CN1389495A - Method for preparing organic polysiloxane emulsion - Google Patents
Method for preparing organic polysiloxane emulsion Download PDFInfo
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- CN1389495A CN1389495A CN 02120247 CN02120247A CN1389495A CN 1389495 A CN1389495 A CN 1389495A CN 02120247 CN02120247 CN 02120247 CN 02120247 A CN02120247 A CN 02120247A CN 1389495 A CN1389495 A CN 1389495A
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Abstract
The invention provides a method for producing an organopolysiloxane emulsion having excellent safety and a low content of a low-molecular weight siloxane. The mixture with special proportion mixed by organopolysiloxane with special degree polymerization which two ends sealed by hydroxy and organoalkoxysilane with amino, epoxy group or sulphydryl emulsifying and dispersing in water solution with surfactant to produce once emulsion whith 50-250 nm average particle diameter, optionally regulating to alkalinity by adding alkaline compound and heating at 70-90 DEG C, organopolysiloxane proceeds reaction of condensation polymerization, adding acidic compound when necessary to neutralize the alkaline compound, then the needed water emulsion is obtained.
Description
Technical field
The present invention relates to excellent in stability, low-molecular-weight siloxane content is few and contains the manufacture method of the organic polysiloxane emulsion of functional group.
Prior art
Organic polysiloxane emulsion, can be used as the releasing agent of synthetic resins, rubber, paper, mold etc., the coating agent of synthetic resin film, sheet material or paper surface, the hydrophobic treatment agent of inorganic fibres such as organic fibre such as natural fiber, synthon, glass fibre etc., softening agent for fibres and smooth agent perhaps use as emulsion coatings and antifoaming constituent.But consider the stability and the high-polymerization degreeization of this organic polysiloxane emulsion, the small particle size product that preferably adopt emulsion polymerization to make.The manufacture method of this emulsion polymer, known for example have a polymerization process (special public clear 34-2041 communique) of making polymerizing catalyst with strong acid or highly basic, and phenyl ether sulfonic acid that replaces with alkyl benzene sulphonate (ABS), alkyl naphthalene sulfonic acid, aliphatic sulfonic, silyl alkyl sulfonic acid, aliphatics and alkyl hydrosulfate etc. make polymerizing catalyst, make organopolysiloxane carry out method of emulsion polymerization (special public clear 41-13995, belgian patent 686812, No. 3360491 communiques of United States Patent (USP)).
But also after can enumerating ring-type 3～6 oligopolymer with organo-siloxane emulsification disperseing in salt type water phase surfactant mixture, in this dispersion system, add ion exchange resin, the polymerization process (special public clear 54-19440 communique) that carries out ion-exchange with above-mentioned salt type tensio-active agent.
In addition, have as the method that obtains the amino functional organic polysiloxane emulsion, with sulfonic acid system or quaternary ammonium salt is tensio-active agent, with ring-type organopolysiloxane and the organotrialkoxysilane emulsification that is combined with functional group, carries out polymeric method (special public clear 56-38609 communique).
In addition, the manufacture method of the organic polysiloxane emulsion that is reduced as volatile low-molecular-weight siloxane content has, make emulsion polymeric method below 40 ℃ (spy opens flat 4-178429 communique) with two terminal hydroxyl organopolysiloxanes and catalyzer composition, the organopolysiloxane of two terminal hydroxyls and two terminal amino group functionality organic polysiloxane emulsion polymeric methods (spy opens flat 4-198321 communique), and carry out method of emulsion polymerization (spy opens flat 11-71522 communique) under two terminal hydroxyl organopolysiloxanes and the existence of specific sulfonic acid.But these methods are the balanced reaction that depends on acidity or basic catalyst, so volatile low-molecular-weight siloxane accounts in the siloxanes total amount about 12 weight %.And aforesaid method all needs long polymerization time, and polymerization is changed rapidly so people wait in expectation.
Summary of the invention
Problem of the present invention is to provide the manufacture method of a kind of excellent in stability, the poor organic polysiloxane emulsion of low-molecular-weight siloxane.
