CN115819778B - Organosilicon emulsifier for emulsifying organosilicon elastomer and preparation method thereof - Google Patents
Organosilicon emulsifier for emulsifying organosilicon elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organosilicon emulsifier for emulsifying an organosilicon elastomer and a preparation method thereof, wherein the molecular formula of the organosilicon emulsifier is [ (CH) 3 ) 3 SiO 1/2 ] a [SiO 4/2 ] b [HO‑SiO 3/2 ] (c‑x) [OH(EO) d (PO) e ‑OSiO 3/2 ] x The method comprises the steps of carrying out a first treatment on the surface of the The organosilicon emulsifier is synthesized by MQ silicon resin and polyether containing EO/PO blocks through catalytic reaction; wherein c-x > 2x-a. The present invention has an effect of improving dispersibility of the silicone elastomer emulsified in an aqueous solvent or DMF solvent.
Description
Technical Field
The present application relates to the field of decorative covers, and more particularly, to a silicone emulsifier for emulsifying silicone elastomers and a method of making the same.
Background
Resin compositions such as urethane resins and acrylic resins include solvent-type resin compositions and aqueous-type resin compositions. Solvent-based resin compositions use organic solvents to improve film formation, but organic solvents are volatile, especially in the higher temperature step of drying, etc. In order to reduce adverse effects on the health of operators, organic solvents having high boiling points such as DMF are often used.
The solvent-based and water-based resin compositions can be subjected to internal or surface treatment to prepare artificial leather or synthetic leather, and are widely used in the fields of automobile sheets, furniture, clothing, etc. For use, the resin composition is required to have good slidability and abrasion resistance. In order to meet the above requirements, a high molecular weight silicone elastomer is usually blended into a resin composition, but in solvent-based resin compositions using a high boiling point organic solvent such as DMF, and aqueous resin compositions, the dispersibility of the silicone elastomer is poor, and emulsification is necessary to improve the dispersing effect.
The dispersant for emulsification usually employs a surfactant, but if a nonionic surfactant, an anionic surfactant or a cationic surfactant is used for emulsifying the silicone elastomer, it is generally difficult to completely emulsify the silicone elastomer, and precipitation is likely to occur. Therefore, it is required to develop an emulsifier which can effectively and stably disperse a silicone elastomer in both a solvent such as DMF and water.
Disclosure of Invention
In order to improve the dispersion effect for emulsifying the silicone elastomer in the water solvent or DMF solvent, the present application provides a silicone emulsifier for emulsifying the silicone elastomer.
A silicone emulsifier for emulsifying a silicone elastomer, wherein the silicone emulsifier has a molecular formula of [ (CH) 3 ) 3 SiO 1/2 ] a [SiO 4/2 ] b [HO-SiO 3/2 ] (c-x) [OH(EO) d (PO) e -OSiO 3/2 ] x The method comprises the steps of carrying out a first treatment on the surface of the The organosilicon emulsifier is synthesized by MQ silicon resin and polyether containing EO/PO blocks through catalytic reaction; wherein c-x > 2x-a.
By adopting the technical scheme, the organic silicon emulsifier adopted in the application contains polysiloxane and polyether molecular structure chain segments, wherein the polysiloxane part endows the organic silicon emulsifier with low surface tension, antistatic property and physiological inertia; the polyoxyethylene group part in the polyether part is hydrophilic, the polyoxypropylene group part is hydrophobic because of having hydrophobicity due to methyl, and the hydrophilicity and lipophilicity of the molecular structure of the polyether can be adjusted by adjusting the polymer and the ratio of the ethylene oxide to the propylene oxide in the polyether part.
Therefore, the organosilicon emulsifier in the application is designed through polysiloxane and polyether chain segments, the ratio of the polysiloxane to the polyether is ensured to be c-x & gt2 x & lt-a, so that the organosilicon emulsifier can form a plurality of adsorption sites on the interface between DMF solvent and the organosilicon elastomer or between water solvent and the organosilicon elastomer, and therefore, compared with the traditional emulsifier, the organosilicon emulsifier in the application has more complete and stable dispersing effect and better emulsifying effect.
