CN111978543A - Propyl phenyl silicone resin and preparation method thereof - Google Patents
Propyl phenyl silicone resin and preparation method thereof Download PDFInfo
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- CN111978543A CN111978543A CN202010910406.9A CN202010910406A CN111978543A CN 111978543 A CN111978543 A CN 111978543A CN 202010910406 A CN202010910406 A CN 202010910406A CN 111978543 A CN111978543 A CN 111978543A
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Abstract
The invention discloses propyl phenyl silicone resin and a preparation method thereof, relating to the technical field of silicone resin and comprising the following steps: s1, adding saturated Na into the high boiling point substance of propyltriethoxysilane2CO3Stirring the solution, and adjusting the pH value to 3-5; s2, adding phenyltriethoxysilane into propyltriethoxysilane high-boiling residues; s3, adding a catalyst solution while stirring, heating to 85-105 ℃, and refluxing for 3-5 h; s4, adding hexamethyldisilazane, distilling at a constant temperature of 100-105 ℃, and then heating to 110-120 ℃ for reflux curing for 5-20 min; s5, adding KOH, increasing the stirring speed, and refluxing for 2-5 h at 110-120 ℃; s6, filtering, washing with water, washing with alcohol and drying to obtain propyl phenyl silicone resin micro powder. The invention has the advantages that the by-product is converted into the silicone resin with important utilization value, the conversion rate is high, and the propylbenzene is preparedThe silicon resin micro powder has uniform grain diameter and no agglomeration.
Description
Technical Field
The invention relates to the technical field of silicone resin, in particular to propyl phenyl silicone resin and a preparation method thereof.
Background
With the rapid development of the world organic silicon industry, the demand for the organic silicon coupling agent is increasing, the byproduct, namely high-boiling-point substances, generated in the synthesis process of the organic silicon coupling agent such as propyltriethoxysilane is increasing, the commercial value of the high-boiling-point substances is low all the time, and a large amount of high-boiling-point substances are accumulated to block a warehouse, so that the serious environmental protection problem and the safety problem are caused, and effective resources are wasted greatly, so that the utilization of the high-boiling-point substances becomes a serious obstacle for restricting the further development of the organic silicon industry.
The silicone resin is a thermosetting polysiloxane system with a high crosslinking structure, and has an organic-inorganic hybrid structure because the main chain of the silicone resin is a Si-O-Si bond and an organic group is connected to a Si atom. According to the kind of organic group bonded to the Si atom, there are classified into methyl silicone resin and phenyl silicone resin. The phenyl silicone resin has been widely paid attention to because phenyl silicone chain links are introduced, so that the thermal elasticity, mechanical property, adhesion, gloss and compatibility with organic matters and inorganic fillers are greatly improved.
Phenyl propyl silicone resin in phenyl silicone resin has important utilization value in the fields of flame retardants, coatings, cosmetics and the like, and phenyl trichlorosilane and propyl trichlorosilane are subjected to cohydrolysis and polycondensation to prepare solid phenyl propyl silicone resin powder with good toluene solubility in the prior art.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides propyl phenyl silicone resin and a preparation method thereof.
The technical solution of the invention is as follows:
the invention provides a propyl phenyl silicone resin, which comprises raw materials of propyl triethoxysilane high-boiling residues, phenyl triethoxysilane and hexamethyldisilazane.
The second aspect of the invention provides a preparation method of propyl phenyl silicone resin, which comprises the following steps:
s1 HomopropyltriethoxyAdding saturated Na into silane high-boiling residue2CO3Stirring the solution, and adjusting the pH value of the system to 3-5;
s2, adding phenyltriethoxysilane into the propyltriethoxysilane high-boiling-point substance treated in the step S1 under stirring, and continuing stirring and uniformly mixing after the addition is finished to obtain a mixed material;
s3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 85-105 ℃, and carrying out reflux reaction for 3-5 hours;
s4, adding hexamethyldisilazane into the material reacted in the step S3, stirring, distilling at a constant temperature of 100-105 ℃, and then heating to 110-120 ℃ for reflux curing for 5-20 min;
s5, adding KOH into the cured material obtained in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction at 110-120 ℃ for 2-5 hours to obtain powdered propyl phenyl silicone resin;
s6, filtering, washing with water, washing with alcohol and drying the powdered propyl phenyl silicone resin in the step S5 to obtain the propyl phenyl silicone resin micro powder which is free of agglomeration and uniform in particle size.
