CN111732730A - High-temperature-resistant borosilicate rubber raw rubber and synthetic method thereof - Google Patents
High-temperature-resistant borosilicate rubber raw rubber and synthetic method thereof Download PDFInfo
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- CN111732730A CN111732730A CN202010377597.7A CN202010377597A CN111732730A CN 111732730 A CN111732730 A CN 111732730A CN 202010377597 A CN202010377597 A CN 202010377597A CN 111732730 A CN111732730 A CN 111732730A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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Abstract
The invention relates to a high-temperature-resistant borosilicate rubber raw rubber and a synthesis method thereof, belonging to the technical field of special rubber synthesis and the field of high-temperature thermal protection materials. The heat-resistant test result of the high-temperature-resistant borosilicate rubber of the invention shows that: the strength of the phenyl vinyl silicone rubber is reduced by 10% at 282 ℃, while the strength of the borosilicate rubber synthesized in the invention is reduced by 10% at 415 ℃, which shows that the borosilicate rubber has far better heat resistance than the phenyl vinyl silicone rubber.
Description
Technical Field
The invention relates to a high-temperature-resistant borosilicate rubber raw rubber and a synthesis method thereof, belonging to the technical field of special rubber synthesis and the field of high-temperature thermal protection materials. High temperature resistance means 150 ℃.
Background
Polyborosiloxane (borosilicate rubber raw rubber) refers to a polymer obtained by substituting some silicon atoms in the siloxane skeleton of polysiloxane with boron atoms, and the structural formula of the polymer can be expressed as follows:
wherein R1 and R2 are hydrogen, alkyl, aryl, etc.; r3 is hydrogen, aryl, etc.
The B-O bond and the Si-O bond in the borosilicate rubber molecule are high bond energy chemical bonds, the bond energy is 537.6kJ/mo1 and 422.5kJ/mol respectively, and p-pi and d-pi conjugation exist in the structure, so that the polyborosiloxane has more excellent high temperature resistance than common organopolysiloxane. At present, common silicon rubber can be used for a long time at about 250 ℃ at most, and borosilicate rubber can be theoretically used for a long time at 450 ℃. Meanwhile, it has been theoretically confirmed that borosilicate rubber shows more excellent adhesion performance at high temperature than silicone rubber, for example, when used at a temperature of 600 ℃ or higher, residues left after a silicone rubber adhesive is heated have too poor adhesion to a substrate to cause falling off and lose the protective performance to the substrate, and if borosilicate rubber is used as the adhesive, a satisfactory effect can be achieved. With the continuous development and progress of science and technology, it has been theoretically proved that borosilicate rubber shows wider application prospects as materials of high-temperature resistant parts, high-temperature resistant thermal protection materials, heat-resistant coatings, flame retardants, borosilicate carbon-oxygen ceramic precursors and the like, and therefore, polyborosiloxane (borosilicate rubber raw rubber) becomes one of research hotspots.
At present, there are many methods for synthesizing borosilicate rubber raw rubber, and the synthetic methods mainly include two methods according to the synthetic reaction mechanism of polyborosiloxane: one is the polycondensation reaction of boric acid (or boric acid ester) and alkoxy (or chlorine) silane, which is called a non-hydrolysis method; the other is cohydrolysis condensation reaction of borate and alkoxy (acyloxy) silane, which is called cohydrolysis polycondensation method, and although both methods have good reference, both methods cannot realize industrial large-scale production, and the reaction process is too complex, most importantly, the borosilicate rubber which is successfully synthesized in the prior publication is few, and the yield of each synthesis mode is low, and is generally lower than 45%.
In the invention, in order to better obtain the borosilicate rubber raw rubber, most importantly, a simpler method for preparing the borosilicate rubber raw rubber is obtained and has high yield, and the novel ester exchange reaction method is adopted to prepare the borosilicate rubber raw rubber, so that the method overcomes the defects or shortcomings of low yield, high cost, complicated working procedures and the like in the borosilicate rubber raw rubber preparation methods mentioned in various documents at present.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, provides high-temperature-resistant borosilicate rubber and a synthetic method thereof
The technical solution of the invention is as follows:
a high-temperature resistant borosilicate rubber raw rubber has a structural formula as follows:
the invention relates to a preparation method of high-temperature-resistant borosilicate rubber raw rubber, wherein all proportions are molar ratios, and the method comprises the following steps:
firstly, mixing and stirring a diethylene glycol monoethyl ether solvent, a dimethyl phenylboronate reactant, a sulfuric acid catalyst and phenylvinyldimethoxysilane for reaction at the temperature of 150-170 ℃ for 200min, wherein the mole number of the phenylvinyldimethoxysilane is 1/4 of that of the dimethyl phenylboronate, and the ratio of the diethylene glycol monoethyl ether solvent to the dimethyl phenylboronate reactant to the sulfuric acid catalyst is as follows: 100 ml: 0.02-0.08 mol: 3.2-7.2 g, and the stirring speed is 200-300 r/min; the concentration of the sulfuric acid catalyst is 55-65%;
secondly, slowly dripping phenyl vinyl dimethoxysilane again, wherein the mol number of the phenyl vinyl dimethoxysilane is 1/4 of that of the dimethyl phenylboronate, the dripping takes 20-30 minutes, and then, continuously reacting for 90-120 minutes;
thirdly, slowly dropwise adding phenyl vinyl dimethoxysilane again, wherein the mole number of the phenyl vinyl dimethoxysilane is 1/2 of that of the dimethyl phenylboronate, the dropwise adding takes 10-20 minutes, and then, continuously reacting for 60-90 minutes;
fourthly, filtering to obtain a light yellow viscoelastic body, namely the high-temperature resistant borosilicate rubber crude rubber;
and (3) curing the obtained high-temperature-resistant borosilicate rubber raw rubber by using dibutyltin dilaurate as a catalyst to obtain the high-temperature-resistant borosilicate rubber.