Further, the kinematic viscosity of the organosilicon emulsifier is controlled to be 0.001m 2 /s～0.004m 2 /s。
Further, wherein the MQ silicone resin is: [ (CH) 3 ) 3 SiO 1/2 ] a [SiO 4/2 ] b [HO-SiO 3/2 ] c M/q=1/10-1/1; molecular weight: 1000-50000.
Further, polyethers include polyether A and polyether B, and are polyethers containing EO/PO blocks of the general formula: h- (EO) d (PO) e -OH；
Wherein, EO/PO=1/10-10/1 of polyether A, the molecular weight is 1000-50000;
wherein EO/PO=1/10-10/1 of polyether B, molecular weight is 100-10000.
Further, in the MQ silicone resin, M/q=1/3, and the molecular weight is 5000; EO/po=1/1 in the polyether a, molecular weight 5000; EO/po=1/4 in the polyether B, the molecular weight is 2000.
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 10-40 parts of MQ silicone resin, 10-60 parts of polyether A, 20-70 parts of polyether B and 20-70 parts of organic solvent, and heating;
s2: heating to 135-150deg.C, refluxing, and dehydrating for 2 hr; adding 0.01-0.5 part of catalyst; reflux reaction is carried out for 5 to 10 hours at constant temperature; water was separated from the separator every hour and the weight was recorded;
s3: after no water is separated out, the kettle temperature is reduced to 80-100 ℃, and 0.01-0.5 part of terminator is added for reaction for half an hour; obtaining a semi-finished product A;
s4: distilling off the organic solvent under reduced pressure at 120 ℃ minus 0.098 MPa;
s5: cooling to 55-70 deg.c and filtering to obtain the organosilicon emulsifier product.
Further, the step S2 is: heating to 140-145 ℃, and refluxing and dehydrating for 1 hour; adding 0.01-0.5 part of catalyst, and carrying out constant temperature reflux reaction for 5-10 hours.
Further, the catalyst comprises dibutyltin dilaurate. And stannous oxide, dibutyl tin dilaurate. And stannous oxide in the mass ratio of 1 to 2-3.
By adopting the technical scheme, firstly, the tin catalyst can effectively inhibit the progress of partial side reaction, and the width of molecular weight distribution is reduced; in the catalyst system after the compounding, the two catalysts can mutually promote, so that the overall catalytic effect is improved.
Further, the control pressure in the step S2 is 1.5-2 MPa.
By adopting the technical scheme, in the catalytic reaction process, the high pressure can reduce the activation energy and the frequency factor of the raw materials, and the activation performance of the raw materials is obviously improved, but the better the activation performance is, the better the performance of the finished organosilicon emulsifier is. When the pressure is too high, on one hand, the requirement on equipment is higher, and the risk of the equipment in the reaction process is higher; on the other hand, the molecular weight of the finished organosilicon emulsifier is too large, the branched chains are obviously increased, and the emulsifying effect is greatly reduced. Therefore, when the pressure in the catalytic reaction process is controlled between 1.5 and 2MPa, the raw materials in the reaction process can have both higher activation performance and generate the organosilicon emulsifier with more proper molecular weight.
Further, the emulsification method for emulsifying the organosilicon elastomer comprises the following steps: adding 5-50 parts of organosilicon emulsifier into 10-80 parts of organosilicon elastomer for 2-5 times, each time for 30 minutes, and finally adding deionized water of which the volume is not more than 50 parts.
In summary, the present application has the following beneficial effects:
1. the organosilicon emulsifier adopted in the application contains polysiloxane and polyether molecular structures, so that the organosilicon emulsifier has better dispersing effect on organosilicon elastomer emulsified in a water solvent or DMF solvent, and the emulsification is more thorough and complete.
