CN114213663A - Acrylate modified silicone oil and preparation method thereof - Google Patents
Acrylate modified silicone oil and preparation method thereof Download PDFInfo
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- CN114213663A CN114213663A CN202111655029.XA CN202111655029A CN114213663A CN 114213663 A CN114213663 A CN 114213663A CN 202111655029 A CN202111655029 A CN 202111655029A CN 114213663 A CN114213663 A CN 114213663A
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Abstract
The application relates to the field of modified silicone oil, and particularly discloses acrylate modified silicone oil and a preparation method thereof. The acrylate modified silicone oil is characterized by being prepared from the following raw materials in parts by weight under the action of a catalyst: 100-120 parts of hydrogen-containing silicone oil, 200 parts of allyl acrylate, 2-5 parts of polymerization inhibitor and 10-12 parts of chain transfer agent; wherein, the catalyst is rhodium catalyst. The preparation method comprises the following steps: s1: uniformly mixing allyl acrylate, a rhodium catalyst and a polymerization inhibitor in proportion, and cooling to 5-8 ℃ to obtain a mixed raw material; s2: adjusting the temperature of the hydrogen-containing silicone oil to 10-15 ℃ to obtain pretreated hydrogen-containing silicone oil; s3: mixing the pretreated hydrogen-containing silicone oil with the mixed raw material to perform hydrosilylation reaction; the step S1 and the step S2 are not in sequence. This application has the advantage that improves product quality.
Description
Technical Field
The application relates to the technical field of UV resin auxiliaries, in particular to acrylate modified silicone oil and a preparation method thereof.
Background
The acrylate modified silicone oil is also called as organosilicon modified acrylate, combines the advantages of organosilicon and acrylate, has the advantages of crosslinking, no migration and the like, and improves the performances of flowing, leveling, substrate wetting, degassing, smoothness, non-sticking, scratch resistance and the like. Can be used as an additive of a UV photocuring system, helps a photocuring coating to improve special properties such as smoothness, substrate wettability, anti-shrinkage cavity, scratch resistance, leveling property and the like, and occupies a very important position in the coating industry.
The common acrylate modified silicone oil is mainly prepared by the reaction of hydrogen-containing silicone oil and acrylate by a hydrosilylation method under the action of a catalyst.
However, the catalyst used in the hydrosilylation reaction which is commonly used at present is a platinum catalyst, and the hydrosilylation reaction carried out by utilizing the platinum catalyst is easy to generate cross linking, so that the self-polymerization phenomenon is generated, the synthesis difficulty of the acrylate modified silicone oil is higher, and the quality and the yield of the produced acrylate modified silicone oil product are lower.
In view of the above-mentioned related technologies, the inventors consider that the quality of the product prepared by the current preparation method of acrylate modified silicone oil is poor, and the preparation method still needs to be improved.
Disclosure of Invention
In order to improve the quality of the preparation of the acrylate modified silicone oil, the application provides the acrylate modified silicone oil and the preparation method thereof.
In a first aspect, the acrylate modified silicone oil provided by the application adopts the following technical scheme:
the acrylate modified silicone oil is prepared from the following raw materials in parts by weight under the action of a catalyst:
100 portions and 120 portions of hydrogen-containing silicone oil;
150-200 parts of allyl acrylate;
2-5 parts of a polymerization inhibitor;
10-12 parts of a chain transfer agent;
wherein, the catalyst is rhodium catalyst.
By adopting the technical scheme, when the hydrogen-containing silicone oil and the allyl acrylate react under the action of the rhodium catalyst chain transfer agent, the crosslinking phenomenon and the self-polymerization phenomenon in the reaction process can be improved, and the synthesis quality of the acrylate modified silicone oil is improved. The polymerization inhibitor and the chain transfer agent are added to effectively prevent the allyl acrylate from self-polymerization during the polymerization process. Therefore, when the hydrogen-containing silicone oil and the allyl acrylate react, the rhodium catalyst is used as the catalyst, and the chain transfer agent is added, so that the crosslinking phenomenon and the self-polymerization phenomenon of the reaction can be effectively reduced, the synthesis difficulty of the acrylate modified silicone oil is reduced, and the synthesis quality and the yield of the acrylate modified silicone oil are improved.