Preferably, in step S1, Na is saturated2CO3The volume ratio of the solution to the propyl triethoxysilane high-boiling residues is 1-4: 100.
Preferably, in the step S2, the addition amount of the phenyltriethoxysilane is 15-35 wt% of the propyltriethoxysilane.
Preferably, in step S3, the catalyst solution is an aqueous solution prepared from one or more of hydrochloric acid, acetic acid, vanadium pentoxide, and tetraisopropyl zirconia, and the concentration of the catalyst solution is 2-5 μ g/L.
Preferably, in the step S3, the addition amount of the catalyst solution is 30-45 wt% of the mixed material.
Preferably, in the step S4, the amount of hexamethyldisilazane added is 0.01-0.05 wt% of the mixture.
Preferably, in the step S5, the addition amount of KOH is 0.01 to 0.05 wt% of the mixture.
Preferably, the particle size of the propylphenyl silicone resin micropowder prepared in step S6 is 0.5-5 μm.
The invention has at least one of the following beneficial effects:
according to the invention, a propyl triethoxysilane high-boiling residue as a byproduct of an organic silicon coupling agent is used as a raw material, phenyl triethoxysilane and the like are added for hydrolysis and polycondensation, so that propyl phenyl silicone resin micro powder with uniform particle size and no agglomeration is prepared, the particle size of the prepared propyl phenyl silicone resin micro powder is 0.5-5 mu m, the yield is 85-90%, the method not only converts the byproducts causing potential safety hazards and environmental hazards into silicone resin with important utilization value in the fields of flame retardants, coatings and the like, but also is mild and controllable, and the yield is high and beneficial to industrial production.
Detailed Description
The following "propyltriethoxysilane high-boiling substance" is a high-boiling substance obtained in the synthesis process of propyltriethoxysilane.
The "propyltriethoxysilane high boilers" in the following examples and comparative examples are the same batch of high boilers produced during the synthesis of propyltriethoxysilane.
The invention provides propyl phenyl silicone resin which takes propyl triethoxy silane high-boiling residue, phenyl triethoxy silane and hexamethyl disilazane as reaction raw materials.
Specifically, the preparation method of the propylphenyl silicone resin comprises the following steps:
s1, placing the propyltriethoxysilane high-boiling residue in the tower kettle, adding saturated Na2CO3Stirring for a moment, neutralizing excessive hydrochloric acid, and adjusting the pH value of the system to 3-5; wherein, saturated Na2CO3The volume ratio of the solution to the propyl triethoxysilane high-boiling residues is 1-4: 100.
S2, adding phenyltriethoxysilane into the propyltriethoxysilane high-boiling-point substance treated in the step S1 under stirring, and continuing stirring for 15-30 min after the addition is completed to uniformly mix to obtain a mixed material; wherein the addition amount of the phenyltriethoxysilane is 15-35 wt% of the propyltriethoxysilane high-boiling components.
S3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 85-105 ℃, and carrying out reflux reaction for 3-5 hours; wherein the catalyst solution is an aqueous solution prepared from one or more of hydrochloric acid, acetic acid, vanadium pentoxide and tetraisopropyl zirconia, the concentration of the catalyst solution is 2-5 mu g/L, and the addition amount of the catalyst solution is 30-45 wt% of the mixed material.
S4, adding hexamethyldisilazane into the material reacted in the step S3, stirring for a moment, distilling at constant temperature of 100-105 ℃, and then heating to 110-120 ℃ for reflux curing for 5-20 min; wherein the addition amount of the hexamethyldisilazane is 0.01-0.05 wt% of the mixed material.
S5, adding KOH into the material ripened in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction at 110-120 ℃ for 2-5 h to obtain powdered propyl phenyl silicone resin; wherein the addition amount of KOH is 0.01-0.05 wt% of the mixed material.
S6, filtering, washing with water, washing with methanol and drying the powdered propyl phenyl silicone resin obtained in the step S5 to obtain propyl phenyl silicone resin micro powder which is free of agglomeration and uniform in particle size, wherein the particle size of the propyl phenyl silicone resin micro powder is 0.5-5 microns.
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
S1, placing the propyltriethoxysilane high-boiling residue in the tower kettle, adding saturated Na2CO3Stirring for a moment, neutralizing excessive hydrochloric acid, and adjusting the pH value of the system to 3-5; wherein, saturated Na2CO3The volume ratio of the solution to the propyltriethoxysilane high-boiling substance is 1: 100.
