Efficient synthesis method for polyaminopropylphenylsilsesquioxane
By using the hydrolytic co-condensation of aminopropyltriethoxysilane and phenyltriethoxysilane, combined with a modified D201 ion exchange resin catalyst, the storage stability and heat resistance issues of polyaminopropylsilsesquioxane were solved, achieving a high-efficiency and low-cost synthesis process suitable for industrial production.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- SHANGHAI PUSHING POLYMER MATERIALS CO LTD
- Filing Date
- 2025-03-17
- Publication Date
- 2026-07-23
Smart Images
Figure CN2025082954_23072026_PF_FP_ABST
Abstract
Description
An efficient synthesis method for polyurethane phenyl silsesquioxane Technical Field
[0001] This invention relates to the field of functional silsesquioxane synthesis technology, and in particular to an efficient synthesis method for polyurethane phenyl silsesquioxane. Background Technology
[0002] Non-functional (cyclic ladder-type polyphenyl silsesquioxane) PPSQ exhibits good heat resistance and oxidation stability, but suffers from poor reactivity, compatibility, and adhesion with substrates. Functional polyaminopropyl silsesquioxane (PASQ) possesses reactivity and interfacial activity, but exhibits poor storage stability and heat resistance. Combining the advantages of both types of substances, polysilsesquioxanes containing both phenyl and aminopropyl groups will possess both thermal stability and reactivity. The hydrolytic co-condensation reaction of phenylsilane monomers and aminopropylsilane monomers can combine their structural units onto the same polysiloxane backbone, obtaining copolymers that combine the advantages of both. Furthermore, by changing the monomer ratio, copolymers with various different properties can be obtained.
[0003] In recent years, there has been considerable research on the crystal structure of polyurethane silsesquioxane ammonium salts, the use of hexahedral cage-like polysilsesquioxanes as reinforcing and toughening modifiers, and their role as reaction intermediates. However, research on polyurethane silsesquioxane-phenyl silsesquioxane copolymers (PAPSQ) is scarce. Tunney's patent reports the hydrolytic cocondensation of APS and PTES in a tetrahydrate solution, but its structure, composition, and properties are not studied. Because the product structure is related to the reaction conditions and methods, the copolymers obtained by cocondensation with different solvents, different catalysts, and different methods exhibit significant differences in structure, composition, properties, and morphology.
[0004] Currently, the raw materials for synthesizing silsesquioxanes are usually trichlorosilanes containing different functional groups. However, the hydrolysis and condensation reaction of trichlorosilanes is intense and complex, and the process conditions are difficult to control. It requires acid removal and solvent recovery, and the acidity changes during the reaction. In addition, the synthesis time of functional silsesquioxanes is too long and the yield is low, which is not conducive to industrialization. Summary of the Invention
[0005] Given the aforementioned background, this method utilizes readily available raw materials, aminopropyltriethoxysilane (APS) and phenyltriethoxysilane (PTES), to hydrolyze and co-condense under various conditions to prepare a novel polysilsesquioxane PAPSQ that contains both phenyl and aminopropyl groups in its composition, is branched or highly cross-linked in structure, and exists in resin or granular form. The hydrolytic co-condensation method introduces amino functional groups into the polyphenylsilsesquioxane system, resulting in a relatively simple method and route.
[0006] The technical solution is as follows:
[0007] An efficient method for synthesizing polyaminopropylphenyl silsesquioxane includes the following steps:
[0008] (1) Add 50-100 parts of ethanol, 0.5-2 parts of alkaline resin catalyst and 20-30 parts of deionized water to a three-necked flask according to the mass number, and maintain a fixed temperature;
[0009] (2) Using a constant pressure dropping funnel, add dropwise a solution of aminopropyltriethoxysilane and phenyltriethoxysilane to a three-necked flask;
[0010] (3) Continue stirring the reaction after the dropwise addition is complete;
[0011] (4) After the timing is over, the powder is washed by distillation and vacuum filtration with H2O / EtOH, and then washed with anhydrous ethanol. The rinsed powder is thoroughly dried under vacuum at room temperature for 16-24 hours. The fixed temperature in step (1) is set to 35-45℃.
[0012] The preparation method of the alkaline resin catalyst in step (1) is as follows:
[0013] The following are by weight parts:
[0014] 1) Add 100-140 parts of D201 ion exchange resin (manufactured in quaternary ammonium salt form), 1000-1500 parts of acryloyl chloride, and 3-8 parts of zinc chloride to a stirred tank 1. Stir and react at 30-40℃ for 30 to 60 minutes. Filter, wash with water, and dry to obtain D201 ion exchange resin containing propylene groups.