The temperature that the rubber can bear when the mechanical property of the obtained high-temperature-resistant borosilicate rubber is reduced by 10 percent in an air environment test is used for measuring the heat resistance of the synthesized rubber.
Advantageous effects
The heat-resistant test result of the high-temperature-resistant borosilicate rubber of the invention shows that: the strength of the phenyl vinyl silicone rubber is reduced by 10% at 282 ℃, while the strength of the borosilicate rubber synthesized in the invention is reduced by 10% at 415 ℃, which shows that the borosilicate rubber has far better heat resistance than the phenyl vinyl silicone rubber.
Detailed Description
A preparation method of high-temperature-resistant borosilicate rubber raw rubber comprises the following steps:
firstly, adding 200-250 ml of diethylene glycol monoethyl ether as a solvent into a three-necked round-bottom flask, keeping the temperature at 150-170 ℃, adding 0.05-0.20 of dimethyl phenyl borate as a reactant, adding 8-18 g of 60% sulfuric acid as a catalyst, stirring at 200-300 r/min mechanically, dropwise adding phenyl vinyl dimethoxysilane in a quarter of the molar amount of dimethyl phenyl borate, consuming 30-40 minutes, and then continuing to react for 120-150 minutes;
the second step is that: slowly dropwise adding phenyl vinyl dimethoxysilane in the molar amount of quarter of dimethyl phenylboronate again, wherein the dropwise adding takes 20-30 minutes, and then continuously reacting for 90-120 minutes;
the third step: slowly dropwise adding phenyl vinyl dimethoxysilane in a half molar amount of the dimethyl phenylboronate again, wherein the dropwise adding takes 10-20 minutes, and then continuously reacting for 60-90 minutes;
the fourth step: concentrating the reaction solution, adding deionized water, evaporating, adding deionized water, and repeatedly evaporating and adding deionized water for many times because water and a solvent are mutually soluble to finally obtain a light yellow viscoelastic body; the fifth step: and (3) testing whether the viscoelastic body has an absorption peak of a B-O-Si bond or not by infrared rays, and testing the temperature which can be born by the rubber when the mechanical property is reduced by 10% in an air environment so as to measure the temperature resistance of the borosilicate rubber.
The invention is further illustrated by the following examples, the application of which is not limited to the examples given, all proportions being in molar ratios:
examples
A preparation method of high-temperature-resistant borosilicate rubber raw rubber comprises the following steps:
the first step is as follows: adding 250ml of diethylene glycol monoethyl ether as a solvent into a three-neck round-bottom flask, keeping the temperature at 150 ℃, adding 0.05mol of dimethyl phenylboronate as a reactant, adding 8 g of 60% sulfuric acid as a catalyst, dropwise adding one fourth (0.0125mol) of phenylvinyldimethoxysilane in the molar amount of the dimethyl phenylboronate at the mechanical stirring speed of 200 r/min, and continuing to react for 120 min, wherein the dropwise adding takes 30 min;
the second step is that: slowly adding one fourth (0.0125mol) of phenyl vinyl dimethoxy silane in the molar amount of dimethyl phenylboronate dropwise again, wherein the dropwise addition takes 20 minutes, and then continuing to react for 90 minutes;
the third step: slowly dropwise adding one-half (0.025mol) of phenyl vinyl dimethoxy silane in the molar amount of dimethyl phenylboronate again, wherein the dropwise adding takes 10 minutes, and then, continuously reacting for 60 minutes;
the fourth step: filtering to obtain a light yellow viscoelastic body;
and testing whether the viscoelastic body has an absorption peak of a B-O-Si bond or not by infrared rays, wherein the borosilicate rubber obtained by curing and synthesizing the dibutyltin dilaurate serving as a catalyst is compared with phenyl vinyl silicone rubber, and the temperature which the rubber can bear when the mechanical property is reduced by 10% is tested in an air environment.
The results show that: the infrared spectrum characterization shows that the concentration is 696-882 cm-1Obvious absorption peaks of B-O-Si bonds appear. The heat resistance test result shows that: the strength of the phenyl vinyl silicone rubber is reduced by 10% at 282 ℃, while the strength of the borosilicate rubber synthesized in the invention is reduced by 10% at 415 ℃, which shows that the borosilicate rubber has far better heat resistance than the phenyl vinyl silicone rubber.