S2, adding the phenyltriethoxysilane into the propyltriethoxysilane high-boiling-point substance treated in the step S1 under stirring, and continuing stirring for 15min after the addition is finished to uniformly mix to obtain a mixed material; wherein the addition amount of the phenyltriethoxysilane is 15 wt% of the propyltriethoxysilane high-boiling components.
S3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 85 ℃, and carrying out reflux reaction for 5 hours; wherein the catalyst solution is hydrochloric acid solution, the concentration of the catalyst solution is 5 mu g/L, and the addition amount of the catalyst solution is 30 wt% of the mixed material.
S4, adding hexamethyldisilazane into the material reacted in the step S3, stirring for a moment, distilling at constant temperature of 100 ℃, and then heating to 110 ℃ for reflux curing for 20 min; wherein the addition amount of hexamethyldisilazane is 0.01 wt% of the mixture.
S5, adding KOH into the material ripened in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction for 5 hours at 110 ℃ to obtain powdered propyl phenyl silicone resin; wherein, the addition amount of KOH is 0.01 percent of the weight of the mixed material.
S6, filtering, washing with water, washing with methanol and drying the powdered propyl phenyl silicone resin in the step S5 to obtain the propyl phenyl silicone resin micro powder which is free of agglomeration and uniform in particle size.
Example 2
S1, placing the propyltriethoxysilane high-boiling residue in the tower kettle, adding saturated Na2CO3Stirring for a moment, neutralizing excessive hydrochloric acid, and adjusting the pH value of the system to 3-5; wherein, saturated Na2CO3The volume ratio of the solution to the propyltriethoxysilane high-boiling substance is 2: 100.
S2, adding the phenyltriethoxysilane into the propyltriethoxysilane high-boiling-point substance treated in the step S1 under stirring, and continuing stirring for 20min after the addition is finished to uniformly mix to obtain a mixed material; wherein the addition amount of the phenyltriethoxysilane is 20 wt% of the high-boiling components of the propyltriethoxysilane.
S3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 90 ℃, and carrying out reflux reaction for 3.5 hours; wherein the catalyst solution is an aqueous solution prepared from vanadium pentoxide, the concentration of the catalyst solution is 4.5 mu g/L, and the adding amount of the catalyst solution is 35 wt% of the mixed material.
S4, adding hexamethyldisilazane into the material reacted in the step S3, stirring for a moment, distilling at a constant temperature of 101 ℃, and then heating to 112 ℃ for reflux curing for 18 min; wherein the addition amount of hexamethyldisilazane was 0.02 wt% of the mixture.
S5, adding KOH into the material ripened in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction at 112 ℃ for 4.5 hours to obtain powdered propyl phenyl silicone resin; wherein, the addition amount of KOH is 0.02 wt% of the mixed material.
S6, filtering, washing with water, washing with methanol and drying the powdered propyl phenyl silicone resin in the step S5 to obtain the propyl phenyl silicone resin micro powder which is free of agglomeration and uniform in particle size.
Example 3
S1, placing the propyltriethoxysilane high-boiling residue in the tower kettle, adding saturated Na2CO3Stirring for a moment, neutralizing excessive hydrochloric acid, and adjusting the pH value of the system to 3-5; wherein, saturated Na2CO3The volume ratio of the solution to the propyltriethoxysilane high-boiling substance is 2.5: 100.
S2, adding the phenyltriethoxysilane into the propyltriethoxysilane high-boiling-point substance treated in the step S1 under stirring, and continuing stirring for 22min after the addition is finished to uniformly mix to obtain a mixed material; wherein the addition amount of the phenyltriethoxysilane is 25 wt% of the propyltriethoxysilane high-boiling components.
S3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 95 ℃, and carrying out reflux reaction for 4 hours; wherein the catalyst solution is an aqueous solution prepared from acetic acid, the concentration of the catalyst solution is 4 mu g/L, and the addition amount of the catalyst solution is 38 wt% of the mixed material.
S4, adding hexamethyldisilazane into the material reacted in the step S3, stirring for a moment, distilling at a constant temperature of 103 ℃, and then heating to 115 ℃ for reflux curing for 15 min; wherein the addition amount of hexamethyldisilazane is 0.03 wt% of the mixture.
