CN115041102B - Method for controlling input amount of alcohol alkali liquor for silicone oil cracking and product thereof - Google Patents

Method for controlling input amount of alcohol alkali liquor for silicone oil cracking and product thereof Download PDF

Info

Publication number
CN115041102B
CN115041102B CN202210782700.5A CN202210782700A CN115041102B CN 115041102 B CN115041102 B CN 115041102B CN 202210782700 A CN202210782700 A CN 202210782700A CN 115041102 B CN115041102 B CN 115041102B
Authority
CN
China
Prior art keywords
alcohol
stage
reaction
viscosity
cracking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210782700.5A
Other languages
Chinese (zh)
Other versions
CN115041102A (en
Inventor
梁广耀
梁广强
梁广伟
潘科学
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Sheensun Technology Co ltd
Original Assignee
Guangdong Sheensun Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Sheensun Technology Co ltd filed Critical Guangdong Sheensun Technology Co ltd
Priority to CN202210782700.5A priority Critical patent/CN115041102B/en
Publication of CN115041102A publication Critical patent/CN115041102A/en
Application granted granted Critical
Publication of CN115041102B publication Critical patent/CN115041102B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/008—Feed or outlet control devices
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/59—Transmissivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

Abstract

The invention relates to the technical field of organic silicon production, and discloses a method for controlling the input amount of alcohol alkali liquor for cracking silicone oil and a product thereof, wherein the method comprises the following steps: s1) dividing the cracking reaction into 8 to 12 stages according to the time schedule, and setting a standard value; s2) calculating the total amount of the alcohol alkali liquor required by the cracking reaction; s3) adding the silicone oil to be cracked and part of the alcohol alkali liquor, and then heating to reach an optimal temperature state; s4) detecting the instant viscosity of the reaction liquid when the stage 1 is close to the end to obtain a corresponding viscosity difference value, supplementing part of alcohol alkali liquid according to the viscosity difference value, and entering the next stage until the viscosity difference value is not greater than zero; s5) repeating the step S4), and finishing the stages 2 to 12; the invention avoids excessive alkali metal ions or excessive macromolecular polymers in the cracking reaction product, and the waterproof material prepared by the method has excellent reaction activity, good waterproof performance and wide application prospect.