The inventor etc. further investigate for solving above-mentioned problem, found that: after the terminal hydroxy group organopolysiloxane is used tensio-active agent and emulsifying water with the organoalkoxysilane that contains functional group, obtain emulsion one time, the median size of this emulsion is reduced to below 250 nanometers, carry out polycondensation in the existence of basic catalyst or under not existing, can obtain the water miscible liquid of the organopolysiloxane of the few and excellent in stability of low-molecular-weight siloxane content, this emulsion can be used as fibre finish, particularly make the cotton treatment agent of bag of synthetic fiber, the style improving agent of wool and man-made fiber uses, thereby has finished the present invention.Particularly owing to the organopolysiloxane that contains functional group is dispersed in the water easily, though so be difficult in organopolysiloxane, import predetermined amount functional group with emulsion polymerization in the past, but by an emulsion particle diameter is reduced to the following aftercondensated of 250 nanometers, make this task become possibility, thereby finished the present invention.
That is to say, the invention provides a kind of excellent in stability, contain the manufacture method of the organic polysiloxane emulsion of functional group, it is characterized in that forming by following operation:
(a) with (A) 100 weight part general formulas (1) expressions, two ends are by the organopolysiloxane of hydroxyl envelope chain
H-(O-SiR
2-)
nThe organoalkoxysilane compound of-OH (1) (in the formula, R represents the monovalence alkyl of 1～20 carbon atom, and n represents 10～200 integers) and the expression of (B) 0.1～20 weight part general formula (2),
R
pR
1Si (OR)
3-p(2) (R is identical with above-mentioned definition in the formula, R
1Be the organic group with the functional group that selects from amino, epoxy group(ing) and sulfydryl, p is 0 or 1) be dispersed in the operation that makes it to be emulsified into a water miscible liquid in (D) aqueous solution that contains (C) tensio-active agent; With
(b) an above-mentioned water miscible liquid is heated under 70～90 ℃ of temperature, makes the operation of the organopolysiloxane polycondensation of above-mentioned terminal hydroxy group envelope chain.The embodiment of invention
Below be described in more detail the present invention.
(A) composition in the inventive method is by general formula (1) expression organopolysiloxane, and preferably be considered impurity, the several cyclic low molecular weight content of siloxane 10 below of Siliciumatom less than 5 weight %, terminal hydroxy group seals the organopolysiloxane of chain.
In the general formula (1), R is the replacement or the unsubstituted monovalence alkyl of 1～20 carbon atom, and n represents to satisfy the integer of 10≤n≤200.
The example of R can be enumerated alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cycloalkyl such as cyclopentyl, cyclohexyl, aryl such as phenyl, tolyl, alkenyl such as vinyl, allyl group, and contained part or all halo alkyl that is replaced by halogen atom of hydrogen atom etc. in these groups.Wherein the methyl ratio account for 90 moles of % of whole R groups above from industrial preferred.
Among the present invention, the Siliciumatom number is less than under 10 the occasion of cyclic low molecular weight content of siloxane greater than 5 weight % in the organopolysiloxane raw material (A), volatile low-molecular-weight siloxane content will be above 5 weight % in the siloxane polymer after the polycondensation, will take place to worsen because of volatile siloxane after the emulsion application makes operating environment, thus bad.So must use lower molecular weight annular siloxane quantity is adjusted to below the 5 weight %, preferably adjusted to below the 3 weight %.In addition,, then be difficult to the Siliciumatom number is adjusted to below the 5 weight % less than 10 cyclic low molecular weight content of siloxane, otherwise, therefore must make n satisfy 10≤n≤200 if stability in storage worsens during greater than 200 emulsions if n is less than 10.
As the organoalkoxysilane that contains functional group that (B) composition in the inventive method is used, be material by general formula (2) expression.In the general formula (2), R is same as described above, R
1It is the organic group that contains the functional group that from amino, epoxy group(ing) and sulfydryl, selects.
Contain amino organic group, can enumerate general formula-(CH
2)
a-(MR
4-CH
2CH
2)
bR
5R
6The group of expression, R
4, R
5And R
6Expression is selected from the monovalence alkyl of hydrogen atom and 1～10 carbon atom separately, and wherein at least one is a hydrogen atom, and a is the integer in 1～6, and b is the integer in 0～3.
As containing of (B) composition in the inventive method amino organic alcoxyl at the specific examples of silane, can enumerate 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) aminopropyltriethoxywerene werene, 3-aminopropyltriethoxywerene werene, 3-TSL 8330,3-(2-amino-ethyl) aminopropyl dimethoxy-methyl silane, 3-aminopropyl diethoxymethyl silane etc.