Preferably, the chain transfer agent is dodecyl mercaptan, and the hydrogen-containing silicone oil with active hydrogen mass fraction of 0.1-0.18% is selected as the hydrogen-containing silicone oil.
By adopting the technical scheme, the lower the mass fraction of active hydrogen in the hydrogen-containing silicone oil is, the easier the reaction is to control, and the higher the mass fraction of active hydrogen is, the gel agglomeration phenomenon can occur in the reaction process. Meanwhile, when the mass fraction of active hydrogen in the hydrogen-containing silicone oil is low, the smoothness of the coating can be improved when the hydrogen-containing silicone oil is used for coating composition, but the compatibility with the coating is poor, and the quality of the coating is influenced. Therefore, the mass fraction of the active hydrogen preferably adopted in the application is 0.1-0.18%, the influence is comprehensively considered, and the dodecanethiol is selected as the chain transfer agent to act together, so that the adverse effect caused by the excessively low mass fraction of the active hydrogen in the hydrogen-containing silicone oil is avoided as far as possible.
Preferably, the ratio of the using amount of the rhodium catalyst to the total mass of the hydrogen-containing silicone oil and the allyl acrylate is 200-300 mu g/g.
By adopting the technical scheme, the ratio of the dosage of the rhodium catalyst to the total mass of the hydrogen-containing silicone oil and the allyl acrylate is preferably 200-300 mu g/g, so that the occurrence of side reactions can be reduced, the reaction can be effectively controlled, and the use cost of the catalyst can be reduced.
In a second aspect, the application provides a preparation method of acrylate modified silicone oil, which adopts the following technical scheme:
a preparation method of acrylate modified silicone oil comprises the following steps:
s1: uniformly mixing allyl acrylate, a rhodium catalyst and a polymerization inhibitor in proportion, and cooling to 5-8 ℃ to obtain a mixed raw material;
s2: adjusting the temperature of the hydrogen-containing silicone oil to 10-15 ℃ to obtain pretreated hydrogen-containing silicone oil;
s3: mixing the pretreated hydrogen-containing silicone oil with the mixed raw material to perform hydrosilylation reaction;
the step S1 and the step S2 are not in sequence.
By adopting the technical scheme, when the acrylate modified silicone oil is prepared, firstly, the catalyst is cooled, so that the catalytic action of the catalyst on side reactions is reduced when the catalyst is added, the inducing effect on the hydrosilylation reaction between the allyl acrylate and the hydrogen-containing silicone oil is achieved, then, the temperature is raised, the phenomena such as self-polymerization, crosslinking and the like in the reaction process can be weakened, the side reactions are weakened, the hydrosilylation reaction between the allyl acrylate and the hydrogen-containing silicone oil is promoted, and the quality of the prepared acrylate modified silicone oil is improved.
Preferably, the specific steps in step S3 are:
a 1: mixing the pretreated hydrogen-containing silicone oil with the mixed raw material, heating to 30-45 ℃ at the speed of 1 +/-0.5 ℃/min after the temperature is stable, and carrying out heat preservation reaction for 2-3h to obtain a primary reaction mixed solution;
a 2: heating the temperature of the primary mixed reaction liquid to 60-70 ℃ at the heating rate of 2 +/-0.5 ℃/min, and carrying out heat preservation reaction for 1-2 h.
By adopting the technical scheme, when the hydrogen-containing silicone oil and the allyl acrylate are subjected to hydrosilylation, the temperature is firstly controlled to rise to 30-45 ℃ at the speed of 1 +/-0.5 ℃/min so as to further ensure the induction of the rhodium catalyst on the hydrosilylation reaction between the allyl acrylate and the hydrogen-containing silicone oil, reduce the side reaction phenomena of self-polymerization, crosslinking and the like, and then the temperature is raised at a higher rising speed so as to reach the most suitable reaction temperature, accelerate the hydrosilylation reaction between the allyl acrylate and the hydrogen-containing silicone oil and improve the production efficiency and the yield of the acrylate modified silicone oil.
Preferably, step S4 is further performed after step S3, and step S4 is:
introducing the product obtained in the step S3 into a thin film evaporator, a common vacuum separation system and a high-pressure vacuum separation system in sequence for low-temperature separation; the vacuum degree of the common vacuum separation system is-0.08 to-0.089 Mpa, and the vacuum degree of the high-pressure vacuum separation system is-0.1 to-0.119 Mpa.