Description

Method for controlling input amount of alcohol alkali liquor for silicone oil cracking and product thereof
Technical Field
The invention relates to the technical field of organic silicon production, in particular to a method for controlling the input amount of alcohol alkali liquor for cracking silicone oil and a product thereof.
Background
The key point of the quality control of the organosilicon waterproofing agent is to control the purity of the cracking reaction product of the silicone oil. The number of silicon oxygen groups contained in a specific product of the silicone oil cracking reaction is related to factors such as heating temperature, stirring speed, reaction time and the like, and the alcohol-base ratio in a reaction liquid is the most important influencing factor.
Taking a silicone oil cracking reaction taking hydroxyl-terminated polysiloxane and a potassium hydroxide alcohol solution as raw materials as an example, according to the theoretical calculation of a chemical reaction, a silicon oxygen group of each structural unit is combined with two potassium ions during the cracking reaction to generate a dimethyl silicon potassium alkoxide molecule. Because the number of the structural units of the siloxy group contained in each molecule of the hydroxyl-terminated polysiloxane can not be accurately determined, the alkali dosage of the required cracking reaction can not be accurately calculated, and the proportion of the polysiloxane and the potassium hydroxide alcohol solution can only be calculated and configured according to a theoretical value, so that the proportion balance of the cracking reaction can be achieved macroscopically.
The silicon oil cracking in the prior art can cause the condition that the addition amount of the alcohol alkali liquor is insufficient or excessive; if the addition amount of the alcohol alkali liquor is insufficient, polymers of the silicone oil cannot be cracked sufficiently, so that the residual polymer macromolecular groups in the final reaction liquid are more; if the addition amount of the alcohol alkali liquor is too much, the residual alkali metal ions in the final reaction liquid are too much; the waterproof material prepared from the reaction products of the two conditions has poor reactivity, seriously influences the waterproof performance of the waterproof material and limits the application range of the waterproof material.
Disclosure of Invention
In view of the above problems, the present invention provides a method for controlling the input amount of an alcohol lye for silicone oil cracking and a product thereof, which can control the supplement amount of the alcohol lye.
In order to achieve the purpose, the invention adopts the following technical scheme:
a control method of the input amount of alcohol alkali liquor for silicone oil cracking comprises the following steps:
s1) dividing the cracking reaction of the silicone oil in the alcohol alkali liquor into 8 to 12 stages according to the time schedule, setting the viscosity standard value of each stage, and defining the difference value between the viscosity detection value near the end of any stage and the viscosity standard value corresponding to the stage as the viscosity difference value;
s2) calculating the theoretical value of the total amount of the alcohol alkali liquor required by the cracking reaction in an equivalent manner according to the average molecular weight of the silicone oil to be cracked;
s3) putting all the silicon oil to be cracked into a reaction kettle, putting part of alcohol alkali liquor into the reaction kettle, starting the cracking reaction by raising the temperature to keep the temperature of the reaction liquid within a set required range, and then entering the stage 1;
s4) detecting the instant viscosity of the reaction liquid when the stage 1 is close to the end, and calculating to obtain a corresponding viscosity difference value, if the viscosity difference value is larger than zero, supplementing an alcohol alkali liquid into the reaction liquid in the stage, otherwise, directly entering the next stage;
and S5) repeating the step S4), sequentially completing the stages 2 to 12, detecting and recording the mass concentration of silicon alkoxide monomer molecules and the mass concentration of silicon oil molecules with the polymerization degree not greater than 10 in the reaction liquid when the stages 8 to 12 are nearly finished, and when the mass concentration of the silicon alkoxide monomer molecules and the mass concentration of the siloxane molecules with the polymerization degree not greater than 10 in the reaction liquid reach the set final control target, determining that the cracking reaction is sufficient, stopping adding the alcohol alkali liquor and heating, detecting and confirming that the mass concentration of free alkali metal ions is less than 0.90%, and finishing the cracking reaction.
Specifically, in the step S3), the initial input amount of the alcohol alkali liquor accounts for 50-60% of the theoretical value of the total amount of the alcohol alkali liquor;
setting the final control target as: the mass concentration of the silicon alkoxide monomer molecules is not less than 60 percent, and the mass concentration of the siloxane molecules with the polymerization degree not more than 10 is not less than 85 percent;
the duration of the 1 st stage is 110-120min, and the duration of each stage from the 2 nd stage to the 12 th stage is set to 40-45min.
In some embodiments, in step S4), the formula for the amount of alcohol lye to be supplemented a is: (X1-X0)/X0X, wherein X1 is a viscosity detection value in the reaction stage, X0 is a viscosity standard value, and Y is a difference value obtained by subtracting the added and supplemented alcohol alkali liquor from a theoretical value of the total amount of the alcohol alkali liquor.
In other embodiments, step S1) further comprises the following: setting a transmittance standard value of each stage, and defining a difference value between the transmittance standard value of any stage and a transmittance detection value near the end of the stage as a transmittance difference value;
accordingly, step S4) is adjusted to: detecting the instant viscosity and transmittance of the reaction liquid when the stage 1 is close to the end, and calculating to obtain a corresponding viscosity difference value and transmittance difference value, if the viscosity difference value and the transmittance difference value are both larger than zero, supplementing the alcohol alkali liquid into the reaction liquid in the stage, wherein the supplement amount A of the alcohol alkali liquid has the calculation formula: (X1-X0)/X0Y, wherein X1 is a viscosity detection value near the end of the reaction stage, X0 is a viscosity standard value corresponding to the stage, and Y is a difference value obtained by subtracting the added and supplemented alcohol alkali liquor from a theoretical value of the total amount of the alcohol alkali liquor; if the viscosity difference is greater than zero and the transmittance difference is less than zero, the amount of the added alcohol alkali solution is too much, the replenishment amount A of the alcohol alkali solution in the reaction solution at the stage needs to be corrected, and the calculation formula of the replenishment amount A of the corresponding alcohol alkali solution is as follows: (X1-X0)/X0Y + (Z0-Z1)/Z0Y, wherein X1 is a viscosity detection value near the end of the reaction stage, X0 is a viscosity standard value corresponding to the stage, Z1 is a transmittance detection value near the end of the reaction stage, Z0 is a transmittance standard value corresponding to the stage, and Y is a difference value obtained by subtracting the added and supplemented alcohol alkali liquor from a theoretical value of the total amount of the alcohol alkali liquor; if the viscosity difference is not larger than zero, directly entering the next stage.