Specific examples as the organoalkoxysilane that contains epoxy group(ing) of (B) composition among the present invention, can enumerate 3-glycidyl oxygen propyl trimethoxy silicane, 3-glycidyl oxygen propyl group diethoxymethyl silane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl dimethoxy-methyl silane etc.
As the specific examples of the organoalkoxysilane that contains sulfydryl of (B) composition among the present invention, can enumerate 3-sulfydryl propyl trimethoxy silicane and 3-sulfydryl propyl group dimethoxy-methyl silane etc.Among the present invention, in the scope of not damaging the object of the invention, also can add the organoalkoxysilane that contains above-mentioned functionality organic group the partial hydrolysis condenses, contain the functionality organic group, have the organo-siloxane oligopolymer of siloxane unit, carry out polycondensation.
The use level of the organoalkoxysilane that contains the functionality organic group of the organopolysiloxane of composition (A) and composition (B), the two adds up to 10～60 weight % that preferably account for the emulsion total amount.Because this resultant is less than 10 weight % or low above stability of emulsion under the occasion of 60 weight %.More preferably 30～55%.And the use level of the organoalkoxysilane that contains the functionality organic group of composition (B), should be between 0.1～20 weight part with respect to the organopolysiloxane of 100 weight part compositions (A), preferably be between 1～10 weight part.Low in the emulsion when composition (B) is lower than 0.1 weight part to the contribution of functionality organic group, on the contrary if surpass 20 weight parts then owing to being recovered under the situation that does not participate in reacting, so bad with composition (A).
The tensio-active agent of conduct (C) composition in the inventive method, so long as make (A) and (B) the just special restriction of nothing of emulsifying agent of composition homogeneous dispersion usefulness in water, for example can use the positively charged ions such as acetate of quaternary ammonium salt, alkylamine is tensio-active agent, amphoterics such as alkyl betaine, alkyl imidazoline, nonionic such as Voranol EP 2001, polyoxyethylene fatty acid ester is a kind of in the tensio-active agent, perhaps is used in combination.
Special preferred cationic is a tensio-active agent in the polycondensation of the present invention.Can enumerate for example chain alkyl trimethyl ammonium chlorides such as decyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride as quaternary ammonium salt.(C) use level of composition accounts for 0.1～10 weight % of emulsion total amount, because emulsion instability when being lower than 0.1 weight %, the release property and the thermotolerance that then make the silicone emulsion that expection obtains that surpass 10 weight % reduce.More preferably be between 0.5～5 weight %.
The emulsion that above-mentioned cooperation can make operation (a) obtain, heating in operation (b) and carry out the polycondensation of composition (A) but for this reaction is well on, must make pH be higher than 7, promptly is alkalescence.The functional group of composition (B) is under the occasion of epoxide group or sulfydryl, must adopt the method for adding basic cpd in emulsion to be adjusted to alkalescence, and when functional group be that the occasion of amino is next not necessarily must the interpolation basic cpd.The stability of the emulsion of the present invention that polycondensation obtains,, no matter whether add the parlkaline compound as described later, all should be added acidic cpd pH is adjusted to below 7 for well with acidity.
In order to improve the stability of the silicone emulsion of the present invention that polycondensation obtains, in the scope of not damaging the object of the invention, after the polycondensation or after the neutralization, also can add other nonionic surface active agent, cationic surfactant or amphoterics.
Organic polysiloxane emulsion of the present invention can be made as follows: preferably in being dissolved with the alkaline aqueous medium of alkaline matter, in the presence of at least a tensio-active agent of from cationic surfactant, amphoterics and nonionic surface active agent, selecting, with above-mentioned organo-siloxane dispersion and emulsion, under 70～90 ℃ of temperature, make it carry out polycondensation then, and then add acidic substance pH4～9 that neutralize.The polycondensation temperature is lower than 70 ℃, and it is slow that reaction is carried out, and impairs the stability of emulsion in the polycondensation and surpass under 90 ℃ the occasion, thereby must be in 70～90 ℃.
The median size of an emulsion must be in 50～250 nanometer range after this emulsification, preferred 100～220 nanometers.When median size surpasses 250 nanometers, make because of stability of emulsion worsens that separation of emulsions is two-layer in the polycondensation, if be lower than 50 nanometers then the necessary tensio-active agent quantity of emulsification increase and impracticable.
