CN115819778A - 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 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 (ii) a The organic silicon emulsifier is synthesized by MQ silicon resin and polyether containing EO/PO block through catalytic reaction; wherein c-x > 2x-a. The invention has the effect of improving the dispersibility of the silicone elastomer emulsified in an aqueous solvent or a DMF solvent.
Description
Technical Field
The present application relates to the field of decorative surfacing, more specifically it relates to a silicone emulsifier for emulsifying silicone elastomers and a process for its preparation.
Background
Resin compositions such as urethane resins and acrylic resins include solvent-based resin compositions and aqueous resin compositions. The solvent-type resin composition uses an organic solvent to improve film formability, but the organic solvent is volatile, particularly in a step of higher temperature such as drying. In order to reduce adverse effects on the health of workers, organic solvents having high boiling points, such as DMF, are often used.
The solvent-based and water-based resin compositions can be made into artificial leather or synthetic leather after internal addition treatment or surface treatment, and are widely used in the fields of automobile sheets, furniture, clothing, clothes and the like at present. The resin composition is required to have good slidability and wear resistance during use. In order to achieve the above requirements, a silicone elastomer having a high molecular weight is generally blended in a resin composition, but in a solvent-type resin composition or an aqueous resin composition using an organic solvent having a high boiling point such as DMF, the silicone elastomer is not well dispersed, and emulsification is required to improve the dispersion effect.
Surfactants are generally used as dispersing agents for emulsification, but if nonionic surfactants, anionic surfactants or cationic surfactants are used to emulsify silicone elastomers, it is generally difficult to completely emulsify the silicone elastomers, and the problem of precipitation tends to occur. Therefore, it is required to develop an emulsifier which can disperse a silicone elastomer efficiently and stably in both a solvent such as DMF and water.
Disclosure of Invention
In order to improve the dispersion effect of emulsification of a silicone elastomer in an aqueous solvent or a DMF solvent, the present application provides a silicone emulsifier for emulsifying a silicone elastomer.
A silicone emulsifier for emulsifying a silicone elastomer, wherein the silicone emulsifier has the molecular formula [ (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 (ii) a The organic silicon emulsifier is synthesized by MQ silicon resin and polyether containing EO/PO block 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, static resistance and physiological inertia; the polyoxyethylene group part in the polyether part is hydrophilic group, the polyoxypropylene group part is hydrophobic due to the methyl group, and is hydrophobic group, and the hydrophilicity and lipophilicity of the molecular structure of the polyether can be adjusted by adjusting the polymer and the ratio of ethylene oxide and propylene oxide in the polyether part.
Therefore, the silicone emulsifier in the application is designed by polysiloxane and polyether chain segments, c-x is more than 2x-a, and the ratio of polysiloxane to polyether is controlled, so that the silicone emulsifier can form a plurality of enough adsorption sites on the interface of DMF solvent and silicone elastomer or hydrosolvent and silicone elastomer, and compared with the traditional emulsifier, the silicone emulsifier in the application has more complete and stable dispersion effect and better emulsification effect.
Further, the kinematic viscosity of the silicone emulsifier is controlled to 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, the polyethers include polyether A and polyether B, and are both polyethers containing EO/PO blocks and having the general formula: h- (EO) d (PO) e -OH；
Wherein, EO/PO =1/10-10/1 of polyether A, and the molecular weight is 1000-50000;
wherein, the EO/PO =1/10-10/1 of the polyether B and the molecular weight is 100-10000.
Further, in the MQ silicon resin, M/Q =1/3, and the molecular weight is 5000; EO/PO =1/1 in the polyether A, and the molecular weight is 5000; the polyether B has EO/PO =1/4 and a molecular weight of 2000.
A method for preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 10-40 parts of MQ silicon resin, 10-60 parts of polyether A, 20-70 parts of polyether B and 20-70 parts of organic solvent, and then heating;
s2: heating to 135-150 deg.c, reflux dewatering for 2 hr; adding 0.01-0.5 part of catalyst; refluxing and reacting for 5-10 hours at constant temperature; every hour, water was separated from the water separator and the weight was recorded;
s3: after no water is separated out, the temperature of the kettle 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 the organic solvent under reduced pressure at 120 deg.C/0.098 MPa;
s5: cooling to 55-70 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
Further, the step S2 is: heating to 140-145 ℃, and dehydrating under reflux for 1 hour; adding 0.01-0.5 part of catalyst, and carrying out reflux reaction at constant temperature for 5-10 hours.