Preferably, in step S3), the detection items of the reaction solution further include density detection, and from the 1 st stage to the 12 th stage, the average value of the density values of the reaction solution obtained by the detection is kept unchanged, and the fluctuation width of the density values is gradually narrowed and tends to be stable.
Preferably, the reaction temperature of the 1 st stage to the 12 th stage is 80 +/-2 ℃; the viscosities of stages 1 to 12 are decreased in order, and the stirring speed of the reaction solution is decreased correspondingly in stages 3 to 12.
Further, the alcohol alkali solution comprises fatty alcohol and alcohol alkali, wherein the fatty alcohol is formed by mixing butanol and ethanol, and the alcohol alkali is prepared by reacting inorganic alkali such as potassium hydroxide or sodium hydroxide with ethanol.
Specifically, the preparation steps of the alcohol lye are as follows:
respectively adding inorganic base, ethanol and butanol into an ultrasonic mixer, stirring and mixing for 0.5-2h, then heating to 80-90 ℃, keeping the temperature and stirring for 1-3h, and continuously separating water generated by the reaction to obtain the alcohol alkali liquor;
the mass ratio of the inorganic base to the fatty alcohol is (1-3): (4-7); the mass ratio of ethanol to butanol in the fatty alcohol is (1-7): (4-13), the frequency of the ultrasonic wave is 20-24kHz, and the stirring speed is 80-85r/min.
Furthermore, the methyl silanolate used in the waterproof material prepared by the method for controlling the input amount of the alcohol alkali liquor for silicone oil cracking is prepared according to the method for controlling the input amount of the alcohol alkali liquor for silicone oil cracking, the mass concentration of the contained free alkali metal ions is 0.2-0.9%, and the mass concentration of the contained siloxane molecules with the polymerization degree of more than 10 is 5-15%.
The technical scheme of the invention has the beneficial effects that: the method for controlling the input amount of the alcohol alkali liquor for silicone oil cracking detects the viscosity of reaction liquid in each reaction stage, obtains a corresponding viscosity difference value by comparing standard values, and controls the input amount of the alcohol alkali liquor in the corresponding stage according to the obtained difference value, thereby controlling the input amount and the total input amount of the alcohol alkali liquor in the whole cracking reaction, further avoiding excessive alkali metal ions or excessive macromolecular polymers from appearing in final products of the cracking reaction, and finally achieving the purpose of improving the high temperature resistance and the ultraviolet resistance of corresponding silicone oil cracking products.
Furthermore, the waterproof material prepared by the methyl silicon alkoxide according to the method for controlling the input amount of the alcohol alkali liquor for cracking the silicone oil contains lower mass concentration of free alkali metal ions and lower mass concentration of siloxane molecules with polymerization degree larger than 10, and has excellent reaction activity, good waterproof performance and wide application prospect.
Drawings
FIG. 1 is a standard value curve of viscosity for silicone oil cracking reaction according to an embodiment of the present invention;
FIG. 2 is a standard curve of transmittance of a silicone oil cleavage reaction according to another embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
In the description herein, references to the description of the terms "embodiment," "example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
A control method of the input amount of alcohol alkali liquor for silicone oil cracking comprises the following steps:
s1) dividing the cracking reaction of the silicone oil in the alcohol alkali liquor into 8 to 12 stages according to the time schedule, setting the viscosity standard value of each stage, and defining the difference value between the viscosity detection value near the end of any stage and the viscosity standard value corresponding to the stage as the viscosity difference value;
s2) calculating the theoretical value of the total amount of the alcohol alkali liquor required by the cracking reaction in an equivalent manner according to the average molecular weight of the silicone oil to be cracked;
s3) putting all the silicon oil to be cracked into a reaction kettle, putting part of alcohol alkali liquor, starting the cracking reaction by raising the temperature, keeping the temperature of the reaction liquid within a set required range, and entering the stage 1;
s4) detecting the instant viscosity of the reaction liquid when the stage 1 is close to the end, and calculating to obtain a corresponding viscosity difference value, if the viscosity difference value is larger than zero, supplementing an alcohol alkali liquid into the reaction liquid in the stage, and entering the next stage until the viscosity difference value in the stage is not larger than zero;
and S5) repeating the step S4), sequentially completing the stages 2 to 12, detecting and recording the mass concentration of silicon alkoxide monomer molecules and the mass concentration of silicon oil molecules with the polymerization degree not greater than 10 in the reaction liquid when the stages 8 to 12 are nearly finished, and when the mass concentration of the silicon alkoxide monomer molecules and the mass concentration of the siloxane molecules with the polymerization degree not greater than 10 in the reaction liquid reach the set final control target, determining that the cracking reaction is sufficient, stopping adding the alcohol alkali liquor and heating, detecting and confirming that the mass concentration of free potassium ions is less than 0.90%, and finishing the cracking reaction.
The method for controlling the input amount of the alcohol alkali liquor for cracking the silicone oil divides the whole cracking reaction into 8-12 stages according to the reaction duration, presets a viscosity standard value of the reaction liquid near the end of the 1 st-12 th stage according to an empirical curve of viscosity change of the similar silicone oil cracking reaction, and also sets that when the mass concentration of silicone alkoxide monomer molecules in the reaction liquid reaches 60 percent and the mass concentration of silicone oil molecules with the polymerization degree not greater than 10 is not less than 85 percent, the cracking reaction is considered to be sufficient, and the cracking reaction can be ended; the viscosity of the reaction liquid is detected when each stage of the 1 st to 12 th stages is close to the end, the corresponding viscosity difference value is obtained by comparing the standard values, and the alcohol alkali liquid supplement amount of the corresponding stage is controlled according to the obtained difference value, so that the alcohol alkali liquid supplement amount and the total input amount of the whole cracking reaction are controlled, excessive alkali metal ions or excessive macromolecular polymers are prevented from appearing in the final product of the cracking reaction, and finally the purposes of improving the reactivity of the corresponding silicon oil lysate product and realizing good waterproof performance are achieved.
The method for controlling the input amount of the alcohol alkali liquor for cracking the silicone oil is suitable for the cracking reaction of the hydroxyl silicone oil and the methyl silicone oil, and the average molecular weight of the silicone oil correspondingly suitable for the method is as follows: 50000-150000.
It should be noted that, as time advances, the cracking reaction continues to occur, the mass concentration of the silicon alkoxide monomer molecules in the reaction liquid and the mass concentration of the silicon oil molecules having a degree of polymerization of not more than 10 are accumulated, and the viscosity of the reaction liquid is continuously decreased.