Cationic surfactant uses under the occasion of quaternary ammonium salt cationic surfactant, owing to a little less than its katalysis, make the oil content viscosity that extracts from the organic polysiloxane emulsion that obtains be reduced to 10, below the 000mPas.Will desire obtain extraction oil content viscosity greater than 10 in addition, the organopolysiloxane of 000mPas is under the occasion of emulsion, must add alkaline matters such as potassium hydroxide, sodium hydroxide, potassium silicate in an emulsion.The addition of alkaline matter should be in 0.01～0.5 weight part scope with respect to 100 weight parts (A) composition.
This polycondensation is also relevant with temperature, is in usually within 1～100 hour, and is in most cases complete in 10～50 hours.Though reaction can be carried out under static condition, preferably under stirring, 1～100 rev/min mitigation carries out.After the polycondensation fully,, the pH value is adjusted to 4～9 by adding the acidic substance neutralization.When the pH value less than 4 or greater than 9 the time, the extended storage stability that obtains silicone emulsion is low, thus should make pH be in 4～9, in preferred 5～8 scopes.As the acidic substance that add this moment, can enumerate mineral acids such as organic acid such as formic acid, acetate, lactic acid, propanedioic acid, oxyacetic acid and hydrochloric acid, sulfuric acid, phosphoric acid.
Obtain organic polysiloxane emulsion of the present invention, the median size of an emulsion is in 50～250 nanometer range.In order to obtain being in the median size in this scope, adopt the high-pressure emulsification machine with (A)～(D) mixture of ingredients dispersion and emulsion under 50～300MPa high shear stress.This shear pressure then is difficult to make the median size that obtains emulsion less than 250 nanometers if be lower than 50MPa, even and it is brought up to can not obtain effect that median size is further reduced than this numerical value more than the 300mPa.Therefore preferred shear pressure is 70～200MPa.
This high-pressure emulsification machine for example can be enumerated ultra-high voltage ガ ウ リ Application homogenizer (ホ モ ジ Na イ ザ-), Micro Fluid machine (マ イ Network ロ Off Le イ ダ イ ザ), nanometer machine (Na ノ マ イ ザ), pulverizer (ア Le テ イ マ イ ザ) (more than be trade(brand)name) etc. alternately.Before this high-pressure emulsification, also can mix machine (コ Application PVC ミ キ サ-) (trade(brand)name), colloidal mill etc. and prepare emulsification with homogenizer, stirring homogenizer (ア ジ ホ モ ミ キ サ-) (trade(brand)name), connection arbitrarily.
Embodiment
Below be described in more detail embodiments of the present invention with embodiment, but the present invention is not limited by following examples.Wherein viscosity in an embodiment all refers to the measured value under 25 ℃.
Embodiment 1
Use homogenizer under 1000 rev/mins of speed of rotation, stir by 472 mol formulas-(O-Si (CH on one side
2)
2)
40The several cyclic low molecular weight content of siloxane below 10 of-OH represents, Siliciumatom are the mixture of terminal dihydroxyl organopolysiloxane, 14 gram 3-(2-amino-ethyl) TSL 8330 and 14 gram 3-(2-amino-ethyl) the aminopropyl dimethoxy-methyl silane of 1.1 weight %, the mixed solution of the palmityl trimethyl ammonium chloride aqueous solution of 150 grams 30 weight %s and 30 gram ground deionized waters slowly splashed into wherein make it phase inversion on one side.After its thickening, stirring velocity is brought up to 5000 rev/mins stirred 15 minutes, add 320 gram deionized water dilutions then.Then under the 100mPa shear pressure, make its decentralized system become emulsion one time with " Na ノ マ イ ザ-LA-31 type " stirrer (Na ノ マ イ ザ-Co., Ltd. produces).Measuring with " Coulter N4+ sub-micro particle size distribution device (Coulter company product) " after the median size of this emulsion is 190 nanometers.Non-volatile content content in this emulsion, through 105 ℃ 3 hours be 50.4 weight % after the drying.Then this emulsion was made it to carry out polycondensation in 24 hours 70 ℃ of heating, add then after 8 gram acetate regulate pH to 7, having obtained median size is the oyster white " latex A " of 180 nanometers.This " latex A " is 48.8 weight % through 105 ℃ of 3 hours dried non-volatile content content, and the cyclic low molecular weight content of siloxane is 3.1 weight %.This " latex A " demonstrates advantages of excellent stability even at room temperature preserve and also do not find a layering in month.Add 200 gram Virahol extraction oil contents in 100 grams this " latex A ", the measured value of dry back oil content viscosity is 2900mPas, and amine equivalent is 4330 gram/moles.Be shown among the table 1 about the physical property measurement value of " latex A " and evaluation result.
