodium, and generally, in consideration of price, chloroplatinic acid or a platinum complex, such as Speier catalyst (chloroplatinic acid isopropanol solution), chloroplatinic acid tetrahydrofuran solution, Karstetd catalyst (tetramethyldivinyldisiloxane-platinum complex), cyclooctadiene-platinum complex, etc.
In the reaction, the molar ratio of active hydrogen to double bonds is 1: 1 to 1: 3, preferably 1: 1. In order to ensure complete reaction of active hydrogen, sometimes the alkenoic acid ester must be in excess, and the excess alkenoic acid ester may be removed by distillation under reduced pressure after completion of the reaction. In general, the molar ratio of active hydrogen in the hydrogen-containing silicone oil to double bonds in the alkenoic acid ester is preferably 1: 1.
The reaction may be carried out in the absence of a solvent or in an inert solvent such as toluene or xylene, but it is preferable to carry out the reaction in the absence of a solvent, which can reduce the number of purification steps.
The reaction temperature is 50-150 ℃, the reaction speed is accelerated by increasing the reaction temperature, side reactions are easy to cause, even the system is gelled, the reaction speed is slow when the temperature is low, and the optimal reaction temperature is 80-120 ℃.
The reaction can be carried out in a reaction flask with a stirrer, a thermometer and a dropping funnel, and the feeding mode can be divided into several types: the alkenoic acid ester can be put into a reaction bottle firstly, heated to a certain temperature, added with the catalyst, and then added with the hydrogen-containing silicone oil dropwise at the reaction temperature; or mixing the alkenoic acid ester, the hydrogen-containing silicone oil and the catalyst at room temperature, and then dropwise adding the mixture into a preheated reaction bottle for reaction; or the alkenoic acid ester and the hydrogen-containing silicone oil are firstly heated to a certain temperature in a reaction bottle, and then the catalyst is added to start the reaction. The best feeding mode is a method of dripping hydrogen-containing silicone oil.
The carboxyl modified silicone oil emulsion is prepared by adding the ester modified silicone oil obtained by the method, micromolecular siloxane, an emulsifier, a polymerization and hydrolysis catalyst, water and the like into a reaction bottle, heating for reaction, performing one-step reaction operation, and simultaneously performing ester hydrolysis and silicone emulsion copolymerization. The emulsion generated by the operation can be used as seed emulsion, and after organic silicon monomer and water are added, emulsion polymerization can be carried out to generate stable carboxyl modified organic silicon emulsion with low carboxyl content and low emulsifier content.
The small molecule siloxane is small molecule organosilicon ring body, such as hexaMethylcyclotrisiloxane (D)3) Octamethylcyclotetrasiloxane (D)4) Decamethylcyclopentasiloxane (D)5) Or mixtures thereof (DMC), and hydrolysis products of dimethyldichlorosilane; or organosilicon cyclic body containing vinyl, phenyl, etc. and its micromolecular siloxane, such as tetramethyl tetraphenyl cyclotetrasiloxane, tetramethyl tetravinyl cyclotetrasiloxane, etc.; mixtures of the various small molecule siloxanes described above are also possible. The small molecule siloxane accounts for the total weight of the emulsion10-40% of the total amount.
The emulsifier is alkylbenzene sulfonate, alkyl sulfate or alkyl phosphate anionic surfactant, such as dodecyl benzene sulfonate, dodecyl sulfate, dodecyl phosphate salt, etc.; or nonionic surfactant such as alkylphenol ethoxylates OP-10 (octylphenol polyoxyethylene ether), NP-40 (nonylphenol polyoxyethylene ether), and fatty alcohol polyoxyethylene ether such as peregal O, AEO-10, AEO-20, etc.; mixtures of the above anionic and nonionic surfactants are also possible. The amount of the emulsifier is 0.1-10% of the total weight of the whole emulsion, generally 0.5-5%.
