CN115785449A - Modified linear polydimethylsiloxane with controllable side chain polymerization degree and preparation method thereof - Google Patents
Modified linear polydimethylsiloxane with controllable side chain polymerization degree and preparation method thereof Download PDFInfo
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Abstract
The invention provides modified linear polydimethylsiloxane with controllable side chain polymerization degree and a preparation method thereof, belonging to the field of organosilicon preparation. Firstly, preparing linear polydimethylsiloxane with a side chain being hydrogen radical and water under the catalysis of a metal catalyst to prepare side chain silicon hydroxyl modified linear polydimethylsiloxane; then, carrying out a side chain growth reaction to obtain side chain silicon hydroxyl terminated linear polydimethylsiloxane with a side chain being grown; and finally, adding end-capped chlorosilane and an acid-binding agent to react to obtain the linear polydimethylsiloxane with controllable side chain polymerization degree. The polymerization degree of the branched chain is controlled by the cycle number of the reaction, and the modified linear polydimethylsiloxane with the controllable side chain polymerization degree is successfully prepared. The low-temperature DSC test of the product shows that the product has excellent low-temperature resistance.
Description
Technical Field
The invention belongs to the field of organic silicon preparation, and particularly relates to modified linear polydimethylsiloxane with controllable side chain polymerization degree and a method thereof.
Background
Conventional linear polydimethylsiloxanes are based on Si (CH) 3 ） 2 O is a main repeating unit, and a molecular chain consisting of Si-O-Si has very good flexibility, air permeability and excellent high-temperature resistance because of large Si-O-Si bond energy and lower rotational energy barrier. However, at around-40 ℃, the polysiloxane segment can crystallize, which greatly limits the use of polysiloxane products.
Chemical modification is a common means for improving the performance of polysiloxane, and groups are introduced at two sides of the main chain of linear polydimethylsiloxane to destroy the crystallization of a polysiloxane chain and improve the application performance of a polysiloxane product. There are two main types of chemical modifications to linear polydimethylsiloxane products: one is to introduce other organic groups by hydrosilylation, but the high temperature resistance of the introduced groups is low, resulting in low high temperature resistance of the polysiloxane product as a whole. The second method is to prepare branched polydimethylsiloxane, which is mainly prepared by hydrolyzing trifunctional or tetrafunctional organosilicon monomer, but the polysiloxane prepared by the method has poor stability and cannot accurately control the structure of the polysiloxane, and the performance of the product greatly fluctuates along with the operating conditions.
Chinese patent document CN109689734a discloses a method for continuously producing alkoxy branched siloxanes by hydrolysis of tetrafunctional, trifunctional, difunctional and monofunctional silicone monomers. The obtained product is a partially crosslinked polysiloxane product, and the branched chain structure and the crosslinking degree in the product are not controllable. Chinese patent document CN103365077a discloses a method for preparing branched polysiloxane, i.e. 3d cross-linked network, by hydrosilylation reaction of Q-type and T-type branched polysiloxane precursors containing vinyl, alkynyl, etc. groups with linear polysiloxane, but the chain length and cross-linking course prepared by the patent are still not controllable.
Therefore, it is necessary to develop a side chain-controllable siloxane-modified linear polydimethylsiloxane.
Disclosure of Invention
The invention provides modified linear polydimethylsiloxane with controllable side chain polymerization degree and a preparation method thereof, aiming at solving the problem that the side chain polymerization degree of the modified linear polydimethylsiloxane is uncontrollable in the prior art.
A modified linear polydimethylsiloxane having a controlled degree of side chain polymerization having the following structural formula:
wherein R is 1 And R 2 The radicals are each identical or different neutral radicals, R 3 、R 4 、R 5 The group is any group; m + n is 2 to 1500, m is 0 to 1499, n is 2 to 1500, and x is 0 to 20.
Preferably, R 1 、R 2 The groups are independently hydrocarbyl of 1 to 18 carbon atoms; more preferred is a hydrocarbon group of 1 to 6 carbon atoms, and still more preferred is a vinyl group, a methyl group or the like. m + n is 2 to 600, m is 0 to 599, n is 2 to 600; x is 0~5.
Preferably, R 3 、R 4 、R 5 The groups are independently a hydrocarbon group or a hydrocarbonoxy group of 1 to 6 carbon atoms, and more preferably a methyl group, a methoxy group, or a benzeneRadicals, vinyl radicals, and the like.
The invention also provides a preparation method of the modified linear polydimethylsiloxane with the controllable side chain polymerization degree, which comprises the following steps:
(1) Synthesizing side chain silicon hydroxyl modified linear polydimethylsiloxane: mixing linear polydimethylsiloxane with a side chain being a hydrogen group, water, an organic solvent and a metal catalyst at the temperature of 5 to 20 ℃, and reacting for 0.5 to 3 hours to obtain a reaction solution; filtering the reaction solution, and removing water to obtain a side chain silicon hydroxyl modified linear polydimethylsiloxane product;
the route is as follows:
the polymer I is polydimethylsiloxane with a side chain being hydrogen radical; wherein R is 1 The radicals being neutral radicals (non-acidic or non-basic radicals), R 2 The radicals being neutral radicals (non-acidic or non-basic radicals), in which R 1 And R 2 May be the same or different; m + n is 2 to 1500, m is 0 to 1499, and n is 2 to 1500.
(2) The second step is a chain extension reaction of the side chain, comprising:
carrying out water removal treatment on the reactant in the step (1), and then adding dimethylchlorosilane and an acid-binding agent for reaction;
(ii) filtering to remove precipitate after the reaction is finished, mixing the filtrate with water and a metal catalyst, and reacting to obtain a reaction solution;
repeating the step (1) and the step (2) to obtain a linear polydimethylsiloxane reaction solution with a side chain extended and terminated by a side chain silicon hydroxyl group; the number of repetitions is the degree of side chain polymerization (i.e., x + 1);
the reaction equation is as follows:
(3) After the final reaction liquid obtained in the step (2) is subjected to water removal treatment, adding end-capped chlorosilane and an acid-binding agent for reaction to obtain linear polydimethylsiloxane with controllable side chain polymerization degree,
the reaction process is as follows:
wherein R is 3 、R 4 、R 5 The groups are independently a hydrocarbyl or hydrocarbyloxy group of 1~6 carbon atoms; methyl, methoxy, phenyl, vinyl, and the like are preferred.
Preferably, R in step (1) 1 And R 2 The groups can be alkyl with 1 to 18 carbon atoms; more preferred are the hydrocarbyl groups of 1~6 carbon atoms, such as vinyl, methyl; m + n is 2 to 600, m is 0 to 599, and n is 2 to 600.
Preferably, the hydrogen content (mass fraction of hydrogen in Si-H in the polymer I) in the linear polydimethylsiloxane with the hydrogen group on the side chain in the step (1) is 0.1 to 1.6 percent. More preferably 0.1 to 0.5%.
Preferably, the metal catalyst in the step (1) is a palladium-carbon catalyst, and the mass content of palladium in the palladium-carbon catalyst is 10%. The adding amount of the catalyst (calculated by metal elements) is 0.02-0.08% of the mass of the total reaction system.
Preferably, the organic solvent in the step (1) is 1,4-dioxane; the dosage of the organic solvent is 45 to 70 percent of the total mass of the reaction system. The total reaction system comprises water, a solvent and linear polydimethylsiloxane with a side chain of hydrogen group.
Preferably, the addition amount of the water in the step (1) is 1.5 to 3.0 times of the theoretical demand. The theoretical requirement amount of the water is the amount of substances of silicon-hydrogen bonds in the linear polydimethylsiloxane with the side chain being hydrogen radical.
Preferably, in the step (i), si-OH and dimethylchlorosilane generate Si-O-Si at the reaction temperature of 0 to 30 ℃.
Preferably, in step (ii), the catalytic Si-H bond is reacted with water to form Si-OH, and the catalyst is a palladium on carbon catalyst. The addition amount (calculated by metal elements) of the catalyst is 0.02-0.08% of the mass of the total reaction system. The overall reaction system here is the same as in step (1).
Preferably, in step (ii), the amount of water added is the same as the theoretical requirement for water in step (i); the reaction temperature of the Si-H bond with water to form Si-OH is 5 to 20 ℃.
Preferably, the water removal treatment in the step (2) and the step (3) is water removal treatment using a neutral water-absorbable inorganic salt, and a more preferred inorganic salt is anhydrous sodium sulfate.
An acid-binding agent is required to be added in the reaction of Si-OH and Si-Cl to generate Si-O-Si, preferably, the acid-binding agent in the step (2) and the step (3) is organic amine, further preferably, the organic amine is tertiary amine, and more preferably, the organic tertiary amine is triethylamine. The amount of the substance containing nitrogen element in the added tertiary amine is 1.0 to 1.05 times of the amount of the blocked chlorosilane substance.
Preferably, the addition amount of the dimethylchlorosilane in the step (2) is 1 to 1.05 times of the amount of substances with Si-H bonds in the polymer I.
Preferably, the end-capped chlorosilane end-capping group in step (3) is a hydrocarbyl or hydrocarbyloxy group having 1 to 6 carbon atoms. The addition amount of the end-capped chlorosilane in the step (3) is 1 to 1.05 times of the amount of substances with Si-H bonds in the polymer I.
Preferably, the reaction temperature in the step (3) is 0 to 30 ℃.
In each reaction step, the reaction process can be characterized according to Fourier infrared spectrum, and the silicon-hydrogen bond is 2200cm -1 The absorption peak at (a) disappeared, confirming that the reaction had been completely completed. The degree of chain growth can be determined by measuring the hydrogen content (mass percent of hydrogen in Si-H to total product) of the nuclear magnetic and silicon-containing hydrogen bond intermediates. The low temperature resistance effect of the resulting final product can be examined by low temperature DSC.
The invention has the advantages of
According to the invention, a stable intermediate of silicon hydroxyl is prepared, the preparation of a siloxane side chain is realized by utilizing the activity of the silicon hydroxyl to react with chlorosilane, the branched polydimethylsiloxane with the controllable degree of polymerization of the siloxane side chain is obtained, and the characteristic that siloxane is easy to balance under the acid or alkali condition is completely avoided in the whole process. The low-temperature DSC test of the product shows that the product has excellent low-temperature resistance.
Since Si-OH has high reactivity, condensation is extremely easy to occur under weak acid or weak alkaline conditions, and the traditional method for preparing hydroxyl modified polysiloxane is a random polymer because a catalyst is acid or alkali, and a linear polymer cannot be obtained. In the invention, linear polydimethylsiloxane with hydrogen radicals on side chains is used for preparing the side chain silicon hydroxyl modified linear polydimethylsiloxane under neutral conditions. In the preparation process, the side chain silicon hydroxyl modified linear polydimethylsiloxane product is dissolved in a specific organic solvent, so that the stable existence of the silicon hydroxyl is ensured, and the side chain silicon hydroxyl modified linear polydimethylsiloxane which exists stably is obtained. In addition, the invention uses the supported catalyst, the reaction occurs on the surface, and the steric hindrance phenomenon of the supported catalyst also inhibits the condensation of silicon hydroxyl.
In the invention, the polymerization degree of the branched chain is controlled by the cycle number of the reaction, although the reaction steps are increased along with the increase of the polymerization degree, the solvent and the catalyst can be repeatedly used, and therefore, the synthesis cost is not additionally increased. The distribution of branched chains on the molecular chain of the polymer I can be controlled by the content of Si-H in the polymer I, and the performance of the product can be improved by regulating and controlling the polymerization degree of the side chain. The invention synthesizes the branched chain modified polydimethylsiloxane with controllable side chain polymerization degree for the first time, and can regulate and control the performance of polysiloxane through the lengths of different side chains, thereby meeting different actual requirements.
Drawings
FIG. 1 is an infrared spectrum of product 3;
FIG. 2 shows a product 3 1 H NMR spectrum;
FIG. 3 product 3 29 SiNMR：
FIG. 4 is an infrared spectrum of intermediate 3-1:
FIG. 5 is an infrared spectrum of intermediate 3-2;
FIG. 6 is a low temperature DSC of conventional polydimethylsiloxane;
FIG. 7 is a low temperature DSC of product 3.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following embodiments.
The raw materials used in the embodiment of the invention are all common commercial products, wherein the linear polydimethylsiloxane with the side chain being hydrogen is purchased from silicone material GmbH in east Shandong Yue. Common polydimethylsiloxanes (n = 75) were purchased from silicone materials, tokyo, shandong, inc. Hydrogen content was measured using the gas method in chemical industry Standard HG/T4804-2015.
Example 1
A modified linear polydimethylsiloxane with controllable side chain polymerization degree and a preparation method thereof,
the structural formula of polymer I is as follows:
step (1): 100g of polymer I, 3.7g of water and 230g of 1, 4-dioxane are put into a flask, stirring is started, the temperature is kept to 20 ℃, then 2.68g of palladium carbon catalyst (the loading amount is 10 wt.%) is added, reaction is carried out for 3 hours, and filtration is carried out to remove the platinum carbon catalyst, so that filtrate A is obtained.
Step (2):
step (1): an appropriate amount of anhydrous sodium sulfate was added to the filtrate a until sodium sulfate did not crystallize, and the sodium sulfate was removed by filtration. Adding 14.57g of triethylamine into the filtrate, starting stirring, keeping the temperature constant to 10 ℃, dropwise adding 13.62g of dimethylchlorosilane into the flask, controlling the temperature not to exceed 30 ℃, and continuing stirring and reacting for 2 hours after dropwise adding. Filtering, and removing salt in the system to obtain filtrate B.
Step (2): adding 3.7g of water into the filtrate B, starting stirring, keeping the temperature to 20 ℃, adding 2.68g of palladium-carbon catalyst, reacting for 3 hours at 20 ℃, filtering, and removing the palladium-carbon catalyst to obtain filtrate C.
Repeating the steps (1) and (2) for four times.
And (3): anhydrous sodium sulfate was added to the filtrate C until the anhydrous sodium sulfate did not crystallize, and the sodium sulfate was removed by filtration. Then add 14.57g of triethylamine is started to stir, the temperature is kept constant to 10 ℃, 15.64g of trimethylchlorosilane is dropwise added into the flask, and the temperature is controlled not to exceed 30 ℃. After the completion of the dropwise addition, the reaction was continued with stirring for 2 hours. Filtering, removing salt in the system, removing solvent from the filtrate at-0.090MPa and 70 deg.C to obtain colorless transparent product 1 with product viscosity of 7103mm 2 And(s) in the presence of a catalyst. The structural formula of product 1 is as follows:
。
example 2
A modified linear polydimethylsiloxane with controllable side chain polymerization degree and a preparation method thereof,
the structural formula of polymer I is as follows:
step (1): 100g of polymer I, 8.02g of water and 108g of 1, 4-dioxane are added into a flask, stirring is started, the temperature is kept to 10 ℃, then 1.09g of palladium carbon catalyst (the loading amount is 10 wt.%) is added, reaction is carried out for 0.5 hour, and filtration is carried out to remove the platinum carbon catalyst, so as to obtain filtrate A.
Step (2):
step (1): an appropriate amount of anhydrous sodium sulfate was added to the filtrate a until sodium sulfate did not crystallize, and the sodium sulfate was removed by filtration. Adding 23.23g of triethylamine into the filtrate, starting stirring, keeping the temperature constant to 10 ℃, dropwise adding 21.72g of dimethylchlorosilane into the flask, controlling the temperature not to exceed 15 ℃, and continuing stirring and reacting for 2 hours after dropwise adding. Filtering, and removing salt in the system to obtain filtrate B.
Step (2): adding 8.02g of water into the filtrate B, starting stirring, keeping the temperature to 10 ℃, adding 1.09g of palladium-carbon catalyst, reacting for 0.5 hour at 10 ℃, filtering, and removing the palladium-carbon catalyst to obtain filtrate C.
And (3):
anhydrous sodium sulfate was added to the filtrate C until the anhydrous sodium sulfate did not crystallize, and the sodium sulfate was removed by filtration. Then 23.23g triethylamine is added, stirring is started, the temperature is kept constant to 10 ℃, and 45.62g triethoxy chloride is addedSilane was added dropwise to the flask, with the temperature controlled not to exceed 15 ℃. After the completion of the dropwise addition, the reaction was continued with stirring for 2 hours. Filtering, removing salt in the system, removing solvent from the obtained filtrate at-0.090MPa and 70 deg.C to obtain colorless transparent product 2 with product viscosity of 120.15mm 2 And s. The structural formula of product 2 is as follows:
example 3
A modified linear polydimethylsiloxane with controllable side chain polymerization degree and a preparation method thereof,
the structural formula of polymer I is as follows:
step (1): 100g of polymer I, 25.18g of water and 102g of 1, 4-dioxane are added into a flask, stirring is started, the temperature is kept at 5 ℃, then 0.46g of palladium-carbon catalyst (with the loading of 10 wt.%) is added, reaction is carried out for 3 hours, and filtration is carried out to remove the platinum-carbon catalyst, so as to obtain filtrate A.
Step (2):
step (1): an appropriate amount of anhydrous sodium sulfate was added to the filtrate a until sodium sulfate did not crystallize, and the sodium sulfate was removed by filtration. Adding 47.65g of triethylamine into the filtrate, starting stirring, keeping the temperature constant to 0 ℃, dropwise adding 44.55g of dimethylchlorosilane into the flask, controlling the temperature not to exceed 5 ℃, and continuing stirring and reacting for 2 hours after dropwise adding. Filtering, removing salt in the system to obtain filtrate B
Step (2): adding 25.18g of water into the filtrate, starting stirring, keeping the temperature to 5 ℃, adding 0.46g of palladium-carbon catalyst, reacting for 3 hours at the temperature of 5 ℃, filtering, and removing the palladium-carbon catalyst to