CN109608640B - High molecular weight MQ silicon resin and synthesis method and application thereof - Google Patents
High molecular weight MQ silicon resin and synthesis method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/08—Preparatory processes characterised by the catalysts used
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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Abstract
The invention provides high molecular weight MQ silicon resin and a synthesis method and application thereof. The synthesis method of the MQ silicon resin comprises the following steps: pre-reacting silicate ester and partial M unit silane monomer in a mixed solution consisting of water, a catalyst and a cosolvent; adding the rest M unit silane monomer and part of the extractant into the mixture to react under the heating condition, then adding the rest extractant, and extracting to obtain an organic phase; adjusting the organic phase to be neutral, and then distilling to obtain high molecular weight MQ silicon resin; wherein the mass ratio of the M unit silane monomer added twice is 10: 1-1: 10. The method has simple flow, does not need a large amount of water washing, has high product yield, does not need to add an additional remover to eliminate silicon hydroxyl and silicon acyloxy in the MQ silicon resin, and can control the molecular weight of a target product through the proportion of the M monomer added in batches and the proportion of the extracting agent added in batches.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to high molecular weight MQ silicon resin and a synthesis method and application thereof.
Background
The MQ organic silicon resin is a very unique siloxane, is a novel organic silicon material with a three-dimensional (nonlinear) structure formed by taking Si-O bonds as a framework, is an organic silicon resin formed by a tetrafunctional siloxane condensation chain (Q) and a monofunctional siloxane chain (M), has the molar mass of 1000-8000 generally, and has the following excellent characteristics: excellent heat resistance and low temperature resistance, and can be used in the temperature environment of-60 ℃ to 300 ℃; good film forming property, moderate flexibility, aging resistance and ultraviolet irradiation resistance; good water repellency; better adhesion performance; excellent barrier properties and durability, making a permanent mold release agent.
MQ silicone resins have the following broad applications with their excellent properties: the high-temperature resistant coating can be prepared and used for insulation, jointing, sealing and the like of an H-level motor; the high-temperature resistant and strong-alkali resistant defoaming agent is prepared, and the foam inhibition performance of the defoaming agent is improved; making various waterproof coatings, and making lipstick and other ideal materials in daily use; the stripping force of the pressure-sensitive adhesive is improved and adjusted, so that the pressure-sensitive adhesive can be used as a stripping force adjusting agent for manufacturing pressure-sensitive adhesive tapes and the like; preparing release agent components in various plastic fields; the adhesive is suitable for being used as an adhesion promoter in the bonding and compounding of inorganic materials and organic materials; the silicon rubber is used as a reinforcing agent, and the reinforced silicon rubber is colorless and transparent and has high mechanical strength.
Patent application CN103242532A discloses a preparation method of an environment-friendly solvent-free liquid silicone resin: pre-reacting an M unit end-capping agent in water and an alcohol solution under an acidic condition, adding a Q unit for reaction, adding an organic silicon micromolecule for extraction, and carrying out polymerization reaction on the extracted reaction liquid under heating. The technology adopts organic silicon low molecules (such as DMC, D4, vinyl ring body, linear silicon oil and the like) as an extracting agent to replace the traditional xylene or toluene solvent, but the low molecules are easy to react with MQ silicon resin in the later high-temperature condensation reaction process, the molecular weight of the MQ silicon resin can be slightly increased, but the structure of the MQ silicon resin is changed, and the method is only the replacement of the extracting agent and cannot radically change the controllable MQ molecular weight.
Patent application CN103937266A discloses a silicone rubber, and the preparation method of MQ silicone resin used in the silicone rubber is as follows: enabling an M unit (hexamethyldisiloxane and tetramethyldivinyl disiloxane) to react in a mixed solution of water, ethanol, concentrated hydrochloric acid and toluene, adding a Q unit (tetraethoxysilane) to react at a high temperature, washing with deionized water, carrying out reduced pressure distillation, and carrying out catalytic reaction on the obtained resin and hydroxy silicone oil to obtain the MQ silicone resin with the M/Q ratio of 0.6-1.0. The method removes acidic ions in the organic layer through water washing, increases the generation amount of wastewater, and seriously causes the low yield of the MQ silicon resin due to the emulsification phenomenon in the water washing process.