2. In the preparation method of the organosilicon emulsifier, the emulsifier with good emulsifying effect on the organosilicon elastomer is achieved by controlling the M/Q value of the MQ silicon resin in the raw materials, the EO/PO value in the polyether and the respective molecular weight.
3. In the preparation method of the organosilicon emulsifier, the prepared organosilicon emulsifier is more favorable for emulsifying the organosilicon elastomer by the selection of the catalyst and the matching of the pressurizing condition, and the lengths of the polysiloxane chain segment and the polyether chain segment in the molecule are more suitable for forming more attachment points in the emulsification process.
Detailed Description
The present application is described in further detail below with reference to examples.
In the following examples, the MQ silicone resin used in the raw materials has the general formula: [ (CH) 3 ) 3 SiO 1/2 ] a [SiO 4/2 ] b [HO-SiO 3/2 ] c ；
Polyethers A and B have the general formula: h- (EO) d (PO) e -OH。
Examples
Example 1
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 30 parts of MQ silicone resin, 40 parts of polyether A, 40 parts of polyether B and 60 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 140 ℃, and refluxing and dehydrating for 1 hour; then adding 0.08 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 125 ℃, 0.2 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 60 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=1/10 in MQ silicone resin; molecular weight: 23000;
EO/po=1/10 for polyether a, molecular weight 21000;
wherein, EO/po=1/10 of polyether B, the molecular weight is 4800.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 2
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 10 parts of MQ silicone resin, 50 parts of polyether A, 59 parts of polyether B and 57 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 135 ℃, and refluxing and dehydrating for 1 hour; then adding 0.33 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 131 ℃, 0.25 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 68 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=1/10 in MQ silicone resin; molecular weight: 2000;
EO/po=0.2 for polyether a, molecular weight 2000;
wherein, EO/po=3 of polyether B, the molecular weight is 1400.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 3
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 16 parts of MQ silicone resin, 16 parts of polyether A, 55 parts of polyether B and 25 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 143 ℃, and refluxing and dehydrating for 1 hour; then adding 0.07 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 129 ℃, 0.01 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 65 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=1/10 in MQ silicone resin; molecular weight: 5000;
EO/po=1.2 for polyether a, molecular weight 4000;
wherein, EO/po=9.6 of polyether B has a molecular weight of 9200.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 4
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 18 parts of MQ silicone resin, 32 parts of polyether A, 34 parts of polyether B and 48 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 148 ℃, and refluxing and dehydrating for 1 hour; then adding 0.24 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 126 ℃, 0.18 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 67 deg.c and filtering to obtain the organosilicon emulsifier product.
Of the above raw materials, M/q=1.4 in MQ silicone resin; molecular weight: 5000;
EO/po=1.9 for polyether a, molecular weight 6000;
wherein, EO/po=6.4 of polyether B, molecular weight is 6300.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 5
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 18 parts of MQ silicone resin, 17 parts of polyether A, 49 parts of polyether B and 27 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 137 ℃, and refluxing and dehydrating for 1 hour; then adding 0.08 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 127 ℃, 0.04 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 58 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=1.7 in MQ silicone resin; molecular weight: 14000;
EO/po=2.2 for polyether a, molecular weight 10000;
wherein, EO/po=5.4 of polyether B, the molecular weight is 5800.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 6
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 20 parts of MQ silicone resin, 34 parts of polyether A, 59 parts of polyether B and 50 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 145 ℃, and refluxing and dehydrating for 1 hour; then adding 0.27 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 124 ℃, 0.19 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 70 ℃, and filtering to obtain the finished organosilicon emulsifier.