Specifically, in the step S3), the initial input amount of the alcohol alkali liquor accounts for 50-60% of the theoretical value of the total amount of the alcohol alkali liquor;
setting the final control target as: the mass concentration of the silicon alkoxide monomer molecules is not less than 60 percent, and the mass concentration of the siloxane molecules with the polymerization degree not more than 10 is not less than 85 percent;
the duration of the 1 st stage is 110-120min, and the duration of each stage from the 2 nd stage to the 12 th stage is set to 40-45min.
Usually, the theoretical value of the total amount of the alcohol alkali liquor is excessive, so that part of the alcohol alkali liquor is added firstly, and then the required alcohol alkali liquor in the reaction process is gradually supplemented through viscosity control, so that the excessive addition of the alcohol alkali liquor can be effectively avoided.
In some embodiments, in step S4), the formula for the amount of alcohol lye to be supplemented a is: (X1-X0)/X0X, wherein X1 is a viscosity detection value in the reaction stage, X0 is a viscosity standard value, and Y is a difference value obtained by subtracting the added and supplemented alcohol alkali liquor from a theoretical value of the total amount of the alcohol alkali liquor.
By comparing with the standard value of the viscosity and controlling the appropriate amount of the alcohol alkali liquor, the cracking of the silicone oil can be gradually and fully reacted in each stage; and the alcohol alkali liquor is added in batches by stages, so that the phenomenon of excessive alcohol alkali liquor added at one time can be avoided.
In other embodiments, step S1) further comprises the following: setting a transmittance standard value of each stage, and defining a difference value between the transmittance standard value of any stage and a transmittance detection value near the end of the stage as a transmittance difference value;
accordingly, step S4) is adjusted to: detecting the instant viscosity and transmittance of the reaction liquid when the stage 1 is close to the end, and calculating to obtain a corresponding viscosity difference value and transmittance difference value, if the viscosity difference value and the transmittance difference value are both larger than zero, supplementing the alcohol alkali liquid into the reaction liquid in the stage, wherein the supplement amount A of the alcohol alkali liquid has the calculation formula: (X1-X0)/X0X, wherein X1 is a viscosity detection value near the end of the reaction stage, X0 is a viscosity standard value corresponding to the stage, and Y is a difference value obtained by subtracting the added and supplemented alcohol lye from a theoretical value of the total amount of the alcohol lye; if the viscosity difference is greater than zero and the transmittance difference is less than zero, the amount of the added alcohol alkali solution is too much, the replenishment amount A of the alcohol alkali solution in the reaction solution at the stage needs to be corrected, and the calculation formula of the replenishment amount A of the corresponding alcohol alkali solution is as follows: (X1-X0)/X0Y + (Z0-Z1)/Z0Y, wherein X1 is a viscosity detection value near the end of the reaction stage, X0 is a viscosity standard value corresponding to the stage, Z1 is a transmittance detection value near the end of the reaction stage, Z0 is a transmittance standard value corresponding to the stage, and Y is a difference value obtained by subtracting the fed and supplemented alcohol alkali liquor from a theoretical value of the total amount of the alcohol alkali liquor; if the viscosity difference is not larger than zero, directly entering the next stage.
Similarly, the standard viscosity value and the standard transmittance value of the reaction solution near the end of the 1 st to 12 th stages can be preset according to the empirical curves of the viscosity change and the transmittance change of the similar silicone oil cracking reaction.
It is worth to be noted that, as the cracking reaction is continuously generated along with the advance of time, the concentration of the macromolecular polyoxosilane in the reaction liquid after cracking the silicone oil is gradually reduced, correspondingly, the mass concentration of the silicon alkoxide monomer molecules and the mass concentration of the silicone oil molecules with the polymerization degree not greater than 10 are continuously increased, the viscosity of the reaction liquid is reduced in a curve manner, the transmittance of the reaction liquid is gradually increased and finally approaches to transparency, and the transmittance at the moment can reach more than 95%; therefore, a transmittance standard value corresponding to the viscosity standard value is set, and then whether the transmittance of each stage near the end is greater than the standard value or not is compared, so that whether the cracking reaction of the stage is faster than the expected reaction progress or not can be judged, if so, the situation that the alcohol alkali liquor which is already added in the previous stage is excessive is shown, and therefore, the formula can be obtained: and (X1-X0)/X0Y + (Z0-Z1)/Z0Y, calculating and correcting the alcohol alkali liquor replenishment quantity A at the stage so as to achieve the purpose of correcting excessive added alcohol alkali liquor and further avoid the phenomenon that the mass concentration of alkali metal ions in the reaction product exceeds 0.90 percent.
Preferably, in step S3), the detection items of the reaction solution further include density detection, and from the 1 st stage to the 12 th stage, the average value of the density values of the reaction solution obtained by the detection is kept unchanged, and the fluctuation width of the density values is gradually narrowed and tends to be stable.
By detecting the density, whether abnormity occurs in the reaction process can be found in time, so that emergency measures can be taken in time, and accidents and quality loss are avoided.
Preferably, the reaction temperature of the 1 st to 12 th stages is 80 +/-2 ℃; the viscosities of stages 1 to 12 are decreased in order, and the stirring speed of the reaction solution is decreased correspondingly in stages 3 to 12.
The silicon-oxygen bond in the silicone oil can be broken by keeping the reaction temperature of 80 +/-2 ℃, so that the cracking reaction is stable and continuous; the viscosity of the cracking reaction in the 1 st to 12 th stages is reduced in sequence, and the stirring speed of the 3 rd to 12 th stages is correspondingly reduced, so that the aim of uniformly distributing the temperature of the reaction liquid can be fulfilled.
Further, the alcohol alkali solution comprises fatty alcohol and alcohol alkali, wherein the fatty alcohol is formed by mixing butanol and ethanol, and the alcohol alkali is prepared by reacting inorganic alkali such as potassium hydroxide or sodium hydroxide with ethanol.
The alcohol alkali liquor is prepared or premixed by adopting ultrasonic waves, so that the inorganic alkali is dispersed more uniformly and is easy to react with ethanol to generate alcohol alkali with stronger alkalinity, the optimal reaction condition is achieved, the cracking efficiency of the cracking reaction is improved, and the method is an important measure for promoting the generation of silicon alkoxide molecules.
Specifically, the preparation steps of the alcohol alkali liquor are as follows:
respectively adding inorganic base, ethanol and butanol into an ultrasonic mixer, stirring and mixing for 0.5-2h, then heating to 80-90 ℃, keeping the temperature and stirring for 1-3h, and continuously separating water generated by the reaction to obtain the alcohol alkali liquor;