Patent application CN102775612A discloses a preparation method of vinyl MQ silicone resin: pre-reacting M units (part of hexamethyldisiloxane and dimethylvinylethoxysilane) in water and hydrochloric acid solution, adding Q units (tetraethoxysilane) to continue reacting, then adding another part of hexamethyldisiloxane to continue reacting, reacting a hydrolysate after acid water removal under an alkaline catalyst, and washing with water to purify. The method also adopts multiple water washing to remove impurities, increases the production amount of wastewater, and seriously causes the emulsification phenomenon in the water washing process to cause the yield of the MQ silicon resin to be lower, and the yield can reach 95 percent at most.
Patent application CN102181055A discloses a preparation method of MQ silicone resin: and (3) reacting an M unit (part of hexamethyldisiloxane) with a Q unit (tetraethoxysilane, tetramethyl divinyl disiloxane and the like) in an ethanol and hydrochloric acid solution, extracting with toluene, washing with water, and distilling under reduced pressure to obtain the MQ silicon resin with the molecular weight of about 3000-6200 and the yield of only 25-60%.
Patent application CN103524741A discloses a synthesis method of methyl vinyl MQ silicon resin, the prepared MQ silicon resin is white powder, and the prepared MQ silicon resin does not contain silicon hydroxyl and silicon alkoxy, can be mixed with each component in LED packaging material, and is not turbid. Elimination of silicon hydroxyl requires elimination agent substances such as hexamethyldisiloxane, hexamethyldisilazane, tetramethyldivinyldisiloxane and the like, so that the reaction process is complicated.
Patent application CN10480419A discloses MQ silicon resin for large-scale integrated circuit encapsulation and a preparation method thereof, the molar ratio of tetraethoxysilane to end-capping reagent is 1.5-3, tetraethoxysilane and end-capping reagent are put into one time in the reaction process, the method can only obtain MQ silicon resin with the molecular weight of about 1000-200, and the treatment and control of silicon hydroxyl and siloxy are not mentioned in the literature.
In summary, the MQ silicone resin preparation method disclosed in the above technology has at least one of the following problems:
the molecular weight of the prepared MQ silicon resin is too low and can only reach the level of 1000-8000, and the molecular weight is uncontrollable;
secondly, only adding a special remover to remove silicon hydroxyl and silicon alkoxide in the resin;
thirdly, the purification method is unreasonable, a large amount of waste water can be generated, and the production is not environment-friendly;
and fourthly, the yield of the MQ silicon resin is lower.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide the high-molecular-weight MQ silicon resin, which has higher molecular weight than the traditional MQ resin, has high light transmittance, has low or even negligible content of silicon hydroxyl and silicon alkoxy in molecules, and has remarkable advantages when being used for materials such as a release agent, a film forming agent, a defoaming agent and the like.
The second objective of the present invention is to provide a method for preparing the above high molecular weight MQ silicone resin, which has a simple process, and does not require a large amount of water washing in the preparation and purification processes, so that a large amount of wastewater is not generated, the emulsification phenomenon during water washing is eliminated, the product yield is improved, and the silicon hydroxyl and silicon acyloxy in the MQ silicone resin are eliminated without adding an additional eliminating agent.
In order to solve the technical problems, the invention provides the following technical scheme:
the high molecular weight MQ silicon resin has a molecular weight of 7000-50000, preferably 15000-45000, m/q of 0.6-0.9, and light transmittance of more than 94%.
The MQ silicon resin provided by the invention not only has improved molecular weight, but also has remarkable advantages compared with the silicon resin with low molecular weight. For example, when used in a release agent, the high molecular weight MQ silicone resin of the invention has higher release force and long retention time.
The invention also provides a preparation method of the MQ silicon resin, which comprises the following steps:
step A: pre-reacting silicate ester and partial M unit silane monomer in a mixed solution consisting of water, a catalyst and a cosolvent;
and B: then reacting the reactant obtained after the pre-reaction in the step A with the rest M unit silane monomer and part of the extracting agent under the heating condition, adding the rest extracting agent, and extracting to obtain an organic phase;
and C: adjusting the organic phase to be neutral, and then distilling to obtain high molecular weight MQ silicon resin;
the mass ratio of the M unit silane monomer added in the step A to the M unit silane monomer added in the step B is 10: 1-1: 10, preferably 1: 1.1-1: 10, more preferably 1.2: 10-1: 10, more preferably 1: 2-1: 10, more preferably 1: 3-1: 10; the proportion of the M unit silane monomer added in the step A in the total amount of the M unit silane monomer is 5-30%, more preferably 5-30%, and still more preferably 7-20%.