Of the above raw materials, M/q=1.8 in MQ silicone resin; molecular weight: 15000;
EO/po=2.8 for polyether a, molecular weight 16000;
wherein, EO/po=8.6 of polyether B, molecular weight is 8300.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 7
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 20 parts of MQ silicone resin, 57 parts of polyether A, 41 parts of polyether B and 64 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 138 ℃, and refluxing and dehydrating for 1 hour; then adding 0.44 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 135 ℃, 0.44 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 69 deg.c and filtering to obtain the organosilicon emulsifier product.
Of the above raw materials, M/q=1.8 in MQ silicone resin; molecular weight: 16000;
EO/po=3 for polyether a, molecular weight 21000;
wherein, EO/po=5.5 of polyether B, the molecular weight is 5900.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 8
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: 21 parts of MQ silicone resin, 25 parts of polyether A, 24 parts of polyether B and 38 parts of xylene organic solvent are stirred and mixed uniformly in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 141 ℃, and refluxing and dehydrating for 1 hour; then adding 0.19 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 134 ℃, 0.15 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 65 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=2.9 in MQ silicone resin; molecular weight: 17000;
EO/po=4 for polyether a, molecular weight 23000;
wherein, EO/po=1.3 of polyether B, molecular weight 800.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 9
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 23 parts of MQ silicone resin, 23 parts of polyether A, 63 parts of polyether B and 39 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 138 ℃, and refluxing and dehydrating for 1 hour; then adding 0.21 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 121 ℃, 0.18 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 68 ℃, and filtering to obtain the finished organosilicon emulsifier.
Of the above raw materials, M/q=3.8 in MQ silicone resin; molecular weight: 17000;
EO/po=2.8 for polyether a, molecular weight 26000;
wherein, EO/po=9.8 of polyether B has a molecular weight of 9400.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 10
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 23 parts of MQ silicone resin, 38 parts of polyether A, 52 parts of polyether B and 63 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 137 ℃, and refluxing and dehydrating for 1 hour; then adding 0.33 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 123 ℃, 0.41 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 62 ℃, and filtering to obtain the finished organosilicon emulsifier.
Of the above raw materials, M/q=4.2 in MQ silicone resin; molecular weight: 19000;
EO/po=4.9 for polyether a, molecular weight 27000;
wherein, EO/po=1.7 of polyether B has a molecular weight of 1100.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 11
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: 26 parts of MQ silicone resin, 58 parts of polyether A, 32 parts of polyether B and 68 parts of xylene organic solvent are stirred and mixed uniformly in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 142 ℃, and refluxing and dehydrating for 1 hour; then adding 0.46 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 132 ℃, 0.48 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 52 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=5.7 in MQ silicone resin; molecular weight: 23000;
EO/po=5.9 for polyether a, molecular weight 30000;
wherein EO/po=2.4 for polyether B, molecular weight 1200.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The silicone emulsifier per second is added to 40 parts of silicone elastomer 2-5 times, each timeAnd (3) adding deionized water with the volume of not more than 50 parts at intervals of 30 minutes.