the mass ratio of the inorganic base to the fatty alcohol is (1-3): (4-7); the mass ratio of ethanol to butanol in the fatty alcohol is (1-7): (4-13), the frequency of the ultrasonic wave is 20-24kHz, and the stirring speed is 80-85r/min.
Ethanol reacts with inorganic base to generate alcohol base, and butanol plays a role of a solvent and can dissolve silicone oil with low polymerization degree to promote the cracking reaction.
Furthermore, the methyl silicon alkoxide used in the waterproof material prepared by the method for controlling the input amount of the alcohol alkali liquor for silicone oil cracking is prepared according to the method for controlling the input amount of the alcohol alkali liquor for silicone oil cracking, the mass concentration of the contained free alkali metal ions is 0.2-0.9%, the mass concentration of the contained siloxane molecules with the polymerization degree of more than 10 is 5-15%, and compared with the methyl silicon alkoxide which contains the free alkali metal ions with the mass concentration of about 5% and the siloxane molecules with the polymerization degree of more than 10 in the prior art, the methyl silicon alkoxide has the advantages of obvious improvement, excellent reaction activity and good waterproof performance.
Example 1
Hydroxyl-terminated polysiloxane with average molecular weight of 110000 to be subjected to cracking treatment, alcohol alkali liquor is a mixed solution of potassium ethoxide and butanol, the final control targets for judging that the cracking reaction is sufficient are that the mass concentration of silicon alkoxide monomer molecules is not less than 65%, the mass concentration of siloxane molecules with polymerization degree not greater than 10 is not less than 85%, and the mass concentration of residual free potassium ions is less than 0.90%, and the corresponding control method of the input amount of the alcohol alkali liquor for the cracking reaction has the following specific steps:
s0) preparing an alcohol alkali solution in advance: respectively adding potassium hydroxide, ethanol and butanol into an ultrasonic mixer, stirring and mixing for 1h, then heating to 85 ℃, stirring and preserving heat for 1.5h, and separating water generated by reaction to obtain the alcohol alkali liquor; wherein the mass ratio of the ethanol to the butanol is 1:3, and the mass ratio of the mass of the potassium hydroxide to the total mass of the ethanol and the butanol is 3; the frequency of the ultrasonic wave is 22kHz, and the stirring speed is 85r/min.
S1) dividing the cracking reaction process into 8 stages according to the viscosity curve of the cracking reaction of the hydroxyl-terminated polysiloxane at 80 ℃ shown in figure 1 according to the time schedule, setting the viscosity standard value of each stage as listed in Table 1, and defining the difference between the viscosity detection value near the end of any stage and the viscosity standard value corresponding to the stage as the viscosity difference;
s2) 500kg of hydroxyl-terminated polysiloxane with the average molecular weight of 110000 to be cracked, and the theoretical value of the total amount of alcohol alkali liquor required by equivalent calculation of the cracking reaction is 3185.9kg;
s3) putting 500kg of hydroxyl-terminated polysiloxane to be cracked into a reaction kettle, putting 1752.2kg of alcohol alkali liquor accounting for 55% of the total mass of the alcohol alkali liquor, heating to 80 ℃ to start the cracking reaction, and maintaining the temperature of reaction liquid at 80 +/-2 ℃ to keep the cracking reaction continuously;
s4) when the step 1 is carried out for 120min, detecting the instant viscosity of the reaction liquid, calculating to obtain a corresponding viscosity difference value, wherein the obtained viscosity difference value is listed in Table 1, and supplementing the alcohol alkali liquid into the reaction liquid as listed in Table 1 until the viscosity difference value of the step is not more than zero;
s5) repeating the step S4), sequentially completing the 2 nd to the 8 th stages, wherein the alcohol alkali liquor supplementation amount A of each stage is listed in the table 1, detecting and recording the mass concentration of silicon alkoxide monomer molecules in the reaction liquid and the mass concentration of silicon oil molecules with the polymerization degree not more than 10 when the 8 th stage is close to the end, wherein the mass concentration of the silicon alkoxide monomer molecules in the reaction liquid is 74.8% at the moment, the mass concentration of the siloxane molecules with the polymerization degree not more than 10 is 91.2%, and the set final control target is reached, considering that the cracking reaction is sufficient, stopping supplementing the alcohol alkali liquor and stopping heating, detecting to obtain the mass concentration of free potassium ions in the reaction liquid at the moment, wherein the mass concentration of the residual free potassium ions is less than 0.6%, and the mass concentration of the residual free potassium ions is less than 0.90%, therefore, confirming that the cracking reaction is finished, entering a dilution extraction stage, and using the obtained dimethyl silicon alkoxide for preparing the organic silicon waterproof material.
TABLE 1 control Standard values and Process parameters for each stage of example 1
Figure DEST_PATH_IMAGE001
According to the data of example 1 recorded in the above table 1, 1752.2kg of alcohol lye is initially charged in the cracking reaction of the hydroxyl-terminated polysiloxane with an average molecular weight of 110000 and the alcohol lye, and after about 400min of cracking reaction, 840kg of alcohol lye is supplemented in the period, 2592.2kg of alcohol lye is charged in total, 593.7kg of the alcohol lye is used less than 3185.9kg of the total amount of the required alcohol lye, and the mass concentration of the silicon alkoxide monomer molecules in the final reaction liquid is 74.8%, the mass concentration of the siloxane molecules with a polymerization degree of not more than 10 is 91.2%, and the mass concentration of the free potassium ions is 0.6%.
Example 2
Hydroxyl-terminated polysiloxane with the average molecular weight of 110000 to be subjected to cracking treatment, wherein an alcohol alkali liquor is a mixed liquor of potassium ethoxide and butanol, the final control target for judging the full cracking reaction is set to be that the mass concentration of silicon alkoxide monomer molecules is not less than 65%, the mass concentration of siloxane molecules with the polymerization degree of not more than 10 is not less than 85%, the mass concentration of residual free potassium ions is less than 0.90%, and the corresponding control method of the input amount of the alcohol alkali liquor of the cracking reaction comprises the following specific steps:
s0) preparing an alcohol alkali solution in advance: respectively adding potassium hydroxide, ethanol and butanol into an ultrasonic mixer, stirring and mixing for 1h, then heating to 85 ℃, stirring and preserving heat for 1.5h, and separating water generated by reaction to obtain the alcohol alkali liquor; wherein the mass ratio of the ethanol to the butanol is 1:3, and the mass ratio of the mass of the potassium hydroxide to the total mass of the ethanol and the butanol is 3; the frequency of the ultrasonic wave is 22kHz, and the stirring speed is 85r/min.
S1) dividing the cracking reaction progress into 8 stages according to the viscosity curve of the cracking reaction of the hydroxyl-terminated polysiloxane at 80 ℃ shown in figure 1 and the transmittance curve shown in figure 2 according to the time schedule, setting the viscosity standard value and the transmittance standard value of each stage as listed in table 2, defining the difference between the viscosity detection value near the end of any stage and the viscosity standard value corresponding to the stage as the viscosity difference, and defining the difference between the transmittance detection value near the end of any stage and the transmittance standard value corresponding to the stage as the transmittance difference;