Further, the catalyst comprises dibutyltin dilaurate. And stannous oxide, dibutyltin dilaurate. The mass ratio of the stannous oxide to the stannous oxide is 1: 2-3.
By adopting the technical scheme, firstly, the tin catalyst can effectively inhibit partial side reactions from proceeding, and the width of molecular weight distribution is reduced; in the compounded catalyst system, the two catalysts can be mutually promoted, so that the integral 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 activation energy of the raw materials can be reduced, the frequency factor can be reduced, 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 product 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 product of the organic silicon emulsifier is too large, the branched chains are obviously increased, and the emulsification effect is greatly reduced. Therefore, when the pressure in the catalytic reaction process is controlled to be between 1.5 and 2MPa, the raw materials in the reaction process can give consideration to higher activation performance and generate the organic silicon emulsifier with more proper molecular weight.
Further, the emulsifying method for emulsifying the silicone elastomer comprises the following steps: adding 5-50 parts of organic silicon emulsifier into 10-80 parts of organic silicon elastomer for 2-5 times at intervals of 30 minutes, and finally adding not more than 50 parts of deionized water.
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 elastomer has a better dispersion effect on the emulsification of the organosilicon elastomer in a water solvent or a DMF solvent, and the emulsification is more thorough and complete.
2. In the preparation method of the organic silicon emulsifier, the emulsifier with better emulsifying effect on the organic silicon 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. According to the preparation method of the organic silicon emulsifier, the prepared organic silicon emulsifier is more beneficial to emulsification of the organic silicon elastomer through selection of the catalyst and matching of the pressurization 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 will be described in further detail with reference to examples.
In the following examples, the MQ silicone resins employed in the raw materials are of 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 of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 30 parts of MQ silicon 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 primary mixture to 140 ℃, and dehydrating under reflux for 1 hour; then 0.08 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 60 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =1/10 in MQ silicon resin; molecular weight: 23000;
polyether a has EO/PO =1/10, molecular weight 21000;
polyether B had EO/PO =1/10 and a molecular weight of 4800.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 2
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 10 parts of MQ silicon 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 primary mixture to 135 ℃, and dehydrating under reflux for 1 hour; then 0.33 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 the organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 68 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =1/10 in MQ silicon resin; molecular weight: 2000;
polyether a has EO/PO =0.2 and a molecular weight of 2000;
polyether B has EO/PO =3 and a molecular weight of 1400.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 3
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 16 parts of MQ silicon 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 primary mixture to 143 ℃, and dehydrating under reflux for 1 hour; then 0.07 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst is dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 65 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =1/10 in MQ silicon resin; molecular weight: 5000;
polyether a has EO/PO =1.2 and a molecular weight of 4000;
polyether B had EO/PO =9.6 and a molecular weight of 9200.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 4
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 18 parts of MQ silicon 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 primary mixture to 148 ℃, and performing reflux dehydration for 1 hour; then 0.24 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 67 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =1.4 in MQ silicon resin; molecular weight: 5000;
polyether a has EO/PO =1.9, molecular weight 6000;
polyether B had EO/PO =6.4 and a molecular weight of 6300.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: controlling the kinematic viscosity of 30 partsIs 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 5
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 18 parts of MQ silicon 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 primary mixture to 137 ℃, and dehydrating under reflux for 1 hour; then 0.08 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 58 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =1.7 in MQ silicon resin; molecular weight: 14000;
polyether a has EO/PO =2.2, molecular weight 10000;
polyether B had EO/PO =5.4 and a molecular weight of 5800.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 6
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 20 parts of MQ silicon 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 primary mixture to 145 ℃, and dehydrating under reflux for 1 hour; then 0.27 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst is dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 70 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =1.8 in MQ silicon resin; molecular weight: 15000;
polyether a has EO/PO =2.8 and a molecular weight of 16000;
polyether B has EO/PO =8.6 and a molecular weight of 8300.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 The organosilicon emulsifier/s is added into 40 parts of organosilicon elastomer for 2-5 times, each time is 30 minutes, and finally deionized water with the weight not more than 50 parts is added.