Embodiment 2
Use homogenizer under 1000 rev/mins of speed of rotation, stir on one side by 472 grams and contain the terminal dihydroxyl organopolysiloxane several cyclic low molecular weight siloxanes 10 below of Siliciumatom, identical with embodiment 1 of 1.1 weight % and the mixture of 28 gram 3-(2-amino-ethyl) TSL 8330, with 150 restrain the palmityl trimethyl ammonium chloride aqueous solution of 30 weight %s and 30 mixed solutions that restrain deionized waters and slowly splash into wherein make it phase inversion on one side.After its thickening, stirring velocity is brought up to 5000 rev/mins stirred 15 minutes, add 320 gram deionized water dilutions then.Then under the 100MPa shear pressure, its decentralized system is become emulsion one time with " Na ノ マ イ ザ-LA-31 type " stirrer (Na ノ マ イ ザ-Co., Ltd. produces).Measuring with " Coulter N4+ submicron particle size measure of spread device (Coulter company product) " after the median size of this emulsion is 190 nanometers.Non-volatile content content in this emulsion, through 105 ℃ 3 hours be 50.0 weight % after the drying.Then this emulsion was made it to carry out polycondensation in 24 hours 70 ℃ of heating, add then after 8 gram acetate regulate pH to 7, having obtained median size is the oyster white " emulsion B " of 180 nanometers.This " emulsion B " is 48.7 weight % through 105 ℃ of 3 hours dried non-volatile content content, and the cyclic low molecular weight content of siloxane is 2.4 weight %.This " emulsion B " demonstrates advantages of excellent stability even at room temperature preserve and also do not find a layering in month.Add 200 gram Virahol extraction oil contents in 100 grams this " emulsion B ", the measured value of dry back oil content viscosity is 11, and 000mPas, amine equivalent are 4140 gram/moles.Be shown among the table 1 about the physical property measurement value of " emulsion B " and evaluation result.
Embodiment 3
Use homogenizer under 1000 rev/mins of speed of rotation, stir on one side the mixture that is contained terminal dihydroxyl organopolysiloxane, 14 gram 3-(2-amino-ethyl) TSL 8330 and 14 gram 3-(2-amino-ethyl) the aminopropyl dimethoxy-methyl the silane several cyclic low molecular weight siloxanes 10 below of Siliciumatom, identical with embodiment 1 of 1.1 weight % by 472 grams ,-Bian restrains the palmityl trimethyl ammonium chloride aqueous solution of 30 weight % and 30 mixed solutions that restrain deionized waters with 150 and slowly splashes into and wherein make it phase inversion.After its thickening, stirring velocity is brought up to 5000 rev/mins stirred 15 minutes, add 300 gram deionized water dilutions then.Then under the 100MPa shear pressure, its emulsification is disperseed to make emulsion one time twice with " LAB40-10RBF1 type " ultra-high voltage ガ ウ リ Application ホ モ ジ Na イ ザ-(APV go-リ Application Co., Ltd. produces).Measuring with " Coulter N4+ submicron particle size measure of spread device (Coulter company product) " after the median size of this emulsion is 200 nanometers.Non-volatile content content in this emulsion, through 105 ℃ 3 hours be 51.0 weight % after the drying.Add 20 grams, 10 weight % potassium hydroxide aqueous solutions in this emulsion, made it to carry out polycondensation in 72 hours 70 ℃ of heating, add then after 10 gram acetate regulate pH to 8, having obtained median size is the oyster white " emulsion C " of 210 nanometers.This " emulsion C " is 47.1 weight % through 105 ℃ of 3 hours dried non-volatile content content, and the cyclic low molecular weight content of siloxane is 7.7 weight %.This " emulsion C " demonstrates advantages of excellent stability even at room temperature preserve and also do not find a layering in month.Add 200 gram Virahol extraction oil contents in 100 grams this " emulsion C ", the measured value of dry back oil content viscosity is 280, and 000mPas, amine equivalent are 4630 gram/moles.Be shown among the table 1 about the physical property measurement value of " emulsion C " and evaluation result.