S5, adding KOH into the material ripened in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction for 4 hours at 115 ℃ to obtain powdered propyl phenyl silicone resin; wherein, the addition amount of KOH is 0.02 wt% of the mixed material.
S6, filtering, washing with water, washing with methanol and drying the powdered propyl phenyl silicone resin obtained in the step S5 to obtain propyl phenyl silicone resin micro powder which is free of agglomeration and uniform in particle size, wherein the particle size of the propyl phenyl silicone resin micro powder is 0.5-5 microns.
Example 4
S1, placing the propyltriethoxysilane high-boiling residue in the tower kettle, adding saturated Na2CO3Stirring for a moment, neutralizing excessive hydrochloric acid, and adjusting the pH value of the system to 3-5; wherein, saturated Na2CO3The volume ratio of the solution to the propyltriethoxysilane high-boiling substance is 3: 100.
S2, adding the phenyltriethoxysilane into the propyltriethoxysilane high-boiling-point substance treated in the step S1 under stirring, and continuing stirring for 25min after the addition is finished to uniformly mix to obtain a mixed material; wherein the addition amount of the phenyltriethoxysilane is 30 wt% of the propyltriethoxysilane high-boiling components.
S3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 100 ℃, and carrying out reflux reaction for 3.5 hours; wherein the catalyst solution is an aqueous solution prepared from tetraisopropyl zirconium oxide, the concentration of the catalyst solution is 3.5 mu g/L, and the addition amount of the catalyst solution is 40 wt% of the mixed material.
S4, adding hexamethyldisilazane into the material reacted in the step S3, stirring for a moment, distilling at a constant temperature of 104 ℃, and then heating to 118 ℃ for reflux curing for 10 min; wherein the addition amount of hexamethyldisilazane was 0.04 wt% of the mixture.
S5, adding KOH into the material ripened in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction at 118 ℃ for 3 hours to obtain powdered propyl phenyl silicone resin; wherein, the addition amount of KOH is 0.04 wt% of the mixed material.
S6, filtering, washing with water, washing with methanol and drying the powdered propyl phenyl silicone resin in the step S5 to obtain the propyl phenyl silicone resin micro powder which is free of agglomeration and uniform in particle size.
Example 5
S1, placing the propyltriethoxysilane high-boiling residue in the tower kettle, adding saturated Na2CO3Stirring for a moment, neutralizing excessive hydrochloric acid, and adjusting the pH value of the system to 3-5; wherein, saturated Na2CO3The volume ratio of the solution to the propyltriethoxysilane high-boiling substance is 4: 100.
S2, adding the phenyltriethoxysilane into the propyltriethoxysilane high-boiling-point substance treated in the step S1 under stirring, and continuing stirring for 30min after the addition is finished to uniformly mix to obtain a mixed material; wherein the addition amount of the phenyltriethoxysilane is 35 wt% of the propyltriethoxysilane high-boiling components.
S3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 105 ℃, and carrying out reflux reaction for 3 hours; wherein the catalyst solution is an aqueous solution prepared from hydrochloric acid and vanadium pentoxide, the mass ratio of the hydrochloric acid to the vanadium pentoxide is 1:1, the concentration of the catalyst solution is 3 mug/L, and the adding amount of the catalyst solution is 35 wt% of the mixed material.
S4, adding hexamethyldisilazane into the material reacted in the step S3, stirring for a moment, distilling at a constant temperature of 105 ℃, and then heating to 120 ℃ for reflux curing for 5 min; wherein the addition amount of hexamethyldisilazane was 0.05 wt% of the mixture.
S5, adding KOH into the material ripened in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction at 120 ℃ for 2 hours to obtain powdered propyl phenyl silicone resin; wherein, the addition amount of KOH is 0.05 wt% of the mixed material.
S6, filtering, washing with water, washing with methanol and drying the powdered propyl phenyl silicone resin in the step S5 to obtain the propyl phenyl silicone resin micro powder which is free of agglomeration and uniform in particle size.
Example 6
S3, the catalyst solution is an aqueous solution prepared from hydrochloric acid and acetic acid, the mass ratio of the hydrochloric acid to the acetic acid is 1:1, the concentration of the catalyst solution is 4 mu g/L, and the addition amount of the catalyst solution is 35 wt% of the mixed material.
The rest is the same as example 1.