Example 7
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 20 parts of MQ silicon 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 primary mixture to 138 ℃, and dehydrating under reflux for 1 hour; then 0.44 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 the organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 69 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =1.8 in MQ silicon resin; molecular weight: 16000;
polyether a has EO/PO =3 and a molecular weight of 21000;
polyether B had EO/PO =5.5 and a molecular weight of 5900.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 8
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 21 parts of MQ silicon resin, 25 parts of polyether A, 24 parts of polyether B and 38 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the primary mixture to 141 ℃, and performing reflux dehydration for 1 hour; then 0.19 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 the organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 65 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =2.9 in MQ silicon resin; molecular weight: 17000;
polyether a has EO/PO =4 and a molecular weight of 23000;
polyether B had EO/PO =1.3 and a molecular weight of 800.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 S ofAnd adding the organic silicon emulsifier into 40 parts of organic silicon elastomer for 2-5 times, wherein each time is 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 9
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: uniformly stirring and mixing 23 parts of MQ silicon 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 primary mixture to 138 ℃, and dehydrating under reflux for 1 hour; then 0.21 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 68 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =3.8 in MQ silicon resin; molecular weight: 17000;
polyether a has EO/PO =2.8, molecular weight 26000;
polyether B had EO/PO =9.8 and a molecular weight of 9400.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 10
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 23 parts of MQ silicon 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 primary mixture to 137 ℃, and dehydrating under reflux for 1 hour; then 0.33 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 62 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =4.2 in MQ silicon resin; molecular weight: 19000;
polyether a has EO/PO =4.9, molecular weight 27000;
polyether B had EO/PO =1.7 and a molecular weight of 1100.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 The organosilicon emulsifier/s is added into 40 parts of organosilicon elastomer for 2-5 times, each time is 30 minutes, and finally deionized water with the weight not more than 50 parts is added.
Example 11
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 26 parts of MQ silicon resin, 58 parts of polyether A, 32 parts of polyether B and 68 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the primary mixture to 142 ℃, and performing reflux dehydration for 1 hour; then 0.46 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 52 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =5.7 in MQ silicon resin; molecular weight: 23000;
polyether a has EO/PO =5.9 and a molecular weight of 30000;
polyether B has EO/PO =2.4 and a molecular weight of 1200.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 12
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 28 parts of MQ silicon 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 primary mixture to 141 ℃, and dehydrating under reflux for 1 hour; then 0.18 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst is dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 58 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =6.6 in MQ silicon resin; molecular weight: 34000;
polyether a has EO/PO =6.4 and a molecular weight of 32000;
polyether B had EO/PO =5.8 and a molecular weight of 6000.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 Organosilicon emulsifiers of the typeAdding the mixture into 40 parts of organic silicon elastomer for 2-5 times, wherein each time is 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 13
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and mixing 29 parts of MQ silicon resin, 46 parts of polyether A, 23 parts of polyether B and 64 parts of xylene organic solvent in a reaction kettle A uniformly to obtain a primary mixture;
s2: heating the primary mixture to 136 ℃, and dehydrating under reflux for 1 hour; then 0.44 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 56 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =6.8 in MQ silicon resin; molecular weight: 35000;
polyether a has EO/PO =7.8 and a molecular weight of 35000;
polyether B has EO/PO =7.8 and a molecular weight of 7300.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 14
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 31 parts of MQ silicon resin, 29 parts of polyether A, 44 parts of polyether B and 60 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the primary mixture to 140 ℃, and dehydrating under reflux for 1 hour; then 0.33 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 55 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =8.3 in MQ silicon resin; molecular weight: 36000;
polyether a has EO/PO =8.1, molecular weight 40000;
polyether B has EO/PO =1/10 and a molecular weight of 100.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
Example 15
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 31 parts of MQ silicon resin, 11 parts of polyether A, 34 parts of polyether B and 38 parts of xylene organic solvent in a reaction kettle A to obtain a primary mixture;
s2: heating the primary mixture to 140 ℃, and dehydrating under reflux for 1 hour; then 0.2 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 62 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =9 in MQ silicon resin; molecular weight: 40000;
polyether a has EO/PO =8.3 and a molecular weight of 43000;
polyether B has EO/PO =1.4 and a molecular weight of 1100.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 The organosilicon emulsifier/s is added into 40 parts of organosilicon elastomer for 2-5 times, each time is 30 minutes, and finally deionized water with the weight not more than 50 parts is added.