The polymerization and hydrolysis catalyst is long-chain alkyl benzene sulfonic acid, such as dodecyl benzene sulfonic acid, and the dosage of the long-chain alkyl benzene sulfonic acid determines the hydrolysis speed of ester groups and the polymerization speed of siloxane; the polymerization and hydrolysis catalyst has emulsifying properties and can be used as part of an emulsifier, and therefore the amount used also affects the particle size of the emulsion. To obtain a faster ester hydrolysis rate, the concentration of the alkylbenzene sulfonic acid in the system must be 0.1-1.0M (its weight is about 3-30% of the emulsion), otherwise the reaction time must be prolonged to achieve a satisfactory ester hydrolysis rate. In the case of requiring less alkylbenzenesulfonic acid, the seed emulsion with higher carboxyl content and alkylbenzenesulfonic acid content can be prepared, so as to ensure that the ester group can be hydrolyzed completely in shorter reaction time. Then adding other small molecular siloxane and water, and stirring to react to obtain the organosilicon emulsion with proper carboxyl content and low alkylbenzene sulfonic acid content.
The amount of the ester-based modified silicone oil to be used is determined depending on the carboxyl group content in the carboxyl silicone oil to be prepared, and the amount of the carboxyl group content depends on the use. Generally, for the purpose of modification, the silicone chain units containing carboxyl groups in the carboxyl-modified silicone oil account for 0.5 to 30%, usually 0.5 to 5%, of the total silicone chain units.
The reaction temperature of the whole reaction is controlled as necessary. In the initial stage of the reaction, in order to accelerate the hydrolysis of ester groups and the polymerization of small molecular siloxane, the reaction temperature is higher and is generally controlled to be 70-95 ℃; when the ester group is basically hydrolyzed completely (at the moment, the micromolecular siloxane is also polymerized), the reaction temperature can be reduced to increase the molecular weight of the polymer, and the temperature can be controlled to be 20-50 ℃.
The carboxyl modified silicone oil emulsion prepared by the method is an anionic or anionic/nonionic composite emulsion, wherein the particle size of emulsified particles can be measured by a dynamic particle size distribution instrument (generally, the particle size measured by the method is larger than the actual particle size), and the particle size of the emulsion prepared by the method is generally tens of nanometers to hundreds of nanometers, so that the emulsion belongs to the size category of microemulsion.
Therefore, the technical scheme of the invention is as follows:
a method for preparing a carboxy silicone oil emulsion, comprising the steps of:
step one, ester-based modified silicone oil, micromolecular siloxane, an emulsifier, a catalyst dodecyl benzene sulfonic acid and water are reacted for 5-15 hours at 70-95 ℃, the dosage of the ester-based modified silicone oil and the micromolecular siloxane is that the organosilicon chain links containing carboxyl in the final product carboxyl modified silicone oil account for 0.5-30% of the total organosilicon chain links, the dosage of the emulsifier accounts for 0.1-10% of the total mass of the emulsion, the dosage of the catalyst dodecyl benzene sulfonic acid accounts for 3-30% of the total mass of the emulsion, after the reaction is finished, a sample is taken for infrared spectrum analysis, and the ester group is basically hydrolyzed completely.
And step two, cooling the reactant, and adding a sodium bicarbonate aqueous solution for neutralization to obtain the carboxyl silicone oil emulsion with higher viscosity.
The preparation method of the carboxyl silicone oil emulsion can add the following steps between the first step and the second step:
and (3) adding micromolecular siloxane and a nonionic surfactant into the reaction mixture prepared in the step one, and reacting for 8-170 hours at room temperature to 80 ℃. The carboxyl-modified silicone oil in the carboxyl-modified silicone oil emulsion thus obtained contains 0.5 to 5.0% of the carboxyl-containing silicone chain units based on the total silicone chain units, and the nonionic surfactant is contained in an amount of 0.1 to 5.0% of the total mass of the emulsion.
The two preparation methods of the carboxyl silicone oil are that the micromolecular siloxane can be hexamethylcyclotrisiloxane (D)3) Octamethylcyclotetrasiloxane (D)4) Decamethylcyclopentasiloxane (D)5) Or a mixture thereof (DMC), or a hydrolyzed low molecular weight organosiloxane of dimethyldichlorosilane, or an organosilicon ring body or a small molecular weight siloxane containing vinyl or phenyl groups.