As described above, the preparation method of the invention completes the reaction of silicate and M unit silane monomer in two steps, and then obtains high molecular weight MQ silicon resin with higher purity and high yield through the purification of step C.
The key factors for controlling the molecular weight and M/q of the product are that the M unit silane monomer is added in two batches and the extracting agent is added in two batches, so that the physicochemical properties of the silicone resin are directly influenced by the proportion of the M unit silane monomer added in two times and the proportion of the extracting agent added in two times, particularly the strength of the silicone resin. For this purpose, the mass ratio of the M unit silane monomer added in the step a to the M unit silane monomer added in the step B is 10:1 to 1:10, within this range, when the first addition ratio is small, the molecular weight of the obtained MQ silicone resin is larger, and therefore the mass ratio before and after is further preferably 1:1.1 to 1:10, more preferably 1.2:10 to 1:10, more preferably 1:2 to 1:10, more preferably 1:3 to 1:10, or the amount of the M monomer added first is limited by a percentage, for example, 5% to 30%, more preferably 7% to 20%, more preferably 9% to 15%, and the like.
On the basis of the above, the process conditions and the selection of raw materials of the invention can be further optimized, as follows.
Preferably, the catalyst is an acidic catalyst, preferably one or a mixture of inorganic and organic acids.
The hydrolysis of the first step is carried out under acidic conditions, the invention is not particularly limited to the type of acid, and both organic and inorganic acids can be used, and the pH of different acids is different, the ionic strength is different, and therefore the reaction kinetics and the degree of condensation are different.
The inorganic acid is preferably one or more of hydrochloric acid, sulfuric acid, hydrofluoric acid and hydrobromic acid;
the organic acid is preferably one or more of trifluoromethanesulfonic acid, formic acid, oxalic acid acetate and benzoic acid;
preferably, the cosolvent is one or more of lower alcohol or lower ketone;
the lower alcohol is preferably one or more of methanol, ethanol, isopropanol, n-butanol and isobutanol, preferably ethanol.
The lower ketone is preferably one or a mixture of acetone and butanone, preferably acetone.
Preferably, the M unit silane monomer is one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane, tetramethyldisiloxane, trimethylmethoxysilane, vinyldimethylmethoxysilane, dimethylmethoxysilane, phenyldimethylmethoxysilane, trimethylethoxysilane, vinyldimethylethoxysilane, dimethylethoxysilane and phenyldimethylethoxysilane, and is preferably one or two of hexamethyldisiloxane and divinyltetramethyldisiloxane.
In addition to controlling the molecular weight of the product by the ratio of the monomers and extractant added in portions, the molecular weight can also be controlled by the type of monomer. When the MQ silicone resin is prepared, the M monomer is optional, only one monomer can be selected, or a plurality of monomers can be mixed, preferably hexamethyldisiloxane and divinyltetramethyldisiloxane are mixed, and the mixing weight ratio of the hexamethyldisiloxane to the divinyltetramethyldisiloxane is preferably 8-14: 1, such as 8:1,9:1,10:1,11:1,12:1,13:1,14:1, and the like.
Preferably, the silicate is one or more of methyl orthosilicate and a polycondensate thereof, ethyl orthosilicate and a polycondensate thereof, and propyl orthosilicate and a polycondensate thereof.
In the preparation of the silicone resins, only one silicate is usually chosen, for example methyl, ethyl or propyl orthosilicate.
Preferably, the extractant is benzene or substituted benzene, preferably benzene, toluene or xylene.
Preferably, the proportion of the extractant added in the first step to the proportion of the extractant added in the second step in the step B is 10: 1-1: 10, preferably 5: 1-1: 5, and more preferably 2: 1-1: 5.
As mentioned above, the extractant not only plays a role in purification, but also plays a role in controlling the molecular weight of the product, and the mixture ratio of the extractant added twice before and after has an important influence on the molecular weight, charge-to-mass ratio and other properties of the product. According to the investigation, the proportion of the raw materials is preferably any proportion within the range of 10: 1-1: 10.
Preferably, it is adjusted with one or more of calcium carbonate, sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium carbonate or potassium bicarbonate.