Example 16
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 32 parts of MQ silicon 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 primary mixture to 144 ℃, and dehydrating under reflux for 1 hour; then 0.31 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 65 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =9.1 in MQ silicon resin; molecular weight: 40000;
polyether a has EO/PO =9.9, molecular weight 45000;
polyether B had EO/PO =0.3 and a molecular weight of 300.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 The organosilicon emulsifier is added into 40 portions in 2-5 timesAnd adding not more than 50 parts of deionized water into the organic silicon elastomer at intervals of 30 minutes.
Example 17
A method of preparing a silicone emulsifier for emulsifying a silicone elastomer, comprising the steps of:
s1: stirring and uniformly mixing 39 parts of MQ silicon 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 primary mixture to 142 ℃, and dehydrating under reflux for 1 hour; then 0.36 part of catalyst is added, and the reflux reaction is continued for 8 hours at constant temperature; the catalyst was dibutyltin dilaurate. The mass ratio of the stannous oxide to the 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 organic solvent xylene under reduced pressure at 120 ℃ and-0.098 MPa;
s5: cooling to 64 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
In the raw materials, M/Q =9.8 in MQ silicon resin; molecular weight: 43000;
polyether a has EO/PO =10, molecular weight 49000;
polyether B had EO/PO =4.5 and a molecular weight of 4200.
A method of preparing a silicone elastomer comprising a silicone emulsifier, comprising the steps of: the kinematic viscosity of 30 parts was controlled to 0.001m 2 And adding the silicone emulsifier/s into 40 parts of the silicone elastomer by 2-5 times at intervals of 30 minutes, and finally adding deionized water of which the amount is not more than 50 parts.
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 the catalyst used was a pure stannous oxide catalyst.
Example 20
Example 20 differs from example 1 in dibutyltin dilaurate. The mass ratio of the stannous oxide to the stannous oxide is 1: 3.
Example 21
Example 21 differs from example 1 in that the pressure in the reaction vessel of step S2 is 1.5MPa.
Example 22
Example 22 differs from example 1 in that 1.8MPa was added to the reaction vessel in step S2.
Example 23
Example 23 differs from example 1 in that 2MPa pressure was applied to the reaction vessel in step S2.
Comparative example
Comparative example 1: the difference from embodiment 1 is that step S3 is: after no water is separated out, the temperature of the reaction kettle is reduced to 115 ℃, and the 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: polyether a had EO/PO =12 and a molecular weight of 51000.
Comparative example 5: the difference from example 1 is that: polyether a had EO/PO =0.05 and a molecular weight of 800.
Comparative example 6: the difference from example 1 is that: polyether B has EO/PO =13 and a molecular weight of 10000.
Comparative example 7: the difference from example 1 is that: polyether B had EO/PO =0.04 and a molecular weight of 500.
Performance testing test 1: taking 7mL of the prepared emulsifier-water mixed solution with the mass concentration of 0.3% and 3g of organic silicon elastomer in a 15mL glass test tube, sealing, placing in a 55 ℃ water bath for constant temperature for 1h, taking out, turning over for 20 times, observing whether the oil phase and the water phase are completely emulsified, continuing placing in the 55 ℃ water bath, observing, and recording that an anhydrous phase is separated out within 24 h.
Test 2: taking 7mL of the prepared 0.3 mass percent emulsifier DMF mixed solution and 3g of organic silicon elastomer in a 15mL glass test tube, sealing, placing in a 55 ℃ water bath for keeping the temperature for 1h, taking out, turning over for 20 times, observing whether the oil phase and the water phase are completely emulsified, continuing placing in the 55 ℃ water bath, observing, and recording that an anhydrous phase is separated out within 24 h.
The results are given in the following table:
test 3: the observation for example 1, 17-23 was continued for 1 month to see if precipitation occurred, and the results are shown in the following table:
and (4) conclusion: it can be seen from the above table that the silicone emulsifier used in the present application can achieve an emulsifier with a good emulsifying effect on the silicone elastomer by controlling the M/Q value of MQ silicone resin in the raw materials, the EO/PO value in polyether and the respective molecular weights, otherwise, the emulsification is easy to be incomplete, or the back precipitation is performed after the emulsification for a certain time. The M/Q value of MQ silicon resin, the EO/PO value in polyether and the respective molecular weight are controlled in the application to ensure that c-x is more than 2x-a in the organic silicon emulsifier so as to achieve better emulsification effect. In the preparation method of the organic silicon emulsifier, the prepared organic silicon emulsifier is more favorable for emulsifying the organic silicon elastomer through the selection of the catalyst and the matching of the pressurization 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 achieve the best emulsification effect, and can completely emulsify the silicone elastomer in the water solvent or DMF solvent for a long time.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A silicone emulsifier for emulsifying a silicone elastomer, wherein the silicone emulsifier has the molecular formula [ (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 (ii) a The organic silicon emulsifier is synthesized by MQ silicon resin and polyether containing EO/PO block through catalytic reaction; wherein c-x > 2x-a.
2. The silicone emulsifier for emulsifying a silicone elastomer according to claim 1, wherein the kinematic viscosity of the silicone emulsifier is controlled to 0.001m 2 /s～0.004m 2 /s。
3. A silicone emulsifier for emulsifying a silicone elastomer according to claim 1, 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.
4. A silicone emulsifier for emulsifying a silicone elastomer according to claim 1, wherein the polyether comprises polyether a and polyether B, and each is a polyether containing EO/PO blocks of the general formula:
H-(EO) d (PO) e -OH；
wherein, EO/PO =1/10-10/1 of polyether A, and the molecular weight is 1000-50000;
wherein, the EO/PO =1/10-10/1 of the polyether B, and the molecular weight is 100-10000.
5. The silicone emulsifier for emulsifying silicone elastomers according to claim 1, wherein M/Q =1/3 and the molecular weight of MQ silicone resin is 5000; EO/PO =1/1 in the polyether A, and the molecular weight is 5000; the polyether B has EO/PO =1/4 and a molecular weight of 2000.
6. The silicone emulsifier for emulsifying a silicone elastomer according to claim 1, wherein the emulsifying method for emulsifying a silicone elastomer comprises the steps of: adding 5-50 parts of organic silicon emulsifier into 10-80 parts of organic silicon elastomer for 2-5 times, wherein the interval is 30 minutes each time, and finally adding not more than 50 parts of deionized water.
7. A process for preparing a silicone emulsifier for emulsifying a silicone elastomer according to any one of claims 1 to 5, comprising the steps of:
s1: stirring and uniformly mixing 10-40 parts of MQ silicon resin, 10-60 parts of polyether A and 20-70 parts of organic solvent, and then heating;
s2: heating to 135-150 ℃, and dehydrating under reflux for 1 hour; adding 0.01-0.5 part of catalyst; refluxing and reacting for 5-10 hours at constant temperature; every hour, water was separated from the water separator and the weight was recorded;
s3: after no water is separated out, the temperature of the kettle 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: adding 20-70 parts of polyether B and 0.01-0.5 part of phosphoric acid into a reaction kettle B, and stirring for 0.5-1 hour;
s5: adding 80-150 parts of the semi-finished product A into a reaction kettle B, and stirring for 0.5-1 hour;
s6: distilling the organic solvent under reduced pressure at 120 deg.C/0.098 MPa;
s7: cooling to 55-70 ℃, and filtering to obtain the finished product of the organic silicon emulsifier.
8. The process according to claim 6, wherein the S2 step is: heating to 140-145 ℃, and dehydrating under reflux for 1 hour; adding 0.01-0.5 part of catalyst, and carrying out reflux reaction at constant temperature for 5-10 hours.
9. The preparation method of the silicone emulsifier for emulsifying the silicone elastomer according to claim 6, wherein the catalyst comprises stannous octoate and stannous oxide, and the mass ratio of the stannous octoate to the stannous oxide is 1: 2-3.
10. The method of claim 6, wherein the pressure in step S2 is controlled to be 1.5-2 MPa.
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| US20070219318A1 (en) * | 2004-04-20 | 2007-09-20 | Shaow Lin | Aqueous Dispersions of Silicone Polyether Block Copolymers |
| 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 |
| US20210246339A1 (en) * | 2018-06-12 | 2021-08-12 | Dow Silicones Corporation | Water-based hybrid pressure sensitive adhesive composition and method of producing the same |
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