By adopting the technical scheme, most of low molecular organic matters in the product obtained in the step S3 can be removed through the thin film evaporator and the common vacuum separation system, and then the low molecular is further removed through the high vacuum separation system, so that the content of the low molecular organic matters in the product is reduced to an extremely low level, and the quality of the acrylate modified silicone oil is improved.
Preferably, the product in step S3 is provided with a section of preheating device outside the pipeline leading into the thin film evaporator, the preheating device includes an accommodating shell sleeved outside the pipeline, water and a heat control sphere capable of expanding with heat and contracting with cold are filled in a cavity between the accommodating shell and the outer wall of the pipeline, a heater is further installed on the side wall of the accommodating shell, a pressure sensor is installed at the bottom of the accommodating shell along the length direction of the accommodating shell, when the heat control sphere is lower than the set temperature of the preheating device, the density of the heat control sphere is contracted to be greater than that of the water, and the pressure sensor is used for acquiring a pressure signal at the bottom of the accommodating shell and transmitting the pressure signal to the heater for heating.
By adopting the technical scheme, the preheating device can heat the material entering the thin film evaporator, so that the temperature of the material entering the thin film evaporator is higher, and the higher temperature can enable the material in the thin film evaporator to be subjected to low-temperature separation more quickly and efficiently.
Preferably, the heat control ball is a hollow rubber ball, the rubber ball is filled with ethanol and scrap iron, the volume of the ethanol is 0.6-0.8 of the volume of the inner cavity of the hollow rubber ball at room temperature, and the addition amount of the scrap iron meets the requirement that the density of the hollow rubber ball is more than 1g/cm at 95 ℃ after the hollow rubber ball is filled with the ethanol3。
Through adopting above-mentioned technical scheme, when preheating device's temperature was higher than the temperature of settlement in the ethanol in the hollow rubber ball, the ethanol gas can be owing to be heated and produce great steam pressure to make the hollow rubber ball inflation, cause the density reduction of hollow rubber ball, make hollow rubber ball and hold shell bottom separation, when pressure-sensitive inductor did not feel heat control ball, pressure sensor sends the heater signal, and the control heater is out of work. And when the temperature of the water in the holding shell is lower than the set temperature, the temperature of the hollow rubber ball can also be reduced through the heat transfer effect, so that the density of the hollow rubber ball is increased, the hollow rubber ball sinks to the bottom of the holding shell, and after the pressure sensor senses the pressure of the hollow rubber ball, the control heater works to heat the water in the holding shell. Therefore, the preheating temperature of the preheating device can be realized by the floating and sinking of the heat control ball, so that the preheating uniformity is realized, the temperature of the material entering the thin film evaporator is more stable, and the efficiency of the low-temperature removal process is higher.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, hydrogen-containing silicone oil and allyl acrylate are reacted under the action of a rhodium catalyst chain transfer agent, so that the crosslinking phenomenon and the self-polymerization phenomenon in the reaction process are improved, and the synthesis quality of the acrylate modified silicone oil is improved.
2. In the application, the catalyst is preferably added in a mode of firstly cooling and then heating, so that the side reaction is weakened, the hydrosilylation reaction between allyl acrylate and hydrogen-containing silicone oil is promoted, and the quality of the prepared acrylate modified silicone oil is improved.
3. In the application, the product is firstly subjected to film evaporator and common vacuum separation, and then the low molecules are further removed by a high vacuum separation system, so that the content of the organic matters with low molecular weight in the product is reduced to an extremely low level, and the quality of the acrylate modified silicone oil is improved.
Drawings
FIG. 1 is a sectional view of a preheating apparatus in example 24 of this application.
Reference numerals: 1. a housing case; 2. a heat control sphere; 3. a resistance heater; 4. a pressure sensor.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
Raw materials
Examples
As shown in Table 1, examples 1 to 14 are different in the ratio of raw materials.