The purpose of adding the medium and strong alkali is at least two points: and secondly, carrying out condensation reaction on silicon hydroxyl and siloxy in the presence of a basic catalyst to obtain the MQ silicon resin without silicon hydroxyl and siloxy.
Preferably, the pre-reaction conditions in step A are 10-50 ℃, such as 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ and the like.
The silicate is preferably added in the following way: and (2) gradually adding silicate ester into a mixed solution consisting of a part of M unit silane monomer, water, a catalyst and a cosolvent, and finishing the addition within 0.5-2 hours.
The slow addition of silicate ester can control the reaction progress, which is beneficial to obtaining silicone resin with more uniform molecular weight.
Preferably, the temperature is kept for 10min to 120min after the silicate ester is added.
Preferably, the heating conditions of step B are: the temperature is raised to 50-80 ℃, and the preferable reaction time is 1-6 hours.
Preferably, the distillation method comprises the steps of heating to 100-150 ℃ to distill off low-boiling-point substances;
preferably, the temperature is kept for 1 to 6 hours at 100 to 150 ℃ after the distillation is finished, so as to further improve the molecular weight of the resin and reduce the content of silicon hydroxyl.
The incubation after distillation can further control the molecular weight of the MQ silicone resin.
In conclusion, the invention realizes the purpose of controlling the molecular weight and other properties of the MQ resin by multiple means, and at least comprises means of monomer batch addition, catalyst batch addition, heat preservation after distillation and the like.
Preferably, in the preparation process, the weight ratio of the water, the catalyst, the cosolvent, the M unit silane monomer, the silicate ester and the extracting agent is 1-10: 2-10: 5-25: 1-15: 15-30: 10-50, preferably 2-10: 2-8: 5-20: 1-10: 15-25: 10-40, and preferably 3-10: 2-6: 5-15: 2-8: 15-25: 20-40.
Wherein, the proportion of the M unit silane monomer and the silicate ester is a more key factor influencing the product.
As described above, the high molecular weight MQ silicon resin prepared by the invention has the advantages of high molecular weight, high light transmittance, proper m/q, no silicon hydroxyl group and silicon siloxy group and the like, so the application field is wide, and the preparation method has outstanding advantages especially for preparing a parting agent, a defoaming agent, a film forming agent or silicon rubber.
In summary, compared with the prior art, the invention achieves the following technical effects:
(1) the high molecular weight MQ silicon resin with the molecular weight distributed at 7000-50000 has the advantages of high light transmittance, proper m/q, no silicon hydroxyl or siloxy, wider application field and the like;
(2) the preparation method of the MQ silicon resin provided by the invention has simple process, and only needs three main processes;
(3) the preparation method does not relate to a washing process, does not generate a large amount of waste water, does not have the emulsification phenomenon during washing, and has higher yield of the MQ silicon resin which can reach more than 98 percent;
(4) the preparation method of the invention does not need a special remover to remove the silicon hydroxyl and the silicon alkoxyl, and the silicon hydroxyl and the silicon alkoxyl can be basically removed or the content is maintained at a very low level by the condensation reaction of the silicon hydroxyl and the silicon alkoxyl under the catalysis of an alkaline reagent.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
1) 250 g of deionized water, 50 g of hydrochloric acid, 500 g of ethanol, 70 g of hexamethyldisiloxane and 5 g of divinyl tetramethyldisiloxane are added into a four-neck flask with a condenser tube, a thermometer and a constant pressure dropping funnel, stirring is started, and the temperature is increased to 30 ℃;
2) dropwise adding 1055 g of tetraethoxysilane for 1 hour, and after the dropwise adding, carrying out thermal insulation hydrolysis for 1 hour;
3) heating to 60 ℃, adding a mixture of 650 g of dimethylbenzene, 350 g of hexamethyldisiloxane and 24 g of divinyltetramethyldisiloxane, and keeping the temperature for 4 hours; then adding 650 g of dimethylbenzene, and standing for liquid separation;
4) adding 30 g of sodium bicarbonate into the organic phase, adjusting the pH to 7, slowly heating to 150 ℃, removing low-boiling-point substances at the same time, and then preserving the heat for 1 hour;
5) and cooling to room temperature, filtering to remove insoluble substances, and removing the solvent from the filtrate to obtain the MQ silicon resin solid. The weight average molecular weight of the obtained methyl vinyl MQ silicon resin is 15000 by gel permeation chromatography analysis.