Example 12
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 28 parts of MQ silicone resin, 11 parts of polyether A, 30 parts of polyether B and 33 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 141 ℃, and refluxing and dehydrating for 1 hour; then adding 0.18 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 128 ℃, 0.14 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 58 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=6.6 in MQ silicone resin; molecular weight: 34000;
EO/po=6.4 for polyether a, molecular weight 32000;
wherein, EO/po=5.8 of polyether B, the molecular weight is 6000.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 13
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: 29 parts of MQ silicone resin, 46 parts of polyether A, 23 parts of polyether B and 64 parts of xylene organic solvent are stirred and mixed uniformly in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 136 ℃, and refluxing and dehydrating for 1 hour; then adding 0.44 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 118 ℃, 0.47 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 56 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=6.8 in MQ silicone resin; molecular weight: 35000;
EO/po=7.8 for polyether a, molecular weight 35000;
wherein, EO/po=7.8 of polyether B has a molecular weight of 7300.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 14
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: 31 parts of MQ silicone resin, 29 parts of polyether A, 44 parts of polyether B and 60 parts of xylene organic solvent are stirred and mixed uniformly in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 140 ℃, and refluxing and dehydrating for 1 hour; then adding 0.33 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 116 ℃, 0.36 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 55 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=8.3 in MQ silicone resin; molecular weight: 36000;
EO/po=8.1 for polyether a, molecular weight 40000;
wherein, EO/po=1/10 of polyether B, the molecular weight is 100.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 15
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: 31 parts of MQ silicone resin, 11 parts of polyether A, 34 parts of polyether B and 38 parts of xylene organic solvent are stirred and mixed uniformly in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 140 ℃, and refluxing and dehydrating for 1 hour; then adding 0.2 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 117 ℃, 0.18 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 62 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=9 in MQ silicone resin; molecular weight: 40000;
EO/po=8.3 for polyether a, molecular weight 43000;
wherein, EO/po=1.4 of polyether B has a molecular weight of 1100.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 16
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 32 parts of MQ silicone resin, 22 parts of polyether A, 31 parts of polyether B and 52 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 144 ℃, and refluxing and dehydrating for 1 hour; then adding 0.31 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 127 ℃, 0.21 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 65 ℃, and filtering to obtain the finished organosilicon emulsifier.
In the above raw materials, M/q=9.1 in MQ silicone resin; molecular weight: 40000;
EO/po=9.9 for polyether a, molecular weight 45000;
wherein, EO/po=0.3 of polyether B, molecular weight 300.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 17
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 39 parts of MQ silicone resin, 32 parts of polyether A, 24 parts of polyether B and 63 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the initial mixture to 142 ℃, and refluxing and dehydrating for 1 hour; then adding 0.36 part of catalyst, and continuously carrying out reflux reaction for 8 hours at constant temperature; the catalyst is dibutyl tin dilaurate. The mass ratio of the mixture to stannous oxide is 1:2.
S3: after no water is separated out, the temperature of the reaction kettle is reduced to 115 ℃, 0.42 part of terminator is added to continue reflux reaction for 0.5 hour at constant temperature, and a semi-finished product A is obtained;
s4: distilling off the xylene as an organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 64 ℃, and filtering to obtain the finished organosilicon emulsifier.
Of the above raw materials, M/q=9.8 in MQ silicone resin; molecular weight: 43000;
EO/po=10 for polyether a, molecular weight 49000;
wherein, EO/po=4.5 of polyether B has a molecular weight of 4200.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: 30 parts of the kinematic viscosity was controlled to 0.001m 2 The organosilicon emulsifier per second is added into 40 parts of organosilicon elastomer for 2-5 times, each time is separated by 30 minutes, and finally, deionized water with the concentration of not more than 50 parts is added.
Example 18
Example 18 differs from example 1 in that the catalyst used was pure dibutyltin dilaurate. A catalyst.
Example 19
Example 19 differs from example 1 in that a pure stannous oxide catalyst was used as the catalyst.
Example 20
Example 20 differs from example 1 in that dibutyltin dilaurate. And stannous oxide in a mass ratio of 1:3.
Example 21
Example 21 differs from example 1 in that 1.5MPa was pressurized in the reaction vessel of step S2.
Example 22
Example 22 differs from example 1 in that 1.8MPa is pressurized in the reaction vessel of step S2.
Example 23
Example 23 differs from example 1 in that 2MPa is pressurized in the reaction vessel of step S2.
Comparative example
Comparative example 1: the difference from example 1 is that step S3 is: and after no water is separated out, the temperature of the reaction kettle is reduced to 115 ℃, and reflux reaction is continued for 0.5 hour at constant temperature, so that a semi-finished product A is obtained.
Comparative example 2: the difference from example 1 is that: m/q=15 in MQ silicone; molecular weight: 60000.
comparative example 3: the difference from example 1 is that: m/q=0.05 in MQ silicone; molecular weight: 1000.
comparative example 4: the difference from example 1 is that: EO/po=12 for polyether a, molecular weight 51000.
Comparative example 5: the difference from example 1 is that: EO/po=0.05 for polyether a, molecular weight 800.
Comparative example 6: the difference from example 1 is that: EO/po=13 for polyether B, molecular weight 10000.
Comparative example 7: the difference from example 1 is that: EO/po=0.04 for polyether B, molecular weight 500.
Performance test 1: 7mL of the emulsifier water mixed solution with the mass concentration of 0.3% and 3g of the organosilicon elastomer prepared by the method are taken and placed in a 15mL glass test tube, the sealing is good, the mixture is placed in a 55 ℃ water bath for 1h at constant temperature, the mixture is taken out and turned over for 20 times, whether the oil-water phase is completely emulsified or not is observed, the mixture is placed in the 55 ℃ water bath continuously, the observation is carried out, and whether the water phase is separated out or not is recorded in 24 h.
Test 2: 7mL of the emulsifier DMF mixture with the mass concentration of 0.3% and 3g of the organosilicon elastomer prepared by the method are taken out, the mixture is sealed in a 15mL glass test tube, the mixture is placed in a 55 ℃ water bath for 1h at constant temperature, the mixture is taken out and turned over for 20 times, whether the oil-water phase is completely emulsified or not is observed, the mixture is placed in the 55 ℃ water bath continuously, and whether the water phase is separated out or not is recorded in 24h is observed.
The results are shown in the following table:
test 3: the results of further observation for examples 1, 17 to 23 for 1 month, and observation of the presence or absence of precipitation are shown in the following table:
conclusion: as can be seen from the table above, the organosilicon emulsifier used in the application can achieve the emulsifier with better emulsification effect on the organosilicon elastomer by controlling the M/Q value of the MQ silicone resin in the raw material, the EO/PO value in the polyether and the respective molecular weight, otherwise, the emulsification is incomplete easily or the emulsifier is inverted out after a certain period of emulsification. In the application, the M/Q value of the MQ silicone resin, the EO/PO value of polyether and the respective molecular weight are controlled so that c-x is more than 2x-a in the organosilicon emulsifier to achieve better emulsification effect. In the preparation method of the organosilicon emulsifier, the prepared organosilicon emulsifier is more favorable for emulsifying the organosilicon elastomer by the selection of the catalyst and the matching of the pressurizing condition, and the lengths of the polysiloxane chain segment and the polyether chain segment in the molecule are more suitable for forming more attachment points in the emulsification process. From the results of test 3, it can be seen that the silicone emulsifier prepared by pressurizing during the preparation process can basically achieve the best emulsifying effect, and the silicone elastomer can be completely emulsified in the water solvent or DMF solvent for a long time.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (5)
1. A silicone emulsifier for emulsifying a silicone elastomer, wherein the silicone emulsifier has a molecular formula of [ (CH) 3 ) 3 SiO 1/2 ] a [SiO 4/2 ] b [HO-SiO 3/2 ] (c-x) [H(EO) d (PO) e -OSiO 3/2 ] x The method comprises the steps of carrying out a first treatment on the surface of the The organosilicon emulsifier is synthesized by MQ silicon resin and polyether containing EO/PO blocks through catalytic reaction; wherein c-x > 2x-a;
the MQ silicone resin comprises the following components: [ (CH) 3 ) 3 SiO 1/2 ] a [SiO 4/2 ] b [HO-SiO 3/2 ] c M/q=1/10-1/1; molecular weight: 1000-50000; polyethers include polyether A and polyether B, both of which are polyethers containing EO/PO blocks of the general formula: h- (EO) d (PO) e -OH; wherein, EO/PO=1/10-10/1 of polyether A, the molecular weight is 1000-50000;
wherein, EO/PO=1/10-10/1 of polyether B, the molecular weight is 100-10000;
the preparation method of the organosilicon emulsifier comprises the following steps:
s1: uniformly stirring and mixing 10-40 parts of MQ silicone resin, 10-60 parts of polyether A, 20-70 parts of polyether B and 20-70 parts of organic solvent, and heating;
s2: heating to 135-150deg.C, refluxing and dehydrating for 1 hr; adding 0.01-0.5 part of catalyst; reflux reaction is carried out for 5 to 10 hours at constant temperature; water was separated from the separator every hour and the weight was recorded;
s3: after no water is separated out, the kettle temperature is reduced to 115-135 ℃, and 0.01-0.5 part of terminator is added for reaction for half an hour; obtaining a semi-finished product A;
s4: distilling off the organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 55-70 ℃, and filtering to obtain a finished organosilicon emulsifier;
the catalyst comprises dibutyl tin dilaurate and stannous oxide, wherein the mass ratio of the dibutyl tin dilaurate to the stannous oxide is 1:2;
and in the step S2, the control pressure is 1.5-2 MPa.
2. The silicone emulsifier for emulsifying a silicone elastomer according to claim 1, wherein the kinematic viscosity of the silicone emulsifier is controlled to be 0.001m 2 /s～0.004m 2 /s。
3. The silicone emulsifier for emulsifying a silicone elastomer according to claim 1, wherein M/q=1/3, molecular weight is 5000 in the MQ silicone resin; EO/po=1/1 in the polyether a, molecular weight 5000; EO/po=1/4 in the polyether B, the molecular weight is 2000.
4. The silicone emulsifier for emulsifying a silicone elastomer according to claim 1, characterized in that its emulsifying method for emulsifying a silicone elastomer comprises the steps of: adding 5-50 parts of organosilicon emulsifier into 10-80 parts of organosilicon elastomer for 2-5 times, each time for 30 minutes, and finally adding deionized water of which the volume is not more than 50 parts.
5. A method for preparing the silicone emulsifier for emulsifying a silicone elastomer according to any one of claims 1 to 4, comprising the steps of:
s1: uniformly stirring and mixing 10-40 parts of MQ silicone resin, 10-60 parts of polyether A, 20-70 parts of polyether B and 20-70 parts of organic solvent, and heating;
s2: heating to 135-150deg.C, refluxing and dehydrating for 1 hr; adding 0.01-0.5 part of catalyst; reflux reaction is carried out for 5 to 10 hours at constant temperature;
water was separated from the separator every hour and the weight was recorded;
s3: after no water is separated out, the kettle temperature is reduced to 115-135 ℃, and 0.01-0.5 part of terminator is added for reaction for half an hour; obtaining a semi-finished product A;
s4: distilling off the organic solvent under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 55-70 ℃, and filtering to obtain a finished organosilicon emulsifier;
the catalyst comprises dibutyl tin dilaurate and stannous oxide, wherein the mass ratio of the dibutyl tin dilaurate to the stannous oxide is 1:2;
and in the step S2, the control pressure is 1.5-2 MPa.
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| CN112795200A (en) * | 2021-01-06 | 2021-05-14 | 杭州崇耀科技发展有限公司 | Organic silicon emulsifier and preparation method and application thereof |
| CN114163656A (en) * | 2021-12-16 | 2022-03-11 | 杭州崇耀科技发展有限公司 | Silicone rubber emulsion, skin-feel emulsion type fabric coating agent and preparation method thereof |
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| CN107075339A (en) * | 2014-06-26 | 2017-08-18 | 道康宁(中国)投资有限公司 | Emulsion-type silicone pressure-sensitive adhesive composition and preparation method thereof |
| CN112795200A (en) * | 2021-01-06 | 2021-05-14 | 杭州崇耀科技发展有限公司 | Organic silicon emulsifier and preparation method and application thereof |
| CN114163656A (en) * | 2021-12-16 | 2022-03-11 | 杭州崇耀科技发展有限公司 | Silicone rubber emulsion, skin-feel emulsion type fabric coating agent and preparation method thereof |
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