[0015] 2) Add 12-24 parts of boron trifluoride ethylamine complex (CAS No.: 75-23-0), 2.4-5.5 parts of N-(3-aminopropyl)diethanolamine, 2-5 parts of triethylamine, 200-340 parts of D201 ion exchange resin containing propylene groups, and 1000-1200 parts of dichloroethane to stirred tank 2. Filter, wash with water, and dry to obtain boron-doped D201 ion exchange resin, quaternary ammonium salt type.
[0016] 3) Then, the boron-doped D201 ion exchange resin, in the quaternary ammonium salt form, is packed into the ion exchange column for transformation to obtain the hydrogen-oxygen type boron-doped D201 ion exchange resin, i.e., the basic resin catalyst.
[0017] In the aforementioned transformation steps:
[0018] The resin volume accounts for 20-30% of the ion exchange column volume; NaOH concentration: 4-10wt%; contact time: 30-60 minutes; forward wash flow rate: 15-25 m / h.
[0019] In step (2), the mass ratio of aminopropyltriethoxysilyl to phenyltriethoxysilane is 1-5:5-9.
[0020] The dripping time in step (2) is 30-60 minutes.
[0021] The reaction time in step (3) is 8-13 hours.
[0022] In step (4), the volume ratio of H2O / EtOH is 1:3.
[0023] Catalyst synthesis mechanism: After the allyl D201 ion exchange resin undergoes an aminoolefin addition reaction with boron trifluoride ethylamine complex and N-(3-aminopropyl)diethanolamine, boron trifluoride complex is grafted onto it and converted to the -OH form, resulting in a modified D201 ion exchange resin.
[0024] The introduction of boron trifluoride ethylamine complex and N-(3-aminopropyl)diethanolamine increases the number of active sites on the resin surface. These sites react with specific groups on the propyl D201 ion exchange resin via aminoolefin addition reactions, forming stable chemical bonds. This bond formation enhances the interaction between the resin and the reactants, thereby improving catalytic efficiency.
[0025] The technical effects of boron trifluoride complex and diethanolamine on improving the conversion rate of hydrolytic polymerization of aminopropyltriethoxysilane and phenyltriethoxysilane include the following aspects:
[0026] 1. Enhanced catalytic activity: Boron trifluoride complexes, as strong Lewis acids, can effectively catalyze the hydrolysis and condensation reactions of silanes. The complex formed with diethanolamine further enhances the catalytic activity, as diethanolamine not only provides additional electron density but may also form hydrogen bonds with silanes through its hydroxyl groups, thereby promoting the hydrolysis reaction.
[0027] 2. Improved stability: The complex formed by the boron trifluoride complex and diethanolamine exhibits high stability under reaction conditions and is not easily decomposed or deactivated. This means that the active site can continue to function during the catalytic process, thereby improving the overall catalytic efficiency and product yield.
[0028] 3. Optimized reaction conditions: Using boron trifluoride complex and diethanolamine as catalysts enables efficient hydrolysis and condensation reactions under relatively mild conditions. This helps reduce side reactions and improves the purity and selectivity of the products.
[0029] Technical effects:
[0030] Compared with existing technologies, this method has the following advantages in synthesizing PAPSQ:
[0031] This method utilizes inexpensive raw materials APS and PTES, and anhydrous ethanol as the solvent. This is because ethanol is also a byproduct of the hydrolysis of ethoxysilanes, ensuring a simpler system composition for easier subsequent separation and purification. Furthermore, the ratio of APS to PTES is adjusted to achieve the highest yield. This method also effectively reduces reaction time and improves economic efficiency. Attached Figure Description
[0032] Figure 1 illustrates the reaction mechanism of this invention. Detailed Implementation
[0033] The features of the present invention are further illustrated below through embodiments, but the scope of protection of the present invention is not limited to the embodiments.
[0034] Catalyst Preparation Example 1
[0035] 1) Add 100g of D201 ion exchange resin (manufactured in quaternary ammonium salt form), 1000g of acryloyl chloride, and 3g of zinc chloride to a stirred tank 1. Stir and react at 30°C for 30 minutes. Filter, wash with water, and dry to obtain D201 ion exchange resin containing propylene groups.
[0036] 2) Add 12g boron trifluoride ethylamine complex (CAS No.: 75-23-0), 2.4g N-(3-aminopropyl)diethanolamine, 2g triethylamine, 200g D201 ion exchange resin containing propylene groups, and 1000g dichloroethane to stirred tank 2. Filter, wash with water, and dry to obtain boron-doped D201 ion exchange resin, quaternary ammonium salt type.
[0037] 3) Then, the boron-doped D201 ion exchange resin, in quaternary ammonium salt form, is packed into the ion exchange column for transformation to obtain the hydrogen-oxygen type boron-doped D201 ion exchange resin, namely the No. 1 alkaline resin catalyst.
[0038] In the aforementioned transformation steps:
[0039] The resin volume accounts for 20% of the ion exchange column volume; NaOH concentration: 4wt%; contact time: 30 minutes; forward wash flow rate: 15 m / h.
[0040] Catalyst Preparation Example 2
[0041] 1) Add 120g of D201 ion exchange resin (manufactured in quaternary ammonium salt form), 1250g of acryloyl chloride, and 5g of zinc chloride to a stirred tank 1. Stir and react at 35°C for 45 minutes. Filter, wash with water, and dry to obtain D201 ion exchange resin containing propylene groups.
[0042] 2) Add 18g of boron trifluoride ethylamine complex (CAS No.: 75-23-0), 4.8g of N-(3-aminopropyl)diethanolamine, 3.5g of triethylamine, 280g of D201 ion exchange resin containing propylene groups, and 1100g of dichloroethane to stirred tank 2. Filter, wash with water, and dry to obtain boron-doped D201 ion exchange resin, quaternary ammonium salt type.
[0043] 3) Then, the boron-doped D201 ion exchange resin, in quaternary ammonium salt form, is packed into the ion exchange column for transformation to obtain the hydrogen-oxygen type boron-doped D201 ion exchange resin, namely the No. 2 alkaline resin catalyst.
[0044] In the aforementioned transformation steps:
[0045] The resin volume is 25% of the ion exchange column volume; NaOH concentration: 7wt%; contact time: 45 minutes; forward wash flow rate: 20 m / h.
[0046] Catalyst Preparation Example 3
[0047] 1) Add 140g of D201 ion exchange resin (manufactured in quaternary ammonium salt form), 1500g of acryloyl chloride, and 8g of zinc chloride to a stirred tank 1. Stir and react at 40°C for 60 minutes. Filter, wash with water, and dry to obtain D201 ion exchange resin containing propylene groups.
[0048] 2) Add 24g of boron trifluoride ethylamine complex (CAS No.: 75-23-0), 5.5g of N-(3-aminopropyl)diethanolamine, 5g of triethylamine, 340g of D201 ion exchange resin containing propylene groups, and 1200g of dichloroethane to stirred tank 2. Filter, wash with water, and dry to obtain boron-doped D201 ion exchange resin, quaternary ammonium salt type.
[0049] 3) Then, the boron-doped D201 ion exchange resin, in quaternary ammonium salt form, is packed into the ion exchange column for transformation to obtain the hydrogen-oxygen type boron-doped D201 ion exchange resin, namely the No. 3 alkaline resin catalyst.
[0050] In the aforementioned transformation steps:
[0051] The resin volume is 30% of the ion exchange column volume; NaOH concentration: 10wt%; contact time: 60 minutes; forward wash flow rate: 25 m / h.
[0052] Example 1
[0053] (1) Add a mixed solution of APS and PTES in different proportions, 75 ml of ethanol, 1 g of No. 1 alkaline resin catalyst, and 25 ml of deionized water to a three-necked flask, and keep the temperature at 40℃.
[0054] (2) Add the solution of APS and PTES dropwise using a constant pressure dropping funnel. The addition time is 60 min.
[0055] (3) Continue stirring for 8 hours after the addition is completed.
[0056] (4) After the timing is completed, the powder is washed with distilled H2O / EtOH (1 / 3 volume) under vacuum filtration, and then washed with pure ethanol. The rinsed powder is then thoroughly dried under vacuum at room temperature for 20 h.
[0057] The steps of Examples 2-8 and Comparative Examples 1-2 are basically the same as those of Example 1, with the differences shown in Table 1:
[0058] Table 1
[0059] As can be seen from Table 1, the preparation time of PAPSQ described in Examples 1 to 5 of the present invention can be shortened to 8 hours, its synthesis steps can be simplified, and a very high yield can be achieved.
[0060] A comparison of Example 1 and Example 6 shows that the yield is not affected even at a lower reaction temperature.
[0061] By comparing Example 1 and Example 7, it can be seen that the water addition time has a low impact on the yield, and the controllable range is within 30 minutes.
[0062] By comparing Example 1 and Example 8, it can be seen that the reaction time of 8 hours and 12 hours has little effect on the yield. This indicates that 8 hours is sufficient for APS and PTES to hydrolyze and condense into polymers, which greatly reduces the reaction time and is beneficial for industrial production.
[0063] A comparison of Examples 1-5 with Comparative Examples 1-2 shows that the initial hydrolysis of APS and PTES yields silanol functional oligomers. These silicon-hydrogen functional reactions are very active, and then condense into silsesquioxanes in an alkaline catalyst. Adding only PTES as the single component results in a white precipitate after the reaction, with a yield exceeding 90%. However, with only APS as the single component, no precipitate forms after the reaction, resulting in a clear solution. This is likely due to the strong interaction between the amino group and the polar ethanol-H2O solvent. Simultaneous hydrolysis of APS and PTES leads to co-condensation, but the product state varies with the APS / PTES molar ratio. When the ratio is low, a white precipitate appears, but the yield decreases with increasing APS content.
[0064] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. Other modifications can be easily made by those skilled in the art. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.
Claims
1. A highly efficient method for synthesizing polyaminopropylphenyl silsesquioxane, characterized in that, Includes the following steps: (1) Add 50-100 parts of ethanol, 0.5-2 parts of alkaline resin catalyst and 20-30 parts of deionized water to a three-necked flask according to the mass number, and maintain a fixed temperature; (2) Using a constant pressure dropping funnel, add dropwise a solution of aminopropyltriethoxysilane and phenyltriethoxysilane to a three-necked flask; (3) Continue stirring the reaction after the dropwise addition is complete; (4) After the timing is over, the powder is washed by distillation and vacuum filtration with H2O / EtOH, and then washed with anhydrous ethanol. The rinsed powder is then thoroughly dried under vacuum at room temperature for 16-24 hours. The alkaline resin catalyst is prepared by reacting a propylene-containing D201 ion exchange resin, a boron trifluoride ethylamine complex, and N-(3-aminopropyl)diethanolamine.
2. The efficient synthesis method of polyurethanepropylphenyl silsesquioxane according to claim 1, characterized in that: In step (1), the fixed temperature is set to 35-45℃.
3. The efficient synthesis method of polyurethanepropylphenyl silsesquioxane according to claim 1, characterized in that: The preparation method of the alkaline resin catalyst in step (1) is as follows: The following are by weight parts: 1) Add 100-140 parts of D201 ion exchange resin (manufactured in quaternary ammonium salt form), 1000-1500 parts of acryloyl chloride, and 3-8 parts of zinc chloride to a stirred tank 1. Stir and react at 30-40℃ for 30 to 60 minutes. Filter, wash with water, and dry to obtain D201 ion exchange resin containing propylene groups. 2) Add 12-24 parts of boron trifluoride ethylamine complex, 2.4-5.5 parts of N-(3-aminopropyl)diethanolamine, 2-5 parts of triethylamine, 200-340 parts of D201 ion exchange resin containing propylene groups, and 1000-1200 parts of dichloroethane to stirred tank 2. Filter, wash with water, and dry to obtain boron-doped D201 ion exchange resin, quaternary ammonium salt type. 3) Then, the boron-doped D201 ion exchange resin, in the quaternary ammonium salt form, is packed into the ion exchange column for transformation to obtain the hydrogen-oxygen type boron-doped D201 ion exchange resin, i.e., the basic resin catalyst.
4. The efficient synthesis method of polyurethanepropylphenyl silsesquioxane according to claim 3, characterized in that: In the aforementioned transformation steps: The resin volume accounts for 20-30% of the ion exchange column volume; NaOH concentration: 4-10wt%; contact time: 30-60 minutes; forward wash flow rate: 15-25 m / h.
5. The efficient synthesis method of polyaminopropylphenyl silsesquioxane according to claim 1, characterized in that: In step (2), the mass ratio of aminopropyltriethoxysilyl to phenyltriethoxysilane is 1-5:5-9.
6. The efficient synthesis method of polyaminopropylphenyl silsesquioxane according to claim 1, characterized in that: The dripping time in step (2) is 30-60 minutes.
7. The efficient synthesis method of polyurethanepropylphenylsilsesquioxane according to claim 1, characterized in that: The reaction time in step (3) is 8-13 hours.
8. The efficient synthesis method of polyaminopropylphenyl silsesquioxane according to claim 1, characterized in that: In step (4), the volume ratio of H2O / EtOH is 1:3.