Example 7
S3, the catalyst solution is an aqueous solution prepared from vanadium pentoxide and acetic acid, the mass ratio of the vanadium pentoxide to the acetic acid is 1:1, the concentration of the catalyst solution is 4.5 mu g/L, and the adding amount of the catalyst solution is 30 wt% of the mixed material.
The rest is the same as example 1.
Example 8
S3, the catalyst solution is an aqueous solution prepared from acetic acid and tetraisopropyl zirconia, the concentration of the catalyst solution is 3.5 mu g/L, and the adding amount of the catalyst solution is 40 wt% of the mixed material.
The rest is the same as example 1.
Comparative example 1
S2, the addition amount of phenyltriethoxysilane was 5 wt% of propyltriethoxysilane.
S3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 70 ℃, and carrying out reflux reaction for 1 h;
s4, adding hexamethyldisilazane into the material reacted in the step S3, stirring for a moment, distilling at a constant temperature of 90 ℃, then heating to 100 ℃, refluxing and curing for 20min, wherein the addition amount of hexamethyldisilazane is 0.005 wt% of the mixed material;
s5, adding KOH into the material ripened in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction at 90 ℃ for 2 hours, wherein the adding amount of the KOH is 0.005 wt% of the mixed material;
the rest is the same as example 1.
Comparative example 2
S2, the addition amount of phenyltriethoxysilane is 40 wt% of propyltriethoxysilane.
S3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 120 ℃, and carrying out reflux reaction for 1 h;
s4, adding hexamethyldisilazane into the material reacted in the step S3, stirring for a moment, distilling at constant temperature of 120 ℃, then heating to 140 ℃, refluxing and curing for 5min, wherein the addition amount of hexamethyldisilazane is 0.1 wt% of the mixed material;
s5, adding KOH into the material ripened in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction at 140 ℃ for 1h, wherein the adding amount of the KOH is 0.1 wt% of the mixed material;
the rest is the same as example 1.
The average particle diameter D50 of the propylphenyl silicone resin fine powders obtained in examples 1 to 8 and comparative examples 1 to 2 was measured, and the yield of the propylphenyl silicone resin fine powder was calculated, the average particle diameter was measured using a laser particle size analyzer, the yield being the actual yield of the propylphenyl silicone resin fine powder/the theoretical calculated yield of the propylphenyl silicone resin fine powder, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the average particle size D50 of the propylphenyl silicone resin micro powder prepared in examples 1 to 8 is between 2 and 3 μm, and the yield is between 85 and 90 percent, so that the propylphenyl silicone resin micro powder prepared by the method of the invention has small particle size, uniform particle size, no agglomeration and high yield. Compared with comparative example 1 and comparative example 2, it can be seen that the average particle size of the propylphenyl silicone resin micro powder prepared in examples 1 to 8 is significantly smaller than that of comparative example 1 (the raw material mixture ratio is different, and the temperatures in steps S3, S4 and S5 are all smaller than that of the examples), comparative example 2 (the raw material mixture ratio is different, and the temperatures in steps S3, S4 and S5 are all larger than that of example 1), and the yield is greater than that of comparative example 1 (the raw material mixture ratio is different, and the temperatures in steps S3, S4 and S5 are all smaller than that of example 1) and comparative example 2 (the temperatures in steps S3, S4 and S5 are all larger than that of the examples), and therefore, the temperature in steps S3, S4 and S5 significantly affects the particle size and yield in the method of the invention, and the propylphenyl silicone resin micro powder with small particle size and high yield is obtained by selecting proper mixture ratio and specific process conditions.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (10)
1. The propyl phenyl silicone resin is characterized by comprising raw materials of propyl triethoxysilane high-boiling residues, phenyl triethoxysilane and hexamethyldisilazane.
2. A preparation method of propyl phenyl silicone resin is characterized by comprising the following steps:
s1, adding saturated Na into the high boiling point substance of propyltriethoxysilane2CO3Stirring the solution, and adjusting the pH value of the system to 3-5;
s2, adding phenyltriethoxysilane into the propyltriethoxysilane high-boiling-point substance treated in the step S1 under stirring, and continuing stirring and uniformly mixing after the addition is finished to obtain a mixed material;
s3, adding the catalyst solution into the mixed material obtained in the step S2 under stirring, heating to 85-105 ℃, and carrying out reflux reaction for 3-5 hours;
s4, adding hexamethyldisilazane into the material reacted in the step S3, stirring, distilling at a constant temperature of 100-105 ℃, and then heating to 110-120 ℃ for reflux curing for 5-20 min;
s5, adding KOH into the cured material obtained in the step S4, increasing the stirring speed, and carrying out reflux polycondensation reaction at 110-120 ℃ for 2-5 hours to obtain powdered propyl phenyl silicone resin;
s6, filtering, washing with water, washing with alcohol and drying the powdered propyl phenyl silicone resin in the step S5 to obtain propyl phenyl silicone resin micro powder.