s2) 500kg of hydroxyl-terminated polysiloxane with the average molecular weight of 110000 to be cracked, and the theoretical value of the total amount of alcohol alkali liquor required by equivalent calculation of the cracking reaction is 3185.9kg;
s3) putting 500kg of hydroxyl-terminated polysiloxane to be cracked into a reaction kettle, putting 1752.2kg of alcohol alkali liquor accounting for 55% of the total mass of the alcohol alkali liquor, heating to 80 ℃ to start the cracking reaction, and maintaining the temperature of reaction liquid at 80 +/-2 ℃ to keep the cracking reaction continuously;
s4) detecting the instant viscosity and transmittance of the reaction liquid when the reaction liquid is carried out for 120min in the stage 1, and calculating to obtain a corresponding viscosity difference value and transmittance difference value, wherein the obtained viscosity difference value and transmittance difference value are listed in a table 2, if the viscosity difference value and the transmittance difference value are both larger than zero, the reaction liquid in the stage is supplemented with the alcohol alkali liquid, and the calculation formula of the supplement amount A of the alcohol alkali liquid is as follows: (X1-X0)/X0X, wherein X1 is a viscosity detection value near the end of the reaction stage, X0 is a viscosity standard value corresponding to the stage, and Y is a difference value obtained by subtracting the added and supplemented alcohol lye from a theoretical value of the total amount of the alcohol lye; if the viscosity difference is greater than zero and the transmittance difference is less than zero, the amount of the alcohol alkali solution added is too large, the replenishment amount A of the alcohol alkali solution in the reaction solution at the stage needs to be corrected, and the calculation formula of the corresponding replenishment amount A of the alcohol alkali solution is as follows: (X1-X0)/X0Y + (Z0-Z1)/Z0Y, wherein X1 is a viscosity detection value near the end of the reaction stage, X0 is a viscosity standard value corresponding to the stage, Z1 is a transmittance detection value near the end of the reaction stage, Z0 is a transmittance standard value corresponding to the stage, and Y is a difference value obtained by subtracting the fed and supplemented alcohol alkali liquor from a theoretical value of the total amount of the alcohol alkali liquor; if the viscosity difference is not greater than zero, directly entering the next stage;
s5) repeating the step S4), sequentially completing the 2 nd to the 8 th stages, wherein the alcohol alkali liquor supplementation amount A of each stage is listed in a table 2, detecting and recording the mass concentration of silicon alkoxide monomer molecules in the reaction liquid and the mass concentration of silicon oil molecules with the polymerization degree not more than 10 when the 8 th stage is close to the end, wherein the mass concentration of the silicon alkoxide monomer molecules in the reaction liquid is 75.4% at the moment, the mass concentration of siloxane molecules with the polymerization degree not more than 10 is 90.9%, the set final control target is reached, considering that the cracking reaction is sufficient, stopping supplementing the alcohol alkali liquor and stopping heating, detecting to obtain the mass concentration of free potassium ions in the reaction liquid at the moment, wherein the mass concentration of the residual free potassium ions is less than 0.5%, and the mass concentration of the residual free potassium ions is less than 0.90%, and therefore, confirming that the cracking reaction is finished, entering a dilution extraction stage, and using the obtained dimethyl silicon alkoxide for preparing the organic silicon waterproof material.
Table 2 control standard values and process parameters corresponding to each stage of example 2
Figure 879162DEST_PATH_IMAGE002
As can be seen from the data of example 2 recorded in Table 2 above, the methylsiliconate used in example 2 and the silicone oil and alcohol lye charged in the initial stage are the same as those in example 1, and after about 400min of cracking reaction, the amount of alcohol lye charged in the course of time is 842.9kg, and the total amount of alcohol lye charged is 2595.1kg, which is different from example 1 in that 590.8kg of alcohol lye is less than 3185.9kg of the theoretical amount of alcohol lye required: example 2 when each stage of the reaction is near to the end, the viscosity and the transmittance are simultaneously detected, the viscosity difference and the transmittance difference are calculated, the transmittance difference finds that the added alcohol lye is excessive in 1-3 stages, and the calculated value of the formula (Z0-Z1)/Z0Y is used for correcting the alcohol lye supplement amount A in 2-4 stages, and the finally obtained reaction product can meet the technical requirements, the total alcohol lye supplement amount in example 2 during the stages 1-8 is 842.9kg, and the total alcohol lye supplement amount in example 1 during the stages 1-8 is 840kg, which shows that the method for correcting the excessive alcohol lye supplement amount A by referring to the transmittance difference is effective.
The viscosity curve shown in FIG. 1 and the transmittance curve shown in FIG. 2 are empirical curves, and the relevant data are from the production record of the conventional single-shot cracking reaction of alcohol lye.
The chemical reaction formula for the cleavage reaction of the hydroxyl terminated polysiloxane of examples 1-2 in alcoholic solution of potassium ethoxide is as follows:
Figure 327461DEST_PATH_IMAGE004
wherein n represents the number of repeated linkages, and the main products obtained by cracking are potassium dimethylsilolate and oligomers thereof.
According to the method for controlling the input amount of the alcohol alkali liquor for silicone oil cracking, the purpose of actively adjusting the formula is achieved by controlling the supplement amount of the alcohol alkali liquor in stages according to the instantaneous state of a cracking reaction, the obtained final reaction product contains free potassium ions with the mass concentration of less than 0.90%, the mass concentration of silicon alkoxide monomer molecules is greater than 70%, the mass concentration of siloxane molecules with the polymerization degree of not greater than 10 is greater than 90%, and the prepared waterproof material has excellent reaction activity, good waterproof performance and wide application prospect.
In summary, in the illustrated embodiment of the present invention, the method for controlling the input amount of the alcohol alkali solution for silicone oil cracking detects the viscosity of the reaction solution in each reaction stage, obtains the corresponding viscosity difference value by comparing with the standard value, and controls the alcohol alkali solution supplement amount in the corresponding stage according to the obtained difference value, so as to control the alcohol alkali solution supplement amount and the total input amount of the whole cracking reaction, thereby avoiding the occurrence of excessive alkali metal ions or excessive macromolecular polymers in the final product of the cracking reaction, and finally achieving the purpose of improving the reactivity of the corresponding silicone oil cracking product and achieving excellent water resistance.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be taken in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive step, and these embodiments will fall within the scope of the present invention.

