CN111019136A - Environment-friendly method for producing MQ silicon resin - Google Patents
Environment-friendly method for producing MQ silicon resin Download PDFInfo
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Abstract
The invention discloses an environment-friendly method for producing MQ silicon resin, which takes potassium silicate as a raw material and obtains the MQ silicon resin and sylvite after hydrolytic polycondensation in the presence of hexamethyldisiloxane, a blocking agent and a catalyst. According to the method, the MQ silicon resin is synthesized by using potassium silicate to replace sodium silicate as a main raw material, NaCl solid three wastes are not generated in byproducts, and the generated potassium salt has a recycling value, can be sold as a byproduct, and is energy-saving and environment-friendly.
Description
Technical Field
The invention relates to an environment-friendly method for producing MQ silicon resin, in particular to a method for producing MQ silicon resin by taking potassium silicate water glass as a raw material, belonging to the field of organic silicon materials.
Background
MQ silicone resin is a monomer functional group (M group) organic siloxane closed chain link R3SiO1/2And tetrafunctional (Q group) organosiloxane mer SiO4/2Polysiloxane with special performance is obtained by hydrolytic condensation. There are two known methods for preparing MQ silicone resins: using ethyl silicate as raw materialMQ silicon resin is prepared from raw materials (ethyl silicate method), and the MQ silicon resin product prepared by the method has good performance but higher cost; the other method is to prepare MQ silicon resin by using sodium silicate as a raw material (water glass method), and the performance of the MQ silicon resin prepared by the method is basically the same as that of the product prepared by the ethyl silicate method, but the price is lower, so the method is also a production method which is widely applied and popularized at present.
With the popularization and application of the water glass method, people find that the performance of the MQ silicon resin prepared by the water glass method is unstable due to the limitation of a plurality of factors such as raw material proportion, temperature selection, hydrolysis time, solvent selection and the like in the preparation process of the water glass method, so that the production benefit of enterprises is influenced. In the prior art, patent document CN103724626A (a novel method for preparing MQ resin, 2014.04.16) discloses a method for preparing MQ silicon resin by reacting and polycondensing a suspension system formed by an organic solvent and solid sodium silicate with halosilane, on one hand, the production cost can be reduced by using solid sodium silicate as a raw material, an acid catalyst is not used in the reaction process, the raw material composition and the complicated operation for treating the acid catalyst are reduced, and the byproduct is NaCl solid, which is small in amount and easy to treat. In order to improve the stability of the properties of MQ silicone resins, prior patent documents CN104910382A (a preparation method of MQ silicone resins, 2015.09.16) and CN109553773A (a methyl MQ resin and a preparation method thereof, 2019.04.02) both disclose methods for preparing MQ silicone resins using sodium silicate as a raw material.
From the above, in the process of producing MQ silicone resin by the water glass method, the byproduct is NaCl, and the current production situation of the enterprise is as follows: when the water glass method is used for production, a large amount of high-concentration NaCl wastewater can be generated while MQ silicon resin is obtained, and the high-concentration saline water can cause harm to soil if the high-concentration saline water is directly discharged, so that a large amount of energy and capital are consumed for distilling the high-concentration NaCl wastewater in the industrial production process, most of NaCl crystals in the high-concentration NaCl wastewater can be discharged after being extracted, but the extracted NaCl crystals are not easy to treat, and the recycling value is low.
Disclosure of Invention
In order to solve the problems of pollution and recovery caused by a byproduct NaCl in the existing production process for producing MQ silicon resin by a water glass method, the invention provides the method for producing the MQ silicon resin in an environment-friendly way.
The invention is realized by the following technical scheme: an environment-friendly method for producing MQ silicon resin is characterized in that potassium silicate is used as a raw material, and the MQ silicon resin and potassium salt are obtained through hydrolytic polycondensation in the presence of hexamethyldisiloxane, an end-capping agent and a catalyst.
50-200 parts of potassium silicate, 100-300 parts of hexamethyldisiloxane, 50-150 parts of catalyst, 180-500 parts of end-capping agent and 100-400 parts of water.