Example 2
1) Adding 250 g of deionized water, 50 g of acetic acid, 500 g of isopropanol, 40g of hexamethyldisiloxane and 5 g of divinyl tetramethyldisiloxane into a four-neck flask with a condenser tube, a thermometer and a constant-pressure dropping funnel, starting stirring, and heating to 20-30 ℃;
2) adding 771 g of methyl orthosilicate dropwise for 1 hour, and reacting at 20-30 ℃ for 1 hour in a heat preservation way;
3) heating to 70 ℃, adding a mixture of 650 g of toluene, 350 g of hexamethyldisiloxane and 24 g of divinyltetramethyldisiloxane, and keeping the temperature for 3 hours; then 650 g of toluene is added, and the mixture is kept stand for liquid separation;
4) adding 30 g of sodium bicarbonate into the organic phase, adjusting the pH to 7, slowly heating to 110 ℃, removing low-boiling-point substances at the same time, and then preserving the heat for 1 hour;
5) and cooling to room temperature, filtering to remove insoluble substances, and removing the solvent from the filtrate to obtain the MQ silicon resin solid. The weight average molecular weight of the obtained methyl vinyl MQ silicon resin is 27000 by gel permeation chromatography analysis.
Example 3
1) 200 g of deionized water, 10 g of trifluoromethanesulfonic acid and 480 g of methanol are added into a four-neck flask with a condenser pipe, a thermometer and a constant-pressure dropping funnel, the temperature is raised to 45 ℃, 30 g of hexamethyldisiloxane and 5 g of divinyltetramethyldisiloxane are added;
2) 1340 grams of propyl orthosilicate is dripped for 2.5 hours, and the reaction is carried out for 1 hour under the condition of heat preservation;
3) heating to 65 ℃, adding a mixture of 750 g of toluene, 360 g of hexamethyldisiloxane and 24 g of divinyltetramethyldisiloxane, and keeping the temperature for 4 hours; then adding 750 g of toluene, standing and separating liquid;
4) adding 30 g of sodium bicarbonate into the organic phase, adjusting the pH value to 7.0, slowly heating to 120 ℃, simultaneously removing low-boiling-point substances, and preserving heat for 3 hours;
5) and cooling to room temperature, filtering to remove insoluble substances, and removing the solvent from the filtrate to obtain the MQ silicon resin solid. The weight average molecular weight of the obtained methyl vinyl MQ silicon resin is 38000 by gel permeation chromatography analysis.
Example 4
1) Adding 180 g of deionized water, 18 g of sulfuric acid and 520g of n-butanol into a four-neck flask with a condenser pipe, a thermometer and a constant-pressure dropping funnel, starting stirring, heating to 50 ℃, and adding 25 g of hexamethyldisiloxane and 8 g of divinyltetramethyldisiloxane;
2) dropwise adding 1200 g of tetraethoxysilane for 2 hours, and reacting for 1 hour at the temperature of 50 ℃;
3) heating to 75 ℃, adding a mixture of 780 g of metered benzene, 390 g of hexamethyldisiloxane and 48 g of divinyltetramethyldisiloxane, and keeping the temperature for 4 hours; 780 g of benzene is added, and the mixture is kept stand for liquid separation;
4) adding 30 g of sodium carbonate into the organic phase to adjust the pH value to 7.0, slowly heating to 100 ℃, simultaneously removing low-boiling-point substances, and preserving the heat at 100 ℃ for 4 hours;
5) and cooling to room temperature, filtering to remove insoluble substances, and removing the solvent from the filtrate to obtain the MQ silicon resin solid. The weight average molecular weight of the obtained methyl vinyl MQ silicon resin is 45000 through gel permeation chromatography analysis.
Example 5
The difference from example 4 is that only one of the hexamethyldisiloxane is added as an M monomer blocking agent, as follows.
1) Adding 180 g of deionized water, 18 g of sulfuric acid and 520g of n-butanol into a four-neck flask with a condenser tube, a thermometer and a constant pressure dropping funnel, starting stirring, heating to 50 ℃, and adding 33 g of hexamethyldisiloxane;
2) dropwise adding 1200 g of tetraethoxysilane for 2 hours, and reacting for 1 hour at the temperature of 50 ℃;
3) heating to 75 ℃, adding a mixture of 780 g of metered benzene and 438 g of hexamethyldisiloxane, and keeping the temperature for 4 hours; 780 g of benzene is added, and the mixture is kept stand for liquid separation;
4) adding 30 g of sodium carbonate into the organic phase to adjust the pH value to 7.0, slowly heating to 100 ℃, simultaneously removing low-boiling-point substances, and preserving the heat at 100 ℃ for 4 hours;
5) and cooling to room temperature, filtering to remove insoluble substances, and removing the solvent from the filtrate to obtain the MQ silicon resin solid.
The weight average molecular weight of the obtained methyl vinyl MQ silicon resin is 43000 by gel permeation chromatography analysis.
The properties and process effects of the silicone resins obtained in examples 1 to 5 were compared, and the results are shown in table 1.
TABLE 1
Example 6
The difference from example 5 is that hexamethyldisiloxane is added in portions, 52 g in the first step and the remaining 519 g in the third step, and the reaction conditions are the same as in example 5.
Example 7
The difference from example 5 is that hexamethyldisiloxane is added in portions, 100 g in the first step and the remaining 471 g in the third step, and the reaction conditions are the same as in example 5.
Example 8
The difference from example 5 is that the hexamethyldisiloxane is added in portions in a different ratio, 285 g in the first step and 286 g in the third step, and the reaction conditions are the same as in example 5.
Example 9
The difference from example 5 is that hexamethyldisiloxane is added in portions, 400 g in the first step and the remaining 171 g in the third step, and the reaction conditions are the same as in example 5.
Example 10
The difference from example 5 is that the hexamethyldisiloxane is added in portions in a different ratio, 519 g is added in the first step and the remaining 52 g is added in the third step, and the reaction conditions are the same as in example 5.
The properties and process effects of the silicone resins obtained in examples 5 to 10 were compared, and the results are shown in Table 2.
TABLE 2
Example 11
The difference from example 5 is that the extraction agent benzene is added twice in different proportions, and 1040g of benzene is added for the first time, and 520g of benzene is added for the second time.
Example 12
The difference from example 5 is that the extraction agent benzene is added twice in different proportions, and the first addition amount is 520g, and the second addition amount is 1040 g.
The properties and process effects of the silicone resins obtained in examples 5, 11 and 12 were compared, and the results are shown in Table 3.
TABLE 3
Example 13
The difference from the embodiment 5 lies in that the mixture ratio of silicate ester and M monomer is different, specifically:
1) adding 180 g of deionized water, 18 g of sulfuric acid and 520g of n-butanol into a four-neck flask with a condenser tube, a thermometer and a constant pressure dropping funnel, starting stirring, heating to 50 ℃, and adding 29.4 g of hexamethyldisiloxane;
2) dropwise adding 1200 g of tetraethoxysilane for 2 hours, and reacting for 1 hour at the temperature of 50 ℃;
3) heating to 75 ℃, adding a mixture of 780 g of metered benzene and 390.5 g of hexamethyldisiloxane, and keeping the temperature for 4 hours; 780 g of benzene is added, and the mixture is kept stand for liquid separation;
4) adding 30 g of sodium carbonate into the organic phase to adjust the pH value to 7.0, slowly heating to 100 ℃, simultaneously removing low-boiling-point substances, and preserving the heat at 100 ℃ for 4 hours;
5) and cooling to room temperature, filtering to remove insoluble substances, and removing the solvent from the filtrate to obtain the MQ silicon resin solid.
Example 14
The difference from the embodiment 5 lies in that the mixture ratio of silicate ester and M monomer is different, specifically:
1) adding 180 g of deionized water, 18 g of sulfuric acid and 520g of n-butanol into a four-neck flask with a condenser tube, a thermometer and a constant pressure dropping funnel, starting stirring, heating to 50 ℃, and adding 36 g of hexamethyldisiloxane;
2) dropwise adding 1200 g of tetraethoxysilane for 2 hours, and reacting for 1 hour at the temperature of 50 ℃;
3) heating to 75 ℃, adding a mixture of 780 g of metered benzene and 477.3 g of hexamethyldisiloxane, and keeping the temperature for 4 hours; 780 g of benzene is added, and the mixture is kept stand for liquid separation;
4) adding 30 g of sodium carbonate into the organic phase to adjust the pH value to 7.0, slowly heating to 100 ℃, simultaneously removing low-boiling-point substances, and preserving the heat at 100 ℃ for 4 hours;
5) and cooling to room temperature, filtering to remove insoluble substances, and removing the solvent from the filtrate to obtain the MQ silicon resin solid.
Example 15
The difference from the embodiment 5 lies in that the mixture ratio of silicate ester and M monomer is different, specifically:
1) adding 180 g of deionized water, 18 g of sulfuric acid and 520g of n-butanol into a four-neck flask with a condenser tube, a thermometer and a constant pressure dropping funnel, starting stirring, heating to 50 ℃, and adding 39.2 g of hexamethyldisiloxane;
2) dropwise adding 1200 g of tetraethoxysilane for 2 hours, and reacting for 1 hour at the temperature of 50 ℃;
3) heating to 75 ℃, adding a mixture of 780 g of metered benzene and 520.7 g of hexamethyldisiloxane, and keeping the temperature for 4 hours; 780 g of benzene is added, and the mixture is kept stand for liquid separation;
4) adding 30 g of sodium carbonate into the organic phase to adjust the pH value to 7.0, slowly heating to 100 ℃, simultaneously removing low-boiling-point substances, and preserving the heat at 100 ℃ for 4 hours;
5) and cooling to room temperature, filtering to remove insoluble substances, and removing the solvent from the filtrate to obtain the MQ silicon resin solid.
The properties and process effects of the silicone resins obtained in examples 5 and 13 to 15 were compared, and the results are shown in Table 4.
TABLE 4
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (23)
1. A preparation method of high molecular weight MQ silicon resin is characterized by comprising the following steps:
step A: pre-reacting silicate ester and partial M unit silane monomer in a mixed solution consisting of water, a catalyst and a cosolvent;
and B: then reacting the reactant obtained after the pre-reaction in the step A with the rest M unit silane monomer and part of the extracting agent under the heating condition, adding the rest extracting agent, and extracting to obtain an organic phase;
and C: adjusting the organic phase to be neutral, and then distilling to obtain high molecular weight MQ silicon resin;
the mass ratio of the M unit silane monomer added in the step A to the M unit silane monomer added in the step B is 10: 1-1: 10;
in the preparation process, the weight ratio of the water, the catalyst, the cosolvent, the M unit silane monomer, the silicate ester and the extracting agent is 1-10: 2-10: 5-25: 1-15: 15-30: 10-50;
the molecular weight of the high molecular weight MQ silicon resin is 7000-50000, m/q is 0.6-0.9, and the light transmittance is more than 94%.
2. The preparation method of the MQ silicone resin with high molecular weight as claimed in claim 1, wherein the mass ratio of the M unit silane monomer added in the step A to the M unit silane monomer added in the step B is 1: 1.1-1: 10.
3. The method for preparing MQ silicone resin with high molecular weight according to claim 1, wherein the mass ratio of the M unit silane monomer added in the step A to the M unit silane monomer added in the step B is 1.2:10 to 1: 10.
4. The preparation method of the MQ silicone resin with high molecular weight as claimed in claim 1, wherein the mass ratio of the M unit silane monomer added in the step A to the M unit silane monomer added in the step B is 1: 2-1: 10.
5. The preparation method of the MQ silicone resin with high molecular weight as claimed in claim 1, wherein the mass ratio of the M unit silane monomer added in the step A to the M unit silane monomer added in the step B is 1: 3-1: 10.
6. The method for preparing MQ silicone resins of high molecular weight according to claim 1, wherein the catalyst is an acidic catalyst.
7. The method for preparing MQ silicone resin with high molecular weight as claimed in claim 1, wherein the catalyst is one or a mixture of inorganic acid and organic acid;
the inorganic acid is selected from one or more of hydrochloric acid, sulfuric acid, hydrofluoric acid and hydrobromic acid;
the organic acid is selected from one or more of trifluoromethanesulfonic acid, formic acid, acetic acid, oxalic acid and benzoic acid.
8. The method for preparing MQ silicone resin with high molecular weight as claimed in claim 1, wherein the cosolvent is one or more of lower alcohol or lower ketone;
the lower alcohol is selected from one or more of methanol, ethanol, isopropanol, n-butanol and isobutanol;
the lower ketone is selected from one or a mixture of acetone and butanone.
9. The method for preparing MQ silicone resin with high molecular weight as claimed in claim 1, wherein the silane monomer with M unit is one or more of hexamethyldisiloxane, divinyltetramethyldisiloxane, tetramethyldisiloxane, trimethylmethoxysilane, vinyldimethylmethoxysilane, dimethylmethoxysilane, phenyldimethylmethoxysilane, trimethylethoxysilane, vinyldimethylethoxysilane, dimethylethoxysilane and phenyldimethylethoxysilane.
10. The method for preparing high molecular weight MQ silicone resin according to claim 1, wherein the M unit silane monomer is one or both of hexamethyldisiloxane and divinyltetramethyldisiloxane.
11. The method for preparing MQ silicone resins of high molecular weight according to claim 9, characterized in that the silicate is one or more of methyl orthosilicate and its polycondensate, ethyl orthosilicate and its polycondensate, propyl orthosilicate and its polycondensate.
12. The method for preparing MQ silicone resins of high molecular weight according to claim 1, wherein the extractant is benzene or substituted benzene;
the substituted benzene is toluene or xylene.
13. The preparation method of the MQ silicone resin with high molecular weight as claimed in claim 1, wherein the ratio of the extractant added in the first step to the extractant added in the second step in the step B is 10: 1-1: 10 respectively.
14. The method for preparing MQ silicone resin with high molecular weight according to claim 13, wherein the ratio of the extractant added in the first step to the extractant added in the second step in step B is 5: 1-1: 5 respectively.
15. The method for preparing MQ silicone resin with high molecular weight according to claim 13, wherein the ratio of the extractant added in the first step to the extractant added in the second step in step B is 2: 1-1: 5 respectively.
16. The method for preparing MQ silicone resin with high molecular weight as claimed in claim 13, wherein the step C is adjusted to neutrality by using one or more of calcium carbonate, sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium carbonate or potassium bicarbonate.
17. The method for preparing MQ silicone resin with high molecular weight as claimed in claim 1, wherein the pre-reaction conditions of step A are 10-50 ℃;
the addition mode of the silicate ester is as follows: gradually adding silicate ester into a mixed solution consisting of a part of M unit silane monomers, water, a catalyst and a cosolvent, and finishing the addition within 0.5-2 hours;
and after the silicate ester is added, the temperature is kept for 10-120 min.
18. The preparation method of MQ silicone resin with high molecular weight according to claim 1 or 17, characterized in that the heating conditions of step B are: heating to 50-80 ℃ and reacting for 1-6 hours.
19. The preparation method of the MQ silicone resin with high molecular weight as claimed in claim 1 or 17, wherein the distillation method comprises heating to 100-150 ℃ to remove low boiling point substances by evaporation.
20. The method for preparing MQ silicone resin with high molecular weight as claimed in claim 19, wherein the temperature is maintained at 100-150 ℃ for 1-6 hours after the distillation is completed.
21. The preparation method of the MQ silicone resin with high molecular weight according to any one of claims 1 to 16, wherein the weight ratio of the water, the catalyst, the cosolvent, the M unit silane monomer, the silicate ester and the extractant is 2-10: 2-8: 5-20: 1-10: 15-25: 10-40.
22. The preparation method of the MQ silicone resin with high molecular weight according to claim 21, wherein the weight ratio of the water, the catalyst, the cosolvent, the M unit silane monomer, the silicate ester and the extractant is 3-10: 2-6: 5-15: 2-8: 15-25: 20-40.
23. The method for preparing MQ silicone resin with high molecular weight as claimed in claim 1, wherein the molecular weight of MQ silicone resin with high molecular weight is 15000-45000.
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| CN113321809B (en) * | 2021-06-28 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method of MQ resin with narrow molecular weight distribution |
| CN114316268A (en) * | 2021-12-09 | 2022-04-12 | 湖北晟特新材料有限公司 | Organic silicon resin and preparation method thereof, mica tape adhesive and preparation method thereof |
| CN114316269B (en) * | 2021-12-28 | 2023-01-13 | 万华化学集团股份有限公司 | Preparation method and application of silicone resin |
| CN116120557A (en) * | 2022-12-29 | 2023-05-16 | 湖北晟特新材料有限公司 | MQ silicon resin without waste emission and preparation method thereof |
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