The following is illustrated by example 1:
the preparation method of the acrylic modified silicone oil provided in embodiment 1 includes the following steps:
s1: stirring allyl acrylate, a rhodium catalyst and a polymerization inhibitor in the proportion in a preparation tank at a stirring speed of 200r/min for 1h, and simultaneously cooling to 8 ℃ in the stirring process to obtain a mixed raw material;
s2: putting hydrogen-containing silicone oil into a charging tank, stirring at a stirring speed of 200r/min, and adjusting the temperature to 15 ℃ to obtain pretreated hydrogen-containing silicone oil;
s3: adding the pretreated hydrogen-containing silicone oil into the mixed raw materials, stirring the mixed solution at a stirring speed of 100r/min, heating to 70 ℃ after the temperature is stabilized, and continuing to perform heat preservation reaction for 2 hours;
step S1 and step S2 are not in order.
After the steps are carried out, the acrylic modified silicone oil can be obtained.
TABLE 1 acrylic acid modified silicone oil raw material ratio
Example 15
The difference from example 13 is that in the preparation of the acrylic-modified silicone oil, the temperature of the mixed raw materials was controlled to 7 ℃ and the temperature of the hydrogen-containing silicone oil was controlled to 14 ℃.
Example 16
The difference from example 13 is that in the preparation of the acrylic-modified silicone oil, the temperature of the mixed raw materials was controlled to 6 ℃ and the temperature of the hydrogen-containing silicone oil was controlled to 12 ℃.
Example 17
The difference from example 13 is that in the preparation of the acrylic-modified silicone oil, the temperature of the mixed raw materials was controlled to 5 ℃ and the temperature of the hydrogen-containing silicone oil was controlled to 10 ℃.
Example 18
The difference from embodiment 13 is that step S3 is:
a 1: stirring and mixing the pretreated hydrogen-containing silicone oil and the mixed raw material at a stirring speed of 100r/min, continuing stirring and heating the mixed solution to 30 ℃ at a speed of 1 +/-0.5 ℃/min after the temperature is stable, and carrying out heat preservation reaction for 2 hours to obtain a primary reaction mixed solution;
a 2: heating the preliminary mixed reaction liquid to 70 ℃ at the heating rate of 2 +/-0.5 ℃/min, and carrying out heat preservation reaction for 2 h.
Example 19
The difference from embodiment 13 is that step S3 is:
a 1: stirring and mixing the pretreated hydrogen-containing silicone oil and the mixed raw material at a stirring speed of 100r/min, continuing stirring and heating the mixed solution to 35 ℃ at a speed of 1 +/-0.5 ℃/min after the temperature is stable, and carrying out heat preservation reaction for 2 hours to obtain a primary reaction mixed solution;
a 2: heating the preliminary mixed reaction liquid to 65 ℃ at the heating rate of 2 +/-0.5 ℃/min, and carrying out heat preservation reaction for 2 h.
Example 20
The difference from embodiment 13 is that step S3 is:
a 1: stirring and mixing the pretreated hydrogen-containing silicone oil and the mixed raw material at a stirring speed of 100r/min, continuing stirring and heating the mixed solution to 40 ℃ at a speed of 1 +/-0.5 ℃/min after the temperature is stable, and carrying out heat preservation reaction for 2 hours to obtain a primary reaction mixed solution;
a 2: heating the preliminary mixed reaction liquid to 60 ℃ at the heating rate of 2 +/-0.5 ℃/min, and carrying out heat preservation reaction for 2 h.
Example 21
The difference from embodiment 13 is that step S3 is:
a 1: stirring and mixing the pretreated hydrogen-containing silicone oil and the mixed raw material at a stirring speed of 100r/min, continuing stirring and heating the mixed solution to 45 ℃ at a speed of 1 +/-0.5 ℃/min after the temperature is stable, and carrying out heat preservation reaction for 2 hours to obtain a primary reaction mixed solution;
a 2: heating the preliminary mixed reaction liquid to 60 ℃ at the heating rate of 2 +/-0.5 ℃/min, and carrying out heat preservation reaction for 2 h.
Example 22
The difference from embodiment 13 is that step S3 is:
a 1: stirring and mixing the pretreated hydrogen-containing silicone oil and the mixed raw material at a stirring speed of 100r/min, continuing stirring and heating the mixed solution to 45 ℃ at a speed of 1 +/-0.5 ℃/min after the temperature is stable, and carrying out heat preservation reaction for 1h to obtain a primary reaction mixed solution;
a 2: heating the preliminary mixed reaction liquid to 60 ℃ at the heating rate of 2 +/-0.5 ℃/min, and carrying out heat preservation reaction for 1 h.
Example 23
The difference from example 13 is that the method for producing an acrylic-modified silicone oil comprises the steps of:
s1: stirring allyl acrylate, a rhodium catalyst and a polymerization inhibitor in the proportion in a preparation tank at a stirring speed of 200r/min for 1h, and simultaneously cooling to 8 ℃ in the stirring process to obtain a mixed raw material;
s2: putting hydrogen-containing silicone oil into a charging tank, stirring at a stirring speed of 200r/min, and adjusting the temperature to 15 ℃ to obtain pretreated hydrogen-containing silicone oil;
s3: adding the pretreated hydrogen-containing silicone oil into the mixed raw materials, stirring the mixed solution at a stirring speed of 100r/min, heating to 70 ℃ after the temperature is stabilized, and continuing to perform heat preservation reaction for 2 hours;
s4: the product obtained in the step S3 is sequentially introduced into a film evaporator, a common vacuum separation system and a high-pressure vacuum separation system for low-temperature separation; controlling the evaporation temperature of the thin film evaporator to be 130 ℃, controlling the temperature of the common vacuum separation system and the high-pressure vacuum separation system to be 160 ℃,
the vacuum degree of the common vacuum separation system is-0.08 Mpa, and the vacuum degree of the high-pressure vacuum separation system is-0.1 Mpa.
Step S1 and step S2 are not in order.
Example 24
The difference from example 23 is that the degree of vacuum of the ordinary vacuum separation system was-0.085 MPa, and that of the high-pressure vacuum separation system was-0.109 MPa.
Example 25
The difference from example 23 is that the degree of vacuum of the ordinary vacuum separation system was-0.089 MPa, and that of the high-pressure vacuum separation system was-0.119 MPa.
Example 26
The difference from example 23 is that, referring to FIG. 1, the product in step S3 was provided with a preheating device having a length of 5m around the tube leading to the thin film evaporator.
The preheating device comprises a containing shell 1 which is sleeved outside the pipeline along the length direction of the pipeline, and a cavity for filling water is formed between the containing shell 1 and the outer wall of the pipeline. The cavity is filled with water and a heat control sphere 2 which can expand with heat and contract with cold.
The heat control sphere 2 is a hollow rubber sphere, the rubber sphere is filled with ethanol and scrap iron, the volume of the added ethanol is 0.8 times of the volume of the inner cavity of the hollow rubber sphere at room temperature, and the addition amount of the scrap iron meets the requirement that the density of the hollow rubber sphere is more than 1g/cm3 at 95 ℃ after the hollow rubber sphere is filled with the ethanol.
The side wall of the accommodating shell 1 is provided with a resistance heater 3, and the bottom of the accommodating shell 1 is provided with a strip-shaped pressure sensor 4 along the length direction of the accommodating shell 1.
When the water temperature is lower than 95 ℃, the heat control sphere 2 conducts heat so that the temperature inside the heat control sphere 2 is lower than 95 ℃, the ethanol gas in the heat control sphere 2 is cooled and shrunk until the density of the heat control sphere 2 is higher than that of water, the heat control sphere 2 falls onto the pressure sensor 4, and the pressure sensor 4 obtains a pressure signal and then transmits the pressure signal to the electric heater for heating.
When the water temperature is higher than 95 ℃, the temperature inside the heat control sphere 2 is raised to 95 ℃ through heat transfer of the heat control sphere 2, the ethanol gas in the heat control sphere 2 is heated and expanded until the density of the heat control sphere 2 is smaller than that of water, the heat control sphere 2 is suspended away from the pressure sensor 4, and after the pressure sensor 4 senses that the pressure disappears, the pressure sensor transmits a signal to the electric heater to stop heating.
Comparative example
Comparative example 1
The difference from example 1 is that a platinum catalyst is used as the catalyst.
Comparative example 2
The difference from example 1 is that no polymerization inhibitor and no chain transfer agent were added to the raw materials of the acrylate-modified silicone oil.
Comparative example 3
The difference from example 1 is that no chain transfer agent is added to the raw material of the acrylate-modified silicone oil.
Comparative example 4
The difference from example 1 is that no polymerization inhibitor is added to the raw material of the acrylate-modified silicone oil.
Performance test
Preparing a sample: the products of each example and comparative example were taken at 200g in a beaker and were labeled as samples 1-30(1-26 for examples 1-26 and 27-30 for comparative examples 1-4), respectively.
A detection step: adding 30% by mass of alcoholic potassium hydroxide solution into each beaker, observing and recording the intensity and time of bubbles generated in the liquid in the beaker, and sequentially classifying the bubble generation intensity into 0-10 grades from bubble-free generation to the state that the bubbles tend to boil according to all experimental results.
TABLE 2 examples to determine the completeness of the reaction
And (4) conclusion: as can be seen from the comparison of examples 1-26 with comparative example 1, the rhodium catalyst is used as the catalyst, and under the experimental conditions of the present application, i.e., lower reaction temperature and shorter reaction time, the reaction is more complete, the amount of the raw materials which are not completely reacted in the product is less, and the product quality is higher. Compared with comparative examples 2, 3 and 4, the chain transfer agent and the polymerization inhibitor have fewer raw materials which are not completely reacted in the product when used together, and the chain transfer agent and the polymerization inhibitor have more raw materials which are not completely reacted in the product when used separately, which shows that the polymerization inhibitor and the chain transfer agent have better effect when used together in the application.
According to the comparison between example 5 and examples 6-10, the mass fraction of active hydrogen in the hydrogen-containing silicone oil also has a certain influence on the completeness of the reaction of the raw materials in the product, and when the mass fraction of active hydrogen in the hydrogen-containing silicone oil is between 0.1 and 0.18 percent, the reaction is more complete, and when the mass fraction of active hydrogen is 0.18 percent, the optimal reaction is achieved.
According to the comparison between example 10 and examples 11-14, the amount of the catalyst has a certain influence on the reaction completeness of the raw materials in the product, and when the mass fraction of active hydrogen in the hydrogen-containing silicone oil is between 0.1 and 0.18 percent, the reaction is more complete, and when the mass fraction of active hydrogen is 0.18 percent, the optimal reaction is achieved.
As is clear from comparison of the data in example 13 with those in examples 15 to 22, in the production of an acrylic modified silicone oil by mixing the starting materials and the catalyst at a low temperature and then gradually increasing the temperature, the amount of unreacted starting materials and the amount of side reactions in the product can be reduced.
As is clear from comparison of the data of example 22, examples 23 to 25 and example 26, in the production of an acrylate-modified silicone oil, step S4 was effective in removing low molecular weight substances which have reacted, whereas example 26, in which the preheating device was added, had a higher removal rate of low molecular weight substances and had almost no unreacted raw material remaining in the product.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The acrylate modified silicone oil is characterized by being prepared from the following raw materials in parts by weight under the action of a catalyst:
100 portions and 120 portions of hydrogen-containing silicone oil;
150-200 parts of allyl acrylate;
2-5 parts of a polymerization inhibitor;
10-12 parts of a chain transfer agent;
wherein, the catalyst is rhodium catalyst.
2. The acrylate-modified silicone oil according to claim 1, wherein: the chain transfer agent adopts dodecyl mercaptan, and the hydrogen-containing silicone oil with active hydrogen mass fraction of 0.1-0.18% is selected as the hydrogen-containing silicone oil.
3. The acrylate-modified silicone oil according to claim 1, wherein: the ratio of the dosage of the rhodium catalyst to the total mass of the hydrogen-containing silicone oil and the allyl acrylate is 200-300 mu g/g.
4. A method for producing the acrylate-modified silicone oil according to any one of claims 1 to 3, comprising the steps of:
s1: uniformly mixing allyl acrylate, a rhodium catalyst and a polymerization inhibitor in proportion, and cooling to 5-8 ℃ to obtain a mixed raw material;
s2: adjusting the temperature of the hydrogen-containing silicone oil to 10-15 ℃ to obtain pretreated hydrogen-containing silicone oil;
s3: mixing the pretreated hydrogen-containing silicone oil with the mixed raw material to perform hydrosilylation reaction;
the step S1 and the step S2 are not in sequence.