The end-capping reagent is selected from one of hexamethyldisiloxane, vinyl single end-capping reagent and vinyl double end-capping reagent, or a mixed solution of a mixture of the end-capping reagent and alcohol.
The end-capping agent is hexamethyldisiloxane, vinyl single end-capping or vinyl double end-capping and alcohol, and comprises, by weight, 20-100 parts of hexamethyldisiloxane, 10-50 parts of vinyl single end-capping or vinyl double end-capping and 150-350 parts of alcohol.
The alcohol is ethanol, propylene alcohol or methanol.
The catalyst is sulfuric acid or hydrochloric acid.
Carrying out hydrolytic polycondensation reaction on the aqueous solution of potassium silicate, a catalyst, an end-capping agent and hexamethyldisiloxane, washing the upper layer of liquid with water, removing a solvent to obtain MQ silicon resin, and neutralizing, rectifying and multi-effect evaporating the lower layer of liquid to obtain the potassium salt.
The hydrolytic polycondensation comprises the following steps:
(1) adding a catalyst into a reaction kettle, and starting stirring;
(2) adding a potassium silicate aqueous solution in the stirring process, keeping stirring and reacting;
(3) after reacting for 0-120 s, adding an end-capping reagent, continuously stirring, and reacting at 40-105 ℃;
(4) continuously heating and stirring, and then adding hexamethyldisiloxane for reaction to obtain the MQ silicon resin and the potassium salt.
The time interval between the addition of the potassium silicate aqueous solution and the addition of the hexamethyldisiloxane is controlled to be 0-50 min.
And (4) controlling the reaction time of the step (3) and the step (4) to be 2-6 h in total.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method adopts potassium silicate to replace sodium silicate as a main raw material to synthesize the MQ silicon resin, adopts the byproduct potassium salt with recycling and utilization values, can be used for solving the process status quo of low wastewater treatment energy consumption and recycling and utilization values caused by the byproduct NaCl in the existing production process for producing the MQ silicon resin by a water glass method, and reduces the environmental protection pressure.
(2) The method of the invention adopts sulfuric acid or hydrochloric acid as a catalyst, and the residual catalyst in the reaction materials can be neutralized by potassium hydroxide to obtain potassium salt (potassium chloride or potassium sulfate), and the potassium salt and the process byproduct potassium salt are recovered and treated together, so that no additional process byproduct is generated, the method is beneficial to the uniform treatment and recovery of the byproduct by enterprises, and the process cost is reduced.
(3) The potassium salt which is a byproduct of the method is mainly potassium chloride and/or potassium sulfate and can be used as a soil fertilizer, so that the method has higher recovery value, and enterprises can sell the byproduct to create certain economic benefit.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
the embodiment relates to an environment-friendly method for producing MQ silicon resin.
The specific production process comprises the following steps:
(1) respectively preparing a potassium silicate solution and an end-capping reagent,
potassium silicate solution: 180g of potassium silicate is added into 400ml of water, and the mixture is stirred and mixed evenly to obtain a potassium silicate solution.
End-capping agent: 65g of hexamethyldisiloxane and 36g of vinyl monocephalide were added to 250g of ethanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 108g of hydrochloric acid into a reaction kettle, wherein the temperature in the reaction kettle is 25 ℃, starting stirring, adding a potassium silicate solution in the stirring process, keeping stirring and reacting, adding an end-capping agent after the potassium silicate solution is added for 60s, continuously stirring and heating, heating to 85 ℃ after the end-capping agent is added, and continuously heating and stirring; and finally, adding 244g of hexamethyldisiloxane for extraction, and carrying out reflux reaction for a certain time to obtain a mixed solution of MQ silicon resin and potassium salt.
In the process, the time interval between the addition of the potassium silicate aqueous solution and the hexamethyldisiloxane is controlled to be 10min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 3 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 30min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 96g of MQ silicon resin. The lower layer liquid mainly contains potassium salt, alcohol, acid and water generated by reaction, after the lower layer liquid is neutralized by potassium hydroxide, alcohol is firstly rectified and recycled, then the residual solution containing the potassium salt is subjected to multi-effect evaporation to reach the discharge standard, and evaporation crystals of 26g of potassium salt are obtained and can be sold as byproducts.
Example 2:
the embodiment relates to an environment-friendly method for producing MQ silicon resin.
The specific production process comprises the following steps:
(1) respectively preparing a potassium silicate solution and an end-capping reagent,
potassium silicate solution: 105g of potassium silicate is added into 350ml of water, and the mixture is stirred and mixed evenly to obtain a potassium silicate solution.
End-capping agent: 40g of hexamethyldisiloxane and 20g of vinyl-bis-head were added to 200g of methanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 80g of sulfuric acid into a reaction kettle, wherein the temperature in the reaction kettle is 20 ℃, starting stirring, adding a potassium silicate solution in the stirring process, keeping stirring and reacting, adding an end-capping agent after the potassium silicate solution is added for 80s, continuously stirring and heating, heating to 65 ℃ after the end-capping agent is added, and continuously heating and stirring; and finally, adding 300g of hexamethyldisiloxane for extraction, and carrying out reflux reaction for a certain time to obtain a mixed solution of MQ silicon resin and potassium salt.
In the process, the time interval between the addition of the potassium silicate aqueous solution and the hexamethyldisiloxane is controlled to be 50min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 4 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 30min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 53g of MQ silicon resin. The lower layer liquid mainly contains sylvite, alcohol, acid and water generated by reaction, after the sylvite, the alcohol and the water are neutralized by potassium hydroxide, the alcohol is firstly rectified and recycled, then the residual sylvite-containing solution is subjected to multi-effect evaporation to reach the discharge standard, and evaporation crystals of 22g of sylvite are obtained and can be sold as byproducts.
Example 3:
the embodiment relates to an environment-friendly method for producing MQ silicon resin.
The specific production process comprises the following steps:
(1) respectively preparing a potassium silicate solution and an end-capping reagent,
potassium silicate solution: 50g of potassium silicate is added to 100ml of water and mixed uniformly with stirring to obtain a potassium silicate solution.
End-capping agent: 20g of hexamethyldisiloxane and 10g of vinyl-bis-end cap were added to 150g of isopropanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 50g of hydrochloric acid into a reaction kettle, keeping the temperature in the reaction kettle at 35 ℃, starting stirring, adding a potassium silicate solution in the stirring process, keeping stirring and reacting, adding an end-capping agent after the potassium silicate solution is added for 120s, continuously stirring and heating, heating to 105 ℃ after the end-capping agent is added, and continuously heating and stirring; and finally, adding 100g of hexamethyldisiloxane for extraction, and carrying out reflux reaction for a certain time to obtain a mixed solution of MQ silicon resin and potassium salt.
In the process, the time interval between the addition of the potassium silicate aqueous solution and the hexamethyldisiloxane is controlled to be 25min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 2 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 25min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 25g of MQ silicon resin. The lower layer liquid mainly contains sylvite, alcohol, acid and water generated by reaction, after the sylvite, the alcohol and the water are neutralized by potassium hydroxide, the alcohol is firstly rectified and recycled, then the residual sylvite-containing solution is subjected to multi-effect evaporation to reach the discharge standard, and evaporation crystals of 7g of sylvite are obtained and can be sold as a byproduct.
Example 4:
the embodiment relates to an environment-friendly method for producing MQ silicon resin.
The specific production process comprises the following steps:
(1) respectively preparing a potassium silicate solution and an end-capping reagent,
potassium silicate solution: 130g of potassium silicate is added into 280ml of water, and the mixture is stirred and mixed evenly to obtain a potassium silicate solution.
End-capping agent: 50g of hexamethyldisiloxane and 35g of vinyl monocephalic were added to 280g of ethanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 120g of hydrochloric acid into a reaction kettle, wherein the temperature in the reaction kettle is 0 ℃, starting stirring, adding the hydrochloric acid in the stirring process, keeping stirring and reacting, immediately adding an end-capping agent after the potassium silicate solution is added, continuously stirring and heating, heating to 40 ℃ for reaction, and continuously heating and stirring; finally, 220g of hexamethyldisiloxane is added for extraction, and the mixed solution of MQ silicon resin and potassium salt is obtained after reflux reaction for a certain time.
In the process, the time interval between the addition of the potassium silicate aqueous solution and the hexamethyldisiloxane is controlled to be 5min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 5 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 20min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 68g of MQ silicon resin. The lower layer liquid mainly contains potassium salt, alcohol, acid and water generated by reaction, after the lower layer liquid is neutralized by potassium hydroxide, alcohol is firstly rectified and recycled, and then the residual solution containing the potassium salt is subjected to multi-effect evaporation to reach the discharge standard, so that 19g of potassium salt evaporation crystal is obtained and can be sold as a byproduct.
Example 5:
the embodiment relates to an environment-friendly method for producing MQ silicon resin.
The specific production process comprises the following steps:
(1) respectively preparing a potassium silicate solution and an end-capping reagent,
potassium silicate solution: 150g of potassium silicate is added to 320ml of water and mixed uniformly with stirring to obtain a potassium silicate solution.
End-capping agent: 34g of hexamethyldisiloxane and 18g of vinyl monocephalic were added to 200g of methanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 95g of sulfuric acid into a reaction kettle, wherein the temperature in the reaction kettle is 15 ℃, starting stirring, adding the sulfuric acid in the stirring process, keeping stirring and reacting, adding an end-capping reagent after the potassium silicate solution is added for 40s, continuously stirring and heating, heating to 100 ℃ after the end-capping reagent is added, and continuously heating and stirring; and finally, adding 195g of hexamethyldisiloxane for extraction, and carrying out reflux reaction for a certain time to obtain a mixed solution of MQ silicon resin and potassium salt.
In the process, the time interval between the addition of the potassium silicate aqueous solution and the hexamethyldisiloxane is controlled to be 20min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 4 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 30min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 78g of MQ silicon resin. The lower layer liquid mainly contains sylvite, alcohol, acid and water generated by reaction, after the sylvite, the alcohol and the water are neutralized by potassium hydroxide, the alcohol is firstly rectified and recycled, then the residual sylvite-containing solution is subjected to multi-effect evaporation to reach the discharge standard, and evaporation crystals of 22g of sylvite are obtained and can be sold as byproducts.
Example 6:
the embodiment relates to an environment-friendly method for producing MQ silicon resin.
The specific production process comprises the following steps:
(1) respectively preparing a potassium silicate solution and an end-capping reagent,
potassium silicate solution: 125g of potassium silicate is added to 250ml of water and mixed uniformly with stirring to obtain a potassium silicate solution.
End-capping agent: 40g of hexamethyldisiloxane and 20g of vinyl monocephalic were added to 200g of ethanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 100g of sulfuric acid into a reaction kettle, wherein the temperature in the reaction kettle is 18 ℃, starting stirring, adding a potassium silicate solution in the stirring process, keeping stirring and reacting, adding an end-capping agent after the potassium silicate solution is added for 20s, continuously stirring and heating, heating to 95 ℃ after the end-capping agent is added, and continuously heating and stirring; and finally, adding 200g of hexamethyldisiloxane for extraction, and carrying out reflux reaction for a certain time to obtain a mixed solution of MQ silicon resin and potassium salt.
In the process, the time interval between the addition of the potassium silicate aqueous solution and the hexamethyldisiloxane is controlled to be 25min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 46 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 20min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 65g of MQ silicon resin. The lower layer liquid mainly contains sylvite, alcohol, acid and water generated by reaction, after the sylvite, the alcohol and the water are neutralized by potassium hydroxide, the alcohol is firstly rectified and recycled, then the residual sylvite-containing solution is subjected to multi-effect evaporation to reach the discharge standard, and evaporation crystals of 18g of sylvite are obtained and can be sold as byproducts.
Example 7:
the embodiment relates to an environment-friendly method for producing MQ silicon resin.
The specific production process comprises the following steps:
(1) respectively preparing a potassium silicate solution and an end-capping reagent,
potassium silicate solution: adding 200g of potassium silicate into 400ml of water, and uniformly mixing the potassium silicate and the water under stirring to obtain a potassium silicate solution.
End-capping agent: 100g of hexamethyldisiloxane and 50g of vinyl-bis-end cap were added to 350g of ethanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 150g of sulfuric acid into a reaction kettle, wherein the temperature in the reaction kettle is 20 ℃, starting stirring, adding a potassium silicate solution in the stirring process, keeping stirring and reacting, adding an end-capping agent after the potassium silicate solution is added for 80s, continuously stirring and heating, heating to 100 ℃ after the end-capping agent is added, and continuously heating and stirring; and finally, adding 300g of hexamethyldisiloxane for extraction, and carrying out reflux reaction for a certain time to obtain a mixed solution of MQ silicon resin and potassium salt.
In the process, the time interval between the addition of the potassium silicate aqueous solution and the hexamethyldisiloxane is controlled to be 50min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 6 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 30min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 102g of MQ silicon resin. The lower layer liquid mainly contains potassium salt, alcohol, acid and water generated by reaction, after the lower layer liquid is neutralized by potassium hydroxide, alcohol is firstly rectified and recycled, then the residual solution containing the potassium salt is subjected to multi-effect evaporation to reach the discharge standard, 29g of potassium salt evaporation crystal is obtained, and the potassium salt evaporation crystal can be sold as a byproduct.
Example 8:
the embodiment relates to an environment-friendly method for producing MQ silicon resin.
The specific production process comprises the following steps:
(1) respectively preparing a potassium silicate solution and an end-capping reagent,
potassium silicate solution: 80g of potassium silicate is added into 200ml of water, and the mixture is stirred and mixed uniformly to obtain a potassium silicate solution.
End-capping agent: 30g of hexamethyldisiloxane and 18g of vinyl monocephalic were added to 180g of ethanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 80g of hydrochloric acid into a reaction kettle, wherein the temperature in the reaction kettle is 18 ℃, starting stirring, adding a potassium silicate solution in the stirring process, keeping stirring and reacting, adding an end-capping agent after the potassium silicate solution is added for 40s, continuously stirring and heating, heating to 90 ℃ after the end-capping agent is added, and continuously heating and stirring; and finally, adding 145g of hexamethyldisiloxane for extraction, and carrying out reflux reaction for a certain time to obtain a mixed solution of MQ silicon resin and potassium salt.
In the process, the time interval between the addition of the potassium silicate aqueous solution and the hexamethyldisiloxane is controlled to be 35min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 3 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 25min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 42g of MQ silicon resin. The lower layer liquid mainly contains sylvite, alcohol, acid and water generated by reaction, after the sylvite, the alcohol and the water are neutralized by potassium hydroxide, the alcohol is firstly rectified and recycled, then the residual sylvite-containing solution is subjected to multi-effect evaporation to reach the discharge standard, evaporation crystals of 11g of sylvite are obtained, and the evaporation crystals can be sold as byproducts.
Comparative example 1:
this comparative example relates to a process for preparing MQ silicone resin using a water glass process.
The specific production process comprises the following steps:
(1) respectively preparing a silicic acid solution and a blocking agent,
sodium silicate solution: 125g of sodium silicate is added into 250ml of water, and the mixture is stirred and mixed evenly to obtain silicic acid solution.
End-capping agent: 40g of hexamethyldisiloxane and 20g of vinyl monocephalic were added to 200g of ethanol to obtain a mixed solution.
(2) The hydrolysis and the polycondensation are carried out,
adding 100g of hydrochloric acid into a reaction kettle, wherein the temperature in the reaction kettle is 20 ℃, starting stirring, adding a sodium silicate solution in the stirring process, keeping stirring and reacting, adding an end-capping reagent after the sodium silicate solution is added for 50s, continuously stirring and heating, heating to 100 ℃ after the end-capping reagent is added, and continuously heating and stirring; and finally, adding 200g of hexamethyldisiloxane for extraction, and carrying out reflux reaction for a certain time to obtain a mixed solution of MQ silicon resin and potassium salt.
In the process, the time interval between the addition of the silicic acid aqueous solution and the hexamethyldisiloxane is controlled to be 30min, in addition, the end-capping agent is added, the timing is started when the temperature in the kettle reaches the specified temperature, and the total reaction time is controlled to be 4 h.
(3) The post-treatment of the product is carried out,
standing and layering the mixed solution obtained by the reaction for 30min, taking the upper layer liquid, washing the upper layer liquid to be neutral, and removing the solvent at high temperature in vacuum to obtain 64g of MQ silicon resin. The lower layer liquid mainly contains sodium salt, alcohol, acid and water generated by the reaction, the residual sodium salt except the solvent and the acid is subjected to multi-effect evaporation in a stainless steel kettle with vacuum to obtain 22g of evaporated crystals of the sodium salt.
Respectively testing the light transmittance of the MQ silicon resins prepared in the embodiments 1-8 and the comparative example 1 by using a 721 spectrophotometer; testing the viscosity according to a GB/T10247-2008 viscosity measurement method; the molecular weight was measured by GB/T21863-2008 Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent, and the performance was determined, and the performance index was shown in Table 1 below. (Table 1 is intended to demonstrate the differences in properties of MQ silicone resins synthesized using potassium silicate instead of sodium silicate as the starting material under the same synthesis process conditions.)
Table 1 MQ silicone resin performance comparison table
The production process related to the above example 6 and the comparative document 1 was continuously operated for 30 days, and the process cost, energy consumption and income thereof were calculated, as shown in the following table 2.
TABLE 2 production Process cost, energy consumption and profit accounting sheet
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. An environment-friendly method for producing MQ silicon resin is characterized in that: taking potassium silicate as a raw material, and obtaining MQ silicon resin and potassium salt through hydrolytic polycondensation in the presence of hexamethyldisiloxane, an end-capping agent and a catalyst.
2. The method for environmentally producing MQ silicone resin according to claim 1, wherein: 50-200 parts of potassium silicate, 100-300 parts of hexamethyldisiloxane, 50-150 parts of catalyst, 180-500 parts of end-capping agent and 100-400 parts of water.
3. The method for environmentally producing MQ silicone resin according to claim 1, wherein: the end-capping reagent is selected from one of hexamethyldisiloxane, vinyl single end-capping reagent and vinyl double end-capping reagent, or a mixed solution of a mixture of the end-capping reagent and alcohol.
4. An environmentally friendly method of producing MQ silicone resin according to claim 3, wherein: the end-capping agent is hexamethyldisiloxane, vinyl single end-capping or vinyl double end-capping and alcohol, and comprises, by weight, 20-100 parts of hexamethyldisiloxane, 10-50 parts of vinyl single end-capping or vinyl double end-capping and 150-350 parts of alcohol.
5. An environmentally friendly method of producing MQ silicone resin according to claim 3, wherein: the alcohol is ethanol, propylene alcohol or methanol.
6. The method for environmentally producing MQ silicone resin according to claim 1, wherein: the catalyst is sulfuric acid or hydrochloric acid.
7. The method for environmentally producing MQ silicone resin according to claim 1, wherein: carrying out hydrolytic polycondensation reaction on the aqueous solution of potassium silicate, a catalyst, an end-capping agent and hexamethyldisiloxane, washing the upper layer of liquid with water, removing a solvent to obtain MQ silicon resin, and neutralizing, rectifying and multi-effect evaporating the lower layer of liquid to obtain the potassium salt.
8. The method for environmentally producing MQ silicone resin according to claim 1, wherein: the hydrolytic polycondensation comprises the following steps:
(1) adding a catalyst into a reaction kettle, and starting stirring;
(2) adding a potassium silicate aqueous solution in the stirring process, keeping stirring and reacting;
(3) after reacting for 0-120 s, adding an end-capping reagent, continuously stirring, and reacting at 40-105 ℃;
(4) continuously heating and stirring, and then adding hexamethyldisiloxane for reaction to obtain the MQ silicon resin and the potassium salt.
9. The method for environmentally producing MQ silicone resin according to claim 8, wherein: the time interval between the addition of the potassium silicate aqueous solution and the addition of the hexamethyldisiloxane is controlled to be 0-50 min.
10. The method for environmentally producing MQ silicone resin according to claim 8, wherein: and (4) controlling the reaction time of the step (3) and the step (4) to be 2-6 h in total.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430329A (en) * | 2020-11-27 | 2021-03-02 | 成都博达爱福科技有限公司 | Method for synthesizing acryloxy MQ silicon resin |
| CN114015049A (en) * | 2021-10-29 | 2022-02-08 | 山东东岳有机硅材料股份有限公司 | Preparation method of MQ silicon resin for synthesizing pressure-sensitive adhesive from organic silicon by-product |
| CN115947943A (en) * | 2021-12-08 | 2023-04-11 | 四川晨光博达新材料有限公司 | MQ silicon resin with ultrahigh vinyl content and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613475A (en) * | 2009-07-17 | 2009-12-30 | 南昌大学 | Preparing MQ silicon resin by organic acid catalysis |
| CN104072776A (en) * | 2014-07-04 | 2014-10-01 | 成都博达爱福科技有限公司 | MQ silicon resin for preparation of medical pressure-sensitive adhesive and preparation process thereof |
| JP5911593B2 (en) * | 2011-11-15 | 2016-04-27 | エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ | Compositions containing block cocondensates of propyl-functional alkali silicates and alkali silicates and methods for their production |
| CN106467442A (en) * | 2016-09-07 | 2017-03-01 | 张家港美景荣化学工业有限公司 | Preparation and treatment methods and application of fermentation liquor of 1, 3-propylene glycol, preparation method of water-soluble fertilizer and water-soluble fertilizer |
-
2019
- 2019-12-25 CN CN201911355710.5A patent/CN111019136A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613475A (en) * | 2009-07-17 | 2009-12-30 | 南昌大学 | Preparing MQ silicon resin by organic acid catalysis |
| JP5911593B2 (en) * | 2011-11-15 | 2016-04-27 | エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ | Compositions containing block cocondensates of propyl-functional alkali silicates and alkali silicates and methods for their production |
| CN104072776A (en) * | 2014-07-04 | 2014-10-01 | 成都博达爱福科技有限公司 | MQ silicon resin for preparation of medical pressure-sensitive adhesive and preparation process thereof |
| CN106467442A (en) * | 2016-09-07 | 2017-03-01 | 张家港美景荣化学工业有限公司 | Preparation and treatment methods and application of fermentation liquor of 1, 3-propylene glycol, preparation method of water-soluble fertilizer and water-soluble fertilizer |
Non-Patent Citations (3)
| Title |
|---|
| 周灿璨等: "脱水缩聚对由硅酸钠制备的MQ硅树脂羟基含量的影响", 《合成树脂及塑料》 * |
| 王亮等: "ＭＱ硅树脂的合成及其对硅压敏胶性能的影响", 《武汉理工大学学报》 * |
| 王兴国等: "《食用油精准适度加工理论与实践》", 31 December 2016, 中国轻工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430329A (en) * | 2020-11-27 | 2021-03-02 | 成都博达爱福科技有限公司 | Method for synthesizing acryloxy MQ silicon resin |
| CN114015049A (en) * | 2021-10-29 | 2022-02-08 | 山东东岳有机硅材料股份有限公司 | Preparation method of MQ silicon resin for synthesizing pressure-sensitive adhesive from organic silicon by-product |
| CN114015049B (en) * | 2021-10-29 | 2023-10-24 | 山东东岳有机硅材料股份有限公司 | Preparation method of MQ silicon resin for synthesizing pressure-sensitive adhesive from organic silicon byproducts |
| CN115947943A (en) * | 2021-12-08 | 2023-04-11 | 四川晨光博达新材料有限公司 | MQ silicon resin with ultrahigh vinyl content and preparation method thereof |
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