3. The method for preparing propylphenyl silicone resin according to claim 2, wherein in step S1, Na is saturated2CO3The volume ratio of the solution to the propyl triethoxysilane high-boiling residues is 1-4: 100.
4. The method according to claim 2, wherein the amount of phenyltriethoxysilane added in step S2 is 15-35 wt% of propyltriethoxysilane.
5. The method according to claim 2, wherein in step S3, the catalyst solution is an aqueous solution prepared from one or more of hydrochloric acid, acetic acid, vanadium pentoxide, and tetraisopropyl zirconia.
6. The method for preparing propylphenyl silicone resin according to claim 2, wherein the concentration of the catalyst solution is 2-5 μ g/L.
7. The method for preparing propylphenyl silicone resin according to claim 2, wherein in step S3, the amount of catalyst solution added is 30-45 wt% of the mixture.
8. The method of claim 2, wherein the hexamethyldisilazane is added in an amount of 0.01-0.05 wt% based on the mixture in step S4.
9. The method according to claim 2, wherein in step S5, KOH is added in an amount of 0.01-0.05 wt% of the mixture.
10. The method for preparing propyl phenyl silicone resin according to claim 2, wherein the particle size of the propyl phenyl silicone resin micropowder prepared in step S6 is 0.5-5 μm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302878A (en) * | 1999-04-21 | 2000-10-31 | Shin Etsu Chem Co Ltd | Impalpable powder of water-repellent silicone resin |
| CN102086267A (en) * | 2010-12-20 | 2011-06-08 | 青岛科技大学 | Amino-containing organic silicon resin fire retardant and preparation method thereof |
| CN102627769A (en) * | 2012-03-15 | 2012-08-08 | 中国科学院化学研究所 | Room temperature curing ultrahigh temperature-resistant adhesive, liquid silicon resin dedicated for the room temperature curing ultrahigh temperature-resistant adhesive and their preparation methods |
| CN105906810A (en) * | 2016-04-26 | 2016-08-31 | 广东标美硅氟新材料有限公司 | Preparation method of organopolysiloxane resin |
| CN108192100A (en) * | 2018-01-02 | 2018-06-22 | 广东工业大学 | A kind of photo-curable silicone resin and preparation method thereof, photosensitive resin and application |
| CN111253575A (en) * | 2020-03-03 | 2020-06-09 | 东莞市溢美材料科技有限公司 | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin |
-
2020
- 2020-09-02 CN CN202010910406.9A patent/CN111978543B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302878A (en) * | 1999-04-21 | 2000-10-31 | Shin Etsu Chem Co Ltd | Impalpable powder of water-repellent silicone resin |
| CN102086267A (en) * | 2010-12-20 | 2011-06-08 | 青岛科技大学 | Amino-containing organic silicon resin fire retardant and preparation method thereof |
| CN102627769A (en) * | 2012-03-15 | 2012-08-08 | 中国科学院化学研究所 | Room temperature curing ultrahigh temperature-resistant adhesive, liquid silicon resin dedicated for the room temperature curing ultrahigh temperature-resistant adhesive and their preparation methods |
| CN105906810A (en) * | 2016-04-26 | 2016-08-31 | 广东标美硅氟新材料有限公司 | Preparation method of organopolysiloxane resin |
| CN108192100A (en) * | 2018-01-02 | 2018-06-22 | 广东工业大学 | A kind of photo-curable silicone resin and preparation method thereof, photosensitive resin and application |
| CN111253575A (en) * | 2020-03-03 | 2020-06-09 | 东莞市溢美材料科技有限公司 | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin |
Non-Patent Citations (2)
| Title |
|---|
| JIAWEI LI，等: "The flame-retardancy and anti-dripping properties of novel poly(ethylene terephalate)/cyclotriphosphazene/silicone composites", 《POLYMER DEGRADATION AND STABILITY》 * |
| 宋新锋等: "苯基丙基硅树脂合成工艺研究", 《有机硅材料》 * |
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