5. The method for preparing an acrylate-modified silicone oil according to claim 4, wherein: the specific steps in step S3 are:
a 1: mixing the pretreated hydrogen-containing silicone oil with the mixed raw material, heating to 30-45 ℃ at the speed of 1 +/-0.5 ℃/min after the temperature is stable, and carrying out heat preservation reaction for 2-3h to obtain a primary reaction mixed solution;
a 2: heating the temperature of the primary mixed reaction liquid to 60-70 ℃ at the heating rate of 2 +/-0.5 ℃/min, and carrying out heat preservation reaction for 1-2 h.
6. The method for preparing an acrylate-modified silicone oil according to claim 4, wherein: step S4 is further performed after step S3, where step S4 is:
introducing the product obtained in the step S3 into a thin film evaporator, a common vacuum separation system and a high-pressure vacuum separation system in sequence for low-temperature separation; the vacuum degree of the common vacuum separation system is-0.08 to-0.089 Mpa, and the vacuum degree of the high-pressure vacuum separation system is-0.1 to-0.119 Mpa.
7. The method for preparing an acrylate-modified silicone oil according to claim 6, wherein: the product in step S3 is equipped with one section preheating device at the pipeline overcoat that lets in the film evaporator, preheating device is including the cover shell (1) that holds outside locating the pipeline, hold cavity intussuseption between shell (1) and the pipeline outer wall and fill water and heat control spheroid (2) that can expand with heat and contract with cold, still install the heater on the lateral wall of holding shell (1), hold the bottom of shell (1) and install pressure-sensitive transducer (4) along the length direction who holds shell (1), when heat control spheroid (2) are less than preheating device settlement temperature, heat control spheroid (2) shrink to the density that heat control spheroid (2) are greater than the density of water, pressure-sensitive transducer (4) are used for acquireing the pressure signal who holds shell (1) bottom and give pressure signal the heater heats.
8. The method for preparing an acrylate-modified silicone oil according to claim 7, wherein: the heat control sphere (2) is a hollow rubber sphere, the rubber sphere is filled with ethanol and scrap iron, the volume of the added ethanol is 0.6-0.8 of the volume of the inner cavity of the hollow rubber sphere at room temperature, and the addition amount of the scrap iron meets the requirement that the density of the hollow rubber sphere is more than 1g/cm at 95 ℃ after the hollow rubber sphere is filled with ethanol3。
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| CN115322740A (en) * | 2022-08-26 | 2022-11-11 | 昆山石梅新材料科技有限公司 | Ultraviolet light curing pressure-sensitive adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1503823A (en) * | 2001-04-19 | 2004-06-09 | 钟渊化学工业株式会社 | Thermoplastic resin composition |
| WO2007023669A1 (en) * | 2005-08-25 | 2007-03-01 | Toagosei Co., Ltd. | Curable resin compositions |
| CN103642045A (en) * | 2013-11-21 | 2014-03-19 | 宜昌科林硅材料有限公司 | Efficient low molecule removal method for low viscosity silicone oil |
| CN113563589A (en) * | 2021-08-17 | 2021-10-29 | 烟台顺明新材料有限公司 | Application of rhodium catalyst in organosilicon addition reaction |
-
2021
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1503823A (en) * | 2001-04-19 | 2004-06-09 | 钟渊化学工业株式会社 | Thermoplastic resin composition |
| WO2007023669A1 (en) * | 2005-08-25 | 2007-03-01 | Toagosei Co., Ltd. | Curable resin compositions |
| CN103642045A (en) * | 2013-11-21 | 2014-03-19 | 宜昌科林硅材料有限公司 | Efficient low molecule removal method for low viscosity silicone oil |
| CN113563589A (en) * | 2021-08-17 | 2021-10-29 | 烟台顺明新材料有限公司 | Application of rhodium catalyst in organosilicon addition reaction |
Non-Patent Citations (3)
| Title |
|---|
| 尤小姿等: ""UV固化丙烯酸酯改性硅油的合成及性能"", 《有机硅材料》 * |
| 张新平等: "《工程材料及热成形技术》", 31 December 2011, 北京：国防工业出版社 * |
| 胡学贵主编: "《高分子化学及工艺学》", 31 May 1991, 北京：化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115322740A (en) * | 2022-08-26 | 2022-11-11 | 昆山石梅新材料科技有限公司 | Ultraviolet light curing pressure-sensitive adhesive and preparation method thereof |
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| CN114213663B (en) | 2022-11-01 |
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