Claims (10)
1. The high-temperature-resistant raw borosilicate rubber is characterized in that: the structural formula of the high-temperature-resistant borosilicate rubber is as follows:
2. a preparation method of high-temperature-resistant borosilicate rubber raw rubber is characterized by comprising the following steps:
firstly, mixing and stirring a diethylene glycol monoethyl ether solvent, a dimethyl phenylboronate reactant, a sulfuric acid catalyst and phenylvinyldimethoxysilane for reaction at the temperature of 150-170 ℃ for 200min, wherein the mole number of the phenylvinyldimethoxysilane is 1/4 of that of the dimethyl phenylboronate, and the ratio of the diethylene glycol monoethyl ether solvent to the dimethyl phenylboronate reactant to the sulfuric acid catalyst is as follows: 100 ml: 0.02-0.08 mol: 3.2-7.2 g, wherein the concentration of the sulfuric acid catalyst is 55% -65%;
secondly, slowly dripping phenyl vinyl dimethoxysilane again, wherein the mole number of the phenyl vinyl dimethoxysilane is 1/4 of that of the dimethyl phenylboronate, and then continuing the reaction;
thirdly, slowly dropwise adding phenyl vinyl dimethoxysilane again, wherein the mole number of the phenyl vinyl dimethoxysilane is 1/2 of that of the dimethyl phenylboronate, and then continuing to react;
and fourthly, filtering to obtain the high-temperature resistant borosilicate rubber raw rubber.
3. The preparation method of the high-temperature-resistant raw borosilicate rubber according to claim 2, wherein the preparation method comprises the following steps: in the first step, the stirring speed is 200-300 r/min.
4. The preparation method of the high-temperature-resistant raw borosilicate rubber according to claim 2, wherein the preparation method comprises the following steps: in the first step, the concentration of the sulfuric acid catalyst is 55-65%.
5. The preparation method of the high-temperature-resistant raw borosilicate rubber according to claim 2, wherein the preparation method comprises the following steps: in the second step, the dripping takes 20-30 minutes.
6. The preparation method of the high-temperature-resistant raw borosilicate rubber according to claim 2, wherein the preparation method comprises the following steps: and in the second step, continuously reacting for 90-120 minutes.
7. The preparation method of the high-temperature-resistant raw borosilicate rubber according to claim 2, wherein the preparation method comprises the following steps: in the third step, the dripping takes 10-20 minutes.
8. The preparation method of the high-temperature-resistant raw borosilicate rubber according to claim 2, wherein the preparation method comprises the following steps: and in the third step, the reaction is continued for 60-90 minutes.
9. The preparation method of the high-temperature-resistant raw borosilicate rubber according to claim 2, wherein the preparation method comprises the following steps: in the first step, the concentration of the sulfuric acid catalyst is 60%.
10. The preparation method of the high-temperature-resistant raw borosilicate rubber according to claim 2, wherein the preparation method comprises the following steps: and in the fourth step, the obtained high-temperature resistant borosilicate rubber crude rubber is a faint yellow viscoelastic body.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637327A (en) * | 2021-09-26 | 2021-11-12 | 深圳市思汇恒实业有限公司 | High-temperature-resistant silicon rubber sealing ring and preparation method thereof |
| CN115044046A (en) * | 2022-07-20 | 2022-09-13 | 广州市白云化工实业有限公司 | Boron-modified 107 adhesive prepolymer, high-temperature ceramic silicone sealant and preparation method thereof |
| CN116694086A (en) * | 2023-06-25 | 2023-09-05 | 金龙电缆科技有限公司 | High-temperature-resistant high-strength torsion-resistant high-flame-retardant cable insulating sheath material and manufacturing method thereof |
| WO2024092881A1 (en) * | 2022-10-31 | 2024-05-10 | 北京宇航系统工程研究所 | High- and low-temperature resistant, anti-vibration and thermal-insulation material, and preparation method therefor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637327A (en) * | 2021-09-26 | 2021-11-12 | 深圳市思汇恒实业有限公司 | High-temperature-resistant silicon rubber sealing ring and preparation method thereof |
| CN115044046A (en) * | 2022-07-20 | 2022-09-13 | 广州市白云化工实业有限公司 | Boron-modified 107 adhesive prepolymer, high-temperature ceramic silicone sealant and preparation method thereof |
| CN115044046B (en) * | 2022-07-20 | 2023-09-05 | 广州市白云化工实业有限公司 | Boron modified 107 glue prepolymer, high-temperature ceramic silicone sealant and preparation method thereof |
| WO2024092881A1 (en) * | 2022-10-31 | 2024-05-10 | 北京宇航系统工程研究所 | High- and low-temperature resistant, anti-vibration and thermal-insulation material, and preparation method therefor |
| CN116694086A (en) * | 2023-06-25 | 2023-09-05 | 金龙电缆科技有限公司 | High-temperature-resistant high-strength torsion-resistant high-flame-retardant cable insulating sheath material and manufacturing method thereof |
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Application publication date: 20201002 |