The emulsifier can be alkylbenzene sulfonate, alkyl sulfate or alkyl phosphate anionic surfactant, or nonionic surfactant, such as alkylphenol ethoxylates (OP-10, NP-40), fatty alcohol polyoxyethylene ether (peregal, AEO-10, AEO-20), or mixture of anionic and nonionic surfactants.
The two preparation methods of the carboxyl silicone oil are characterized in that the ester groupmodified silicone oil and the micromolecular siloxane are used in amounts such that the carboxyl-containing organosilicon chain links in the final product carboxyl silicone oil account for 0.5-30% of the total organosilicon chain links.
The dosage of the emulsifier is 0.1-10% of the total mass of the emulsion.
The carboxyl-based silicone oil emulsion prepared by the method is an anionic or anionic/nonionic composite emulsion, wherein the particle size of emulsified particles can be measured by a dynamic particle size distribution instrument, and generally, the particle size of emulsion particles prepared by the method is from tens of nanometers to hundreds of nanometers, so that the particle size of the emulsion particles is already in the size range of nano-emulsion.
The technical advantages of the invention are obvious: the method of the invention simultaneously hydrolyzes ester group and polymerizes siloxane by simple operation, and the hydrolysis rate of ester group can reach more than 90% and the polymerization rate of siloxane can reach 90% (the theoretical highest conversion rate) in about 5-15 hours. Meanwhile, the particle size of the generated carboxyl silicone oil emulsion can be changed by means of adjusting the dosage of the alkyl benzene sulfonic acid and the nonionic emulsifier, and the like, and even the carboxyl silicone oil emulsion can be made into microemulsion. The emulsion produced by this method has very good stability and good centrifugal stability, and can be stored for a long time without generating floating oil.
The emulsion or microemulsion prepared by the above method can be used as a surface lubricant, modifier or treating agent, such as sewing thread lubricant, release agent, coating additive, etc. Can be used as polyester fiber finishing agent alone or in combination with other silicone oil emulsion, so that the fiber has soft, smooth and elastic hand feeling.
Drawings
FIG. 1 shows an ester-based modified silicone oil and D4An infrared spectrogram of a product obtained after emulsion polymerization reaction of a dodecyl benzene sulfonic acid system at 80 ℃ for 8 hours;
FIG. 2 shows an ester-based modified silicone oil and D4An infrared spectrogram of a product obtained after emulsion polymerization reaction for 8 hours at 80 ℃ in a p-toluenesulfonic acid system;
FIG. 3 is an infrared spectrum of the product of ester-based modified silicone oil and D4 emulsion polymerization in dodecylbenzene sulfonic acid system at 80 ℃ for 15 hours.
Detailed Description
Example 1 preparation of ester-modified Silicone oil
153.5 g of 10-methyl undecylenate is added into a 500ml four-necked flask, the mixture is heated to 80 ℃, chloroplatinic acid catalyst (the dosage is 20ppm of the total reactant quantity) is added, 50 g of high hydrogen silicone oil with 1.55 percent of hydrogen content is dripped into the system from a dropping funnel, the dripping speed and the heating speed are controlled, the temperature of the system is kept between 80 ℃ and 150 ℃, the reactant is kept at about 120 ℃ for 2 hours after the dripping is finished, and the reaction is finishedAnd distilling under reduced pressure to remove low-boiling-point substances to obtain the ester modified silicone oil modified by methyl undecylate. Infrared spectrum analysis found at 2155cm-1The Si-H absorption peak disappears, which shows that the active hydrogen in the hydrogen-containing silicone oil has reacted completely. The product is yellow transparent liquid with certain viscosity and refractive index nD 201.4560, η (20 ℃) 152 cp.
Example 2 preparation of ester-modified Silicone oil
165 g of 10-ethyl undecylenate is used for replacing methyl undecylenate, and the reaction is repeated to obtain the ester modified silicone oil modified by ethyl undecylenate. The product is yellow transparent liquid with certain viscosity and refractive index nD 201.4570, η (20 ℃) 160 cp.
Example 3 preparation of a Carboxylic silicon oil emulsion
50 g of the ester-based modified silicone oil obtained in example 2, octamethylcyclotetrasiloxane, was charged into a 500ml four-necked flask75 g of an alkane, 200 g of water and 41 g of dodecylbenzenesulfonic acid, stirring at an elevated temperature and maintaining the temperature at 80 ℃ for 8 hours, taking a sample and carrying out infrared spectroscopic analysis, and finding that the ester group is mostly hydrolyzed (see the attached figure 1), wherein the concentration is 1715.9cm-1The absorption peak at (A) is the carbonyl absorption peak in the carboxyl group, and 1743cm-1The absorption peak is the carbonyl absorption peak in the unreacted ester group and is 3500-2500 cm-1A broad and weak carboxyl absorption peak occurs. After the reaction mass was cooled, 42.4 g of 25% aqueous sodium bicarbonate solution was added, and the mixture was stirred at room temperature for 30 minutes, and then the stirring was stopped, thereby obtaining a tan-colored carboxyl silicone oil emulsion having a large viscosity.
Comparative example 1
Into a 250ml four-necked flask were charged 20 g of the ester-based modified silicone oil of production example 1, 30 g of octamethylcyclotetrasiloxane, 80 g of water, and 9.6 g of p-toluenesulfonic acid (containing a crystal water), and the mixture was stirred while being warmed and allowed to react at 85 ℃ for 8 hours. After the reaction mixture was cooled, 17 g of 25% sodium hydrogencarbonate was added thereto, and the mixture was stirred at room temperature for 30 minutes, whereupon the stirring was stopped.
The reaction product does not form a stable emulsion but is immediately divided into three layers, the upper layer being a nearly colorless transparent liquid of low viscosity and the middle layer being yellow silicon of slightly higher viscosityThe oil layer, the lower layer is dark yellow liquid. The upper layer was analyzed to be an unreacted octamethylcyclotetrasiloxane layer and the lower layer was an aqueous phase. The middle layer is the product of hydrolysis reaction of ester-modified silicone oil, and analysis shows that the hydrolysis degree of ester group is very small after washing with salt solution, and the infrared spectrum is 1714cm-1No distinct carboxyl absorption peak was found (see fig. 2). This indicates that the ester-based modified silicone oil is not hydrolyzed and that the silicone is not copolymerized well.
By comparing example 3 with comparative example 1, we can find that: under the same molar concentration of the alkylbenzene sulfonic acid, example 3 can be an emulsion system, so that not only the polymerization speed of siloxane is high, but also the hydrolysis speed of ester groups is high; in contrast, in comparative example 1, since p-toluenesulfonic acid had no emulsifying property, an emulsion reaction system could not be formed, and the polymerization rate of siloxane and the hydrolysis rate of ester group were very slow.
Example 4 preparation of a high carboxy content carboxy Silicone oil emulsion
16 g of the ester-based modified silicone oil, 24 g of octamethylcyclotetrasiloxane, 91 g of water and 13.2 g of dodecylbenzene sulfonic acid in example 1 were charged into a 500ml four-necked flask, and when the mixture was heated and stirred and kept at 70 ℃ for reaction 15, the reaction was terminated, and a sample was taken for infrared spectroscopic analysis to confirm that the ester group had been substantially hydrolyzed.
Cooling the reactant, adding 20% sodium bicarbonate water solution to neutralize dodecylbenzene sulfonic acid, continuing stirring for half an hour, and stopping stirring to obtain an emulsion with high tawny viscosity and stable carboxyl molar chain link contentIs 14% of a carboxyl silicone oil emulsion. After infrared spectroscopic analysis (see FIG. 3), 1743cm was found-1The carbonyl absorption peak in the ester group at position (A) was substantially disappeared at 1712.7cm-1A carbonyl absorption peak in carboxyl is appeared nearby, and 3600-2600 cm-1The absorption peak of carboxyl group is strong, which indicates that the ester group has been substantially hydrolyzed into carboxyl group.
The solids content of the emulsion was analyzed to be 34.1% (theoretical calculation 36.5%). Centrifuge stability experiment (3000 rpm, 30 min): stable without floating oil or precipitation; the emulsion was diluted with water to a silicone concentration of 0.5%, and the particle size, as measured by a particle size distribution meter 90Plus manufactured by Brookhaven Instruments corporation, was 248.9nm with a polydispersity of 0.313.
Example 5 preparation of a Carboxylic silicon oil emulsion with Low carboxyl content
25 g of the reaction product before neutralization in example 4, 24 g of octamethylcyclotetrasiloxane, 1 g of octylphenol polyoxyethylene ether (OP-10) and 80 g of water were charged into a 500ml four-necked flask, stirred at room temperature for 30 minutes and then heated to 80 ℃ to react for 8 hours. Thereaction mass was allowed to cool and left overnight, and 1.32 g of sodium bicarbonate was added to neutralize it, and stirring was stopped at room temperature for 30 minutes to give a milky-white slightly blue-tinged carboxy silicone oil emulsion with a molar chain length of carboxy groups of 2.5%.
Centrifuge stability experiment (3000 rpm, 30 min): stable without floating oil or precipitation; after the emulsion was diluted with water to a concentration of 0.5%, the average particle diameter was 86.8nm as measured by laser light scattering, and the polydispersity was 0.205.
Demulsifying the emulsion with ethanol, washing with ethanol for three times, and oven drying at 150 deg.C to obtain light yellow transparent liquid with viscosity of 2400 cp.
Example 6 preparation of a high molecular weight carboxy-silicone oil emulsion with Low carboxy content
Example 5 was repeated, and after 8 hours at 80 ℃ the reaction product was left at room temperature for 7 days and then neutralized with sodium bicarbonate to give a milky-white slightly blue-tinged carboxyl silicone oil emulsion having a carboxyl molar chain segment content of 2.5% and a high molecular weight.
Centrifuge stability experiment (3000 rpm, 30 min): stable without floating oil or precipitation; after diluting the emulsion with water to a concentration of 0.5%, the average particle size was 75.9rm as determined by laser light scattering, with a polydispersity of 0.186.
Demulsifying the emulsion with ethanol, washing with ethanol for three times, and oven drying at 150 deg.C to obtain light yellow transparent liquid with viscosity of 32600 cp.
Example 7 preparation of a Carboxylic silicon oil emulsion with Low carboxyl content
Example 5 was repeated using 24 g of silicone mixed ring DMC instead of octamethylcyclotetrasiloxane, and a milky-white slightly blue-lustrous carboxy silicone oil emulsion with a carboxy molar chain segment content of 2.5% was obtained.
Centrifuge stability experiment (3000 rpm, 30 min): stable without floating oil or precipitation; after the emulsion was diluted with water to a concentration of 0.5%, the average particle size was 106.3nm as measured by laser light scattering, and the polydispersity was 0.285.
Demulsifying the emulsion with ethanol, washing with ethanol for three times, and oven drying at 150 deg.C to obtain light yellow transparent liquid with viscosity of 1830 cp.
EXAMPLE 8 preparation of vinyl-containing carboxy-silicone oil emulsion
50 g of the reaction product before neutralization in production example 3, 28 g of octamethylcyclotetrasiloxane, 20 g of tetramethyltetravinylcyclotetrasiloxane, 0.8 g of hexamethyldisiloxane, 234 g of alkyl alcohol polyoxyethylene ether AEO-234 and 160 g of water were charged into a 500ml four-necked flask, stirred at room temperature for 30 minutes, and then heated to 95 ℃ to react for 10 hours. And (3) cooling the reaction product, standing overnight, adding 1.32 g of sodium bicarbonate for neutralization the next day, stirring at room temperature for 30 minutes, and stopping stirring to obtain the milky-white slightly blue carboxyl silicone oil emulsion with the carboxyl molar content of 2.6% and the vinyl molar content of 31.2% in the organosilicon chain segment.
Centrifuge stability experiment (3000 rpm, 30 min): stable without floating oil or precipitation; after the emulsion was diluted with water to a concentration of 0.5%, the average particle diameter was 138.8nm as measured by laser light scattering, and the polydispersity was 0.325.
Demulsifying the emulsion with ethanol, washing with ethanol for three times, and oven drying at 150 deg.C to obtain yellowish transparent liquid with viscosity of 1910 cp.
Application example 1
30 g of the carboxyl silicone oil emulsion in the manufacturing example 5 and 70 g of the nonionic amino silicone oil emulsion with the solid content of 30% are added into a 1000ml beaker, 900 g of deionized water is added into the beaker, the mixture is stirred uniformly, 100 g of unprocessed polyester staple fiber is added into the beaker, the mixture is taken out after being soaked for a plurality of seconds, the mixture is dried by a drying machine until the weight is about 110 g, the mixture is placed in an enamel tray and is placed in a 150 ℃ drying oven for drying for 20 minutes, and the mixture is taken out and cooled. The treated fiber has smooth hand feeling, high elasticity and good filling power, and can be used as filling material for toys, bedding, clothes and the like.
Claims (3)
1. A preparation method of carboxyl silicone oil emulsion is characterized by comprising the following steps:
step one, ester-based modified silicone oil, micromolecular siloxane, an emulsifier, a catalyst dodecyl benzene sulfonic acid and water are reacted for 5 to 15 hours at the temperature of 70 to 95 ℃, the dosage of the ester-based modified silicone oil and the micromolecular siloxane is that organic silicon chain links containing carboxyl in the final product carboxyl silicone oil account for 0.5 to 30 percent of the total organic silicon chain links, the micromolecular siloxane is hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane or a mixture thereof, or hydrolysis material low molecular organic siloxane of dimethyldichlorosilane, or organic silicon ring bodies containing phenyl or vinyl,the dosage of the emulsifier is 0.1 to 10 percent of the total mass of the emulsion, the dosage of the catalyst dodecyl benzene sulfonic acid is 3 to 30 percent of the total mass of the emulsion,
and step two, cooling the reactant, and adding a sodium bicarbonate aqueous solution for neutralization to obtain the carboxyl silicone oil emulsion.
2. A process for the preparation of a carboxy silicone oil emulsion according to claim 1, characterised in that between step one and step two there is added the following step:
and (2) adding micromolecular siloxane and a nonionic surfactant into the reaction mixture prepared in the step one, and reacting for 8-170 hours at room temperature to 80 ℃, wherein the carboxyl-containing organosilicon chain segments in the carboxyl silicone oil emulsion accounts for 0.5-5.0% of the total organosilicon chain segments, and the content of the nonionic surfactant accounts for 0.1-5.0% of the total mass of the emulsion.
3. A process for the preparation of a carboxy silicone oil emulsion according to claim 1 or 2, characterized in that: the emulsifier is alkylbenzene sulfonate, alkyl sulfate or alkyl phosphate anionic surfactant, or nonionic surfactant, or a mixture of anionic surfactant and nonionic surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410041395 CN1253492C (en) | 2004-07-16 | 2004-07-16 | Preparation of carboxy silicon oil emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410041395 CN1253492C (en) | 2004-07-16 | 2004-07-16 | Preparation of carboxy silicon oil emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1613893A CN1613893A (en) | 2005-05-11 |
| CN1253492C true CN1253492C (en) | 2006-04-26 |
Family
ID=34763697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410041395 Expired - Fee Related CN1253492C (en) | 2004-07-16 | 2004-07-16 | Preparation of carboxy silicon oil emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1253492C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3385303A1 (en) * | 2006-10-10 | 2018-10-10 | Dow Silicones Corporation | Silicone polymer emulsions |
| CN101386679B (en) * | 2008-10-23 | 2011-06-01 | 南京工业大学 | Method for preparing cationoid hydroxyl silicon oil emulsion |
| CN101402735B (en) * | 2008-11-11 | 2011-02-02 | 宁波润禾化学工业有限公司 | Process for producing long-chain alkyl-silicone oil |
| CN104861175B (en) * | 2014-02-20 | 2019-03-19 | 瓦克化学（中国）有限公司 | A kind of modified resin aqueous liquid dispersion |
| CN105694044B (en) * | 2016-04-11 | 2019-10-01 | 南京大学 | A kind of polysiloxanes of carboxyl functional and preparation method thereof |
| WO2018032523A1 (en) * | 2016-08-17 | 2018-02-22 | 周吉国 | Microemulsion mold release agent and preparation method thereof |
| CN112513148A (en) * | 2018-07-26 | 2021-03-16 | 瓦克化学股份公司 | Modified resin aqueous dispersion liquid |
| CN109234058A (en) * | 2018-08-01 | 2019-01-18 | 广东雷邦高新材料有限公司 | A kind of organosilicon detergent and preparation method thereof |
| CN113788959B (en) * | 2018-12-28 | 2023-11-17 | 浙江深蓝新材料科技有限公司 | Preparation method of organic silicon emulsion |
| CN111072994A (en) * | 2019-12-25 | 2020-04-28 | 广东省稀有金属研究所 | Long-chain alkyl silicone oil waterproof emulsion and preparation method thereof |
| CN113637172A (en) * | 2021-09-08 | 2021-11-12 | 杭州包尔得新材料科技有限公司 | Terminal carboxyl silicone oil containing MTQ resin and preparation method thereof |
-
2004
- 2004-07-16 CN CN 200410041395 patent/CN1253492C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1613893A (en) | 2005-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2732357C (en) | Process for the preparation of amine-amide-functional siloxanes | |
| Brook et al. | New synthetic strategies for structured silicones using B (C 6 F 5) 3 | |
| EP1957563B1 (en) | Process for the production of organosilsesquioxanes | |
| TWI718173B (en) | Branched polyorganosiloxanes and related curable compositions, methods, uses and devices | |
| CN1253492C (en) | Preparation of carboxy silicon oil emulsion | |
| CN100500675C (en) | Synthesis method of multi-amino polyhedral oligomeric silsesquioxanes | |
| CN107254051B (en) | Preparation and application of polycyclic polyether siloxane copolymer | |
| JP2002212294A (en) | Multibranched polycarbosilane, polycarbosiloxane, polycarbosilazene and copolymer thereof | |
| CN109280170A (en) | A kind of functional polysiloxanes copolymer preparation method of phosphonitrile catalysis | |
| CN104045831A (en) | Siloxane bridged ladderlike polysiloxane and preparation method thereof | |
| KR20140011308A (en) | Methods of modifying metal-oxide nanoparticles | |
| CN101636434A (en) | Heteroelement siloxane compounds and polymers | |
| Liao et al. | Living synthesis of silicone polymers controlled by humidity | |
| KR20170083105A (en) | Sulfur-containing polyorganosiloxane compositions and related aspects | |
| JP2678624B2 (en) | Organosiloxane compound having amino group | |
| CN110156997A (en) | It is a kind of can moisture solidification organic silicon block copolymer and preparation method thereof | |
| CN111423731B (en) | High-strength copolymerized fluorosilicone rubber composition and preparation method thereof | |
| CN104327268B (en) | Siloxane copolymer containing ethyl phenyl silica chain links and preparation method thereof | |
| JP6099661B2 (en) | Olefin-functionalized siloxane oligomer composition based on alkoxysilanes with low chloride content | |
| JPH0532783A (en) | Diphenylsiloxane-dimethylsiloxane copolymer and its production | |
| CN107312175A (en) | A kind of preparation method of line style polyborosiloxane | |
| CN109796597B (en) | Preparation method of branched silane and polyether alkyl co-modified silicone oil | |
| JP2013129809A (en) | Acid anhydride group-containing organosiloxane and method for producing the same | |
| CN1252142C (en) | Polyorganosiloxane mixtures for treating fiber materials | |
| Vitry et al. | Hybrid copolymer latexes cross-linked with methacryloxy propyl trimethoxy silane. Film formation and mechanical properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Anhui Lixing Chemical Co.,Ltd. Assignor: Nanjing University Contract record no.: 2011340000169 Denomination of invention: Preparation of carboxy silicon oil emulsion Granted publication date: 20060426 License type: Exclusive License Open date: 20050511 Record date: 20110721 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060426 Termination date: 20160716 |