Embodiment 4
Use homogenizer under 1000 rev/mins of speed of rotation, stir on one side by 472 grams and contain the terminal dihydroxyl organopolysiloxane several cyclic low molecular weight siloxanes 10 below of Siliciumatom, identical with embodiment 1 of 1.1 weight % and the mixture of 28 gram 3-glycidoxypropyltrimewasxysilane, with 150 restrain the palmityl trimethyl ammonium chloride aqueous solution of 30 weight %s and 30 mixed solutions that restrain deionized waters and slowly splash into wherein make it phase inversion on one side.After its thickening, stirring velocity is brought up to 5000 rev/mins stirred 15 minutes, add 300 gram deionized water dilutions then.Then under the 100MPa shear pressure, its emulsification is disperseed to make emulsion one time twice with " LAB40-10RBF1 type " ultra-high voltage ガ ウ リ Application ホ モ ジ Na イ ザ-(APV go-リ Application Co., Ltd. produces).Measuring with " Coulter N4+ submicron particle size measure of spread device (Coulter company product) " after the median size of this emulsion is 180 nanometers.Non-volatile content content in this emulsion, through 105 ℃ 3 hours be 51.0 weight % after the drying.Add 20 grams, 10 weight % potassium hydroxide aqueous solutions in this emulsion, made it to carry out polycondensation in 72 hours 70 ℃ of heating, add then after 2.5 gram acetate regulate pH to 7, having obtained median size is the oyster white " emulsion D " of 190 nanometers.This " emulsion D " is 47.5 weight % through 105 ℃ of 3 hours dried non-volatile content content, and the cyclic low molecular weight content of siloxane is 6.9 weight %.This " emulsion D " demonstrates advantages of excellent stability even at room temperature preserve and also do not find a layering in month.Add 200 gram Virahol extraction oil contents in 100 grams this " emulsion D ", the measured value of dry back oil content viscosity is 850,000mPas.Be shown among the table 1 about the physical property measurement value of " emulsion D " and evaluation result.
Reference examples 1
Except " the Na ノ マ イ ザ-LA-31 type " that will be among the embodiment 1 uses makes ガ ウ リ Application ホ モ ジ Na イ ザ-" 15M-8TA " (APV go-リ Application Co., Ltd. produces) into and shear pressure is changed into the 30MPa from 100MPa, obtained a milky emulsion similarly to Example 1.The median size of this emulsion is 310 nanometers.Just directly be separated into two-layer 70 ℃ of emulsions that obtain after heating 24 hours down without neutralization this emulsion similarly to Example 1.Similarly to Example 1 in the condition and after to have obtained median size be milky " the emulsion E " of 300 nanometers." emulsion E " at room temperature preserves after 7 days and is separated into two-layer with regard to discovery.Add 200 gram Virahol extraction oil contents in 100 grams this " emulsion E ", the measured value of dry back oil content viscosity is 200mPas, and the almost not polymerization of raw material organopolysiloxane is described.Be shown among the table 1 about the physical property measurement value of " emulsion E " and evaluation result.
Reference examples 2
Except the terminal dihydroxyl organopolysiloxane that will use among the embodiment 3 is modified to the octamethylcyclotetrasiloxane of measuring, and the shear pressure of ultra-high voltage ガ ウ リ Application ホ モ ジ Na イ ザ-" LAB-10RBFI " (APV go-リ Application Co., Ltd. produce) changed into outside the 30MPa from 100MPa, obtained milky " emulsion F " similarly to Example 3.Polycondensation is the non-volatile content content of an emulsion up till now, through 105 ℃ 3 hours be 46.6 weight % after the drying.And the median size of emulsion F is 270 nanometers after the polycondensation, and 105 ℃ of 3 hours dry back non-volatile content content are 41.3 weight %, and the cyclic low molecular weight content of siloxane is 10.5 weight %.Add 200 gram Virahol extraction oil contents in 100 grams " emulsion F ", the measured value of dry back oil content viscosity is 95,000mPas.Be shown among the table 1 about the physical property measurement value of " emulsion F " and evaluation result.
Active constituent content is adjusted to the treatment solution of 0.7 weight % in the emulsion that preparation 100 grams obtain the foregoing description and reference examples, its full dose is sprayed on the fabric of 20 gram 6 DENIER * 64mm trevira length, pick up is decided to be 100%, and then 150 ℃ of thermal treatments 20 minutes.The slipperiness and the flexibility that obtain handling cloth are touched evaluation by following standard hand:
Slipperiness: zero is fabulous, and △ is fairly good, * poor
Flexibility: zero is fabulous, and △ is fairly good, * poor
Wherein utilize following formula to calculate the cyclic low molecular weight content of siloxane:
The cyclic low molecular weight content of siloxane=
100 * (non-volatile content content in the emulsion-
Non-volatile content content in the emulsion after the polycondensation)/50 ... (4)
Table 1
| The kind of emulsion | Cyclic low molecular weight content of siloxane (with respect to siloxanes weight %) | Extraction oil content viscosity (mPas) | Extraction oil content functional group's equivalent (g/mol) | Handle evaluation result | |||
| Slipperiness | Flexibility | ||||||
| Embodiment | 1 | Latex A | ?3.1 | ?2,900 | ?4,330 | ?△ | ?○ |
| 2 | Emulsion B | ?2.4 | ?11,000 | ?4,140 | ?○ | ?○ | |
| 3 | Emulsion C | ?7.7 | ?280,000 | ?4,630 | ?○ | ?○ | |
| 4 | Emulsion D | ?6.9 | ?850,000 | ?4,050 | ?- | ?- | |
| Reference examples | 1 | Emulsion E | ?- | ?200 | ?8,800 | ?× | ?× |
| 2 | Emulsion F | ?10.5 | ?95,000 | ?4,800 | ?△ | ?△ | |
The effect of invention
Can make excellent in stability, contain the organic polysiloxane emulsion of functional group according to the present invention.
Claims (6)
1, a kind of manufacturing has the method for the organopolysiloxane water miscible liquid of functional group, comprising following steps:
(a) the following general formula of (A) 100 weight parts is represented, each molecular chain-end is by the organopolysiloxane of hydroxyl envelope chain
H-(-O-SiR
2-)
n-OH??????????????????????????(1)
In the formula, R represents the monovalence alkyl of 1～20 carbon atom, and n represents 10～200 positive integers, has the organoalkoxysilane compound of the functional group that is represented by following general formula with (B) 0.1～20 weight part,
R
pR
1Si(OR)
3-p?????????????????????????????(2)
R is identical with above-mentioned definition in the formula, R
1Be the organo-functional group with amino, epoxy group(ing) or sulfydryl, p is 0 or 1
Be dispersed in the operation of a water miscible liquid of siloxanes that makes it to be emulsified into particle median size 50～250nm in (D) aqueous solution that is dissolved with (C) tensio-active agent; With
(b) water miscible liquid of above-mentioned siloxanes is heated under 70～90 ℃ of temperature, make above-mentioned organopolysiloxane carry out the operation of polycondensation.
2, according to the described manufacture method of claim 1 with organopolysiloxane water miscible liquid of functional group, wherein in step (b) the pH value of a water miscible liquid of siloxanes greater than 7, and after step (b), carry out neutralization procedure (c), add in the acidic cpd and the basicity in the said aqueous siloxane emulsion.
3, according to the described manufacture method of claim 2, wherein radicals R with organopolysiloxane water miscible liquid of functional group
1Be organo-functional group, and water miscible liquid of siloxanes is mixed with basic cpd, make the pH value greater than 7 with epoxy group(ing) or sulfydryl.
4, according to the described manufacture method that contains the organopolysiloxane water miscible liquid of functional group of claim 1, the wherein emulsification of said siloxanes in the implementation step (a) under 50～300MPa shear pressure.
5, according to the described manufacture method with organopolysiloxane water miscible liquid of functional group of claim 1, wherein said tensio-active agent is a cationic surfactant in (C).