Claims (9)

1. A control method of the input amount of alcohol alkali liquor for silicone oil cracking is characterized by comprising the following steps:
s1) dividing the cracking reaction of the silicone oil in the alcohol alkali liquor into 8 to 12 stages according to the time schedule, setting the viscosity standard value of each stage, and defining the difference value between the viscosity detection value near the end of any stage and the viscosity standard value corresponding to the stage as the viscosity difference value;
s2) calculating the theoretical value of the total amount of the alcohol alkali liquor required by the cracking reaction in an equivalent manner according to the average molecular weight of the silicone oil to be cracked;
s3) putting all the silicon oil to be cracked into a reaction kettle, putting part of alcohol alkali liquor into the reaction kettle, starting the cracking reaction by raising the temperature to keep the temperature of the reaction liquid within a set required range, and then entering the stage 1;
s4) detecting the instant viscosity of the reaction liquid when the stage 1 is close to the end, and calculating to obtain a corresponding viscosity difference value, if the viscosity difference value is larger than zero, supplementing an alcohol alkali liquid into the reaction liquid in the stage, otherwise, directly entering the next stage;
and S5) repeating the step S4), sequentially completing the stages 2 to 12, detecting and recording the mass concentration of silicon alkoxide monomer molecules and the mass concentration of silicon oil molecules with the polymerization degree not greater than 10 in the reaction liquid when the stages 8 to 12 are nearly finished, and when the mass concentration of the silicon alkoxide monomer molecules and the mass concentration of the siloxane molecules with the polymerization degree not greater than 10 in the reaction liquid reach the set final control target, determining that the cracking reaction is sufficient, stopping adding the alcohol alkali liquor and heating, detecting and confirming that the mass concentration of free alkali metal ions is less than 0.90%, and finishing the cracking reaction.
2. The method for controlling the dosage of the alcohol lye for cracking silicone oil as claimed in claim 1, wherein in step S3), the initial dosage of the alcohol lye is 50-60% of the theoretical value of the total amount of the alcohol lye;
setting the final control target as: the mass concentration of the silicon alkoxide monomer molecules is not less than 60 percent, and the mass concentration of the siloxane molecules with the polymerization degree not more than 10 is not less than 85 percent;
the duration of stage 1 is 110-120min, and the duration of each stage from stage 2 to stage 12 is set to 40-45min.
3. The method for controlling the input amount of the alcohol alkali liquor for silicone oil cracking as claimed in claim 1, wherein in step S4), the formula for the supplement amount a of the alcohol alkali liquor is: (X1-X0)/X0X, wherein X1 is a stage viscosity detection value, X0 is a viscosity standard value, and Y is a difference value obtained by subtracting the added and supplemented alcohol lye from a theoretical value of the total amount of the alcohol lye.
4. The method for controlling the dosage of the alcohol lye for cracking silicone oil as claimed in claim 1 wherein step S1) further comprises the following steps: setting a transmittance standard value of each stage, and defining a difference value between the transmittance standard value of any stage and a transmittance detection value near the end of the stage as a transmittance difference value;
accordingly, step S4) is adjusted to: detecting the instant viscosity and transmittance of the reaction liquid when the stage 1 is close to the end, and calculating to obtain a corresponding viscosity difference value and transmittance difference value, if the viscosity difference value and the transmittance difference value are both larger than zero, supplementing the alcohol alkali liquid into the reaction liquid in the stage, wherein the supplement amount A of the alcohol alkali liquid has the calculation formula: (X1-X0)/X0X, wherein X1 is a viscosity detection value near the end of the stage, X0 is a viscosity standard value corresponding to the stage, and Y is a difference value obtained by subtracting the added and supplemented alcohol lye from a theoretical value of the total amount of the alcohol lye; if the viscosity difference is greater than zero and the transmittance difference is less than zero, the amount of the alcohol alkali solution added is too large, the replenishment amount A of the alcohol alkali solution in the reaction solution at the stage needs to be corrected, and the calculation formula of the corresponding replenishment amount A of the alcohol alkali solution is as follows: (X1-X0)/X0Y + (Z0-Z1)/Z0Y, wherein X1 is a viscosity detection value near the end of the stage, X0 is a viscosity standard value corresponding to the stage, Z1 is a transmittance detection value near the end of the stage, Z0 is a transmittance standard value corresponding to the stage, and Y is a difference value obtained by subtracting the fed and supplemented alcohol alkali liquor from a theoretical value of the total amount of the alcohol alkali liquor; if the viscosity difference is not more than zero, directly entering the next stage.
5. The method for controlling the dosage of the alcohol lye for cracking silicon oil as claimed in claim 1 wherein, in step S3), the test items of the reaction solution further include density test, the average value of the density values of the reaction solution obtained by the test from stage 1 to stage 12 is kept constant, and the fluctuation width of the density values is gradually narrowed and stabilized.
6. The method for controlling the input amount of the alcohol lye for cracking silicone oil according to claim 1 wherein the reaction temperatures of the 1 st to 12 th stages are all 80 ± 2 ℃; the viscosities of stages 1 to 12 are decreased in order, and the stirring speed of the reaction solution is decreased correspondingly in stages 3 to 12.
7. The method for controlling the dosage of the alcohol lye used for silicone oil cracking of claim 1 wherein the alcohol lye comprises fatty alcohol and alcohol alkali, the fatty alcohol is formed by mixing butanol and ethanol, the alcohol alkali is formed by the reaction of the inorganic alkali which is potassium hydroxide or sodium hydroxide and ethanol.
8. The method for controlling the input amount of the alcohol alkali liquor for silicone oil cracking as claimed in claim 7, wherein the preparation steps of the alcohol alkali liquor are as follows:
respectively adding inorganic base, ethanol and butanol into an ultrasonic mixer, stirring and mixing for 0.5-2h, then heating to 80-90 ℃, keeping the temperature and stirring for 1-3h, and continuously separating water generated by the reaction to obtain the alcohol alkali liquor;
the mass ratio of the inorganic base to the fatty alcohol is (1-3): (4-7); the mass ratio of ethanol to butanol in the fatty alcohol is (1-7): (4-13), the frequency of the ultrasonic wave is 20-24kHz, and the stirring speed is 80-85r/min.
9. The waterproof material obtained by the method for controlling the input amount of the alcohol lye for silicone oil splitting according to any one of claims 1 to 8 wherein the methylsiliconate used is obtained by the method for controlling the input amount of the alcohol lye for silicone oil splitting and contains free alkali metal ions at a mass concentration of 0.2% to 0.9% and siloxane molecules having a degree of polymerization of more than 10 at a mass concentration of 5% to 15%.
CN202210782700.5A 2022-07-05 2022-07-05 Method for controlling input amount of alcohol alkali liquor for silicone oil cracking and product thereof Active CN115041102B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210782700.5A CN115041102B (en) 2022-07-05 2022-07-05 Method for controlling input amount of alcohol alkali liquor for silicone oil cracking and product thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210782700.5A CN115041102B (en) 2022-07-05 2022-07-05 Method for controlling input amount of alcohol alkali liquor for silicone oil cracking and product thereof