6, according to the described manufacture method with organopolysiloxane water miscible liquid of functional group of claim 3, wherein the content of said basic cpd is 0.01～0.5 weight part with respect to 100 weight part compounds (A).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001167949A JP3966538B2 (en) | 2001-06-04 | 2001-06-04 | Method for producing organopolysiloxane emulsion |
| JP167949/2001 | 2001-06-04 |
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| Publication Number | Publication Date |
|---|---|
| CN1389495A true CN1389495A (en) | 2003-01-08 |
| CN1223625C CN1223625C (en) | 2005-10-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02120247 Expired - Fee Related CN1223625C (en) | 2001-06-04 | 2002-05-21 | Method for preparing organic polysiloxane emulsion |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3966538B2 (en) |
| CN (1) | CN1223625C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910186A (en) * | 2007-11-02 | 2010-12-08 | 莫门蒂夫性能材料股份有限公司 | Copolymers of epoxy compounds and amino silanes |
| CN1814654B (en) * | 2005-02-04 | 2011-07-06 | 信越化学工业株式会社 | Method for preparing organic polysiloxane containing amino |
| CN102898883A (en) * | 2011-07-29 | 2013-01-30 | 道康宁(中国)投资有限公司 | Coating composition, method of using the composition to coat material surface and material with surface treated by the composition |
| CN103865064A (en) * | 2012-12-12 | 2014-06-18 | 董方民 | Siloxane emulsion with semi-interpenetrating network structure |
| CN106040562A (en) * | 2016-08-09 | 2016-10-26 | 东莞市卓越新材料科技有限公司 | Method for improving surface friction coefficient of aluminum plastic film and equipment thereof |
| CN109880561A (en) * | 2017-12-06 | 2019-06-14 | 上海本诺电子材料有限公司 | A kind of epoxy resin embedding adhesive composition and preparation method thereof |
| CN111116917A (en) * | 2019-12-18 | 2020-05-08 | 宁波辉宏新材料有限公司 | Method for synthesizing emulsion type MDQ silicon resin by emulsion polymerization method |
| CN113573737A (en) * | 2019-02-21 | 2021-10-29 | 硅循环股份有限公司 | Direct nano emulsion method for synthesizing spherical organic siloxane submicron/nano particles |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0302840D0 (en) * | 2003-02-07 | 2003-03-12 | Dow Corning | Process for making silicone emulsions |
| DE102004014218A1 (en) * | 2004-03-23 | 2005-10-13 | Wacker-Chemie Gmbh | Process for the preparation of amino-functional organopolysiloxanes |
| JP4717435B2 (en) * | 2004-12-27 | 2011-07-06 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Silicone emulsion composition and mold release agent |
| DE102005022100A1 (en) * | 2005-05-12 | 2006-11-16 | Wacker Chemie Ag | Process for the preparation of dispersions of crosslinked organopolysiloxanes |
| DE102005022099A1 (en) * | 2005-05-12 | 2006-11-16 | Wacker Chemie Ag | Process for the preparation of dispersions of crosslinked organopolysiloxanes |
| JP4697447B2 (en) * | 2006-05-01 | 2011-06-08 | 信越化学工業株式会社 | Method for producing functional group-containing diorganopolysiloxane emulsion |
-
2001
- 2001-06-04 JP JP2001167949A patent/JP3966538B2/en not_active Expired - Fee Related
-
2002
- 2002-05-21 CN CN 02120247 patent/CN1223625C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814654B (en) * | 2005-02-04 | 2011-07-06 | 信越化学工业株式会社 | Method for preparing organic polysiloxane containing amino |
| CN101910186A (en) * | 2007-11-02 | 2010-12-08 | 莫门蒂夫性能材料股份有限公司 | Copolymers of epoxy compounds and amino silanes |
| CN101910186B (en) * | 2007-11-02 | 2016-11-09 | 莫门蒂夫性能材料股份有限公司 | Epoxide and the copolymer of amino silane |
| CN102898883A (en) * | 2011-07-29 | 2013-01-30 | 道康宁(中国)投资有限公司 | Coating composition, method of using the composition to coat material surface and material with surface treated by the composition |
| CN103865064A (en) * | 2012-12-12 | 2014-06-18 | 董方民 | Siloxane emulsion with semi-interpenetrating network structure |
| CN106040562A (en) * | 2016-08-09 | 2016-10-26 | 东莞市卓越新材料科技有限公司 | Method for improving surface friction coefficient of aluminum plastic film and equipment thereof |
| CN109880561A (en) * | 2017-12-06 | 2019-06-14 | 上海本诺电子材料有限公司 | A kind of epoxy resin embedding adhesive composition and preparation method thereof |
| CN113573737A (en) * | 2019-02-21 | 2021-10-29 | 硅循环股份有限公司 | Direct nano emulsion method for synthesizing spherical organic siloxane submicron/nano particles |
| CN111116917A (en) * | 2019-12-18 | 2020-05-08 | 宁波辉宏新材料有限公司 | Method for synthesizing emulsion type MDQ silicon resin by emulsion polymerization method |
| CN111116917B (en) * | 2019-12-18 | 2022-02-08 | 宁波辉宏新材料有限公司 | Method for synthesizing emulsion type MDQ silicon resin by emulsion polymerization method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1223625C (en) | 2005-10-19 |
| JP2002363408A (en) | 2002-12-18 |
| JP3966538B2 (en) | 2007-08-29 |
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