Publications (2)

Publication Number Publication Date
CN115041102A CN115041102A (en) 2022-09-13
CN115041102B true CN115041102B (en) 2022-12-27

Family

ID=83164702

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210782700.5A Active CN115041102B (en) 2022-07-05 2022-07-05 Method for controlling input amount of alcohol alkali liquor for silicone oil cracking and product thereof

Country Status (1)

Country Link
CN (1) CN115041102B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103204992B (en) * 2013-02-19 2014-12-24 浙江中天氟硅材料有限公司 Method for preparing low-viscosity high-boiling silicone oil from raw material of chlorosilane high boiling residue
CN103951693A (en) * 2014-05-16 2014-07-30 泸州北方化学工业有限公司 Method for monitoring cracking reaction of dimethyldichlorosilance hydrolyzates
CN109651426A (en) * 2018-12-29 2019-04-19 杭州帝景化工有限公司 A kind of synthesis technology of methyltrimethoxysilane high-boiling components production waterproofing agent
CN113461951B (en) * 2021-08-20 2022-08-05 厦门大学 Preparation method of low-oxygen high-purity polycarbosilane

Also Published As

Publication number Publication date
CN115041102A (en) 2022-09-13

Similar Documents

Publication Publication Date Title
CN103881398A (en) Method for improving water resistance of polyvinyl alcohol film by using poly(trimethylene carbonate) and poly(p-dioxanone)
CN103555120A (en) Polyacrylate grafted modified polyester water-based coating and preparation method thereof
CN103360561A (en) Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone
CN109575311A (en) A kind of preparation method of vinyl copolymer emulsion
CN115041102B (en) Method for controlling input amount of alcohol alkali liquor for silicone oil cracking and product thereof
CN104829838A (en) Preparation method of hydroxyl terminated polyfluorosiloxane
CN105949859B (en) A kind of powdery paints optical brightener and preparation method and application
CN102174139B (en) Method for preparing polytetrafluoroethylene resin for coating
CN107033272A (en) A kind of extraordinary hardware acrylic resin and preparation method thereof
CN112679721B (en) Preparation method of high-molecular-weight low-viscosity sorbitol-based polyether polyol and obtained polyether polyol
CN112708002B (en) Vinyl acetate-ethylene copolymer emulsion having excellent compatibility with cement at high temperature
CN111205799A (en) Production process of cardanol modified phenolic resin adhesive
JP7240660B2 (en) Hardening accelerator for rice cake dough and method for producing rice cake dough with reduced refrigeration time for hardening
CN107936255B (en) Method for continuously producing polyether amide
CN105153345A (en) Preparation method of PVDC emulsion for water-based environment-friendly tableware
CN105085786A (en) Preparation method of low-compression permanent-deformation carboxylic acrylate rubber
CN1166719C (en) Ether-ketone copolymer containing 1,5-naphthalene ring polyether and its synthesis
CN102443116A (en) Method for preparing polycarboxylic acid water reducing agent
CN112759693A (en) Single-component emulsion suitable for coating surface of PP (polypropylene) artificial synthetic paper and synthetic method thereof
CN106832309B (en) Modified polyvinyl acetate and preparation process thereof
CN115894792B (en) High-molecular emulsifier for high-charge-density AKD (alkyl ketene dimer) as well as preparation method and application thereof
CN105153348B (en) A kind of modified ethylene acetate acrylate copolymer emulsion of high-dissolvability and high glass transition temperature and preparation method thereof
CN110945032A (en) Controlled preparation of low molecular weight cellulose ethers
CN109021157A (en) A kind of chlorinated polyether resin of Narrow Molecular Weight Distribution and preparation method thereof
CS221813B2 (en) Method of preparation of water dispersions of the styrene copolymere of the acryl or methacryl acid and butyles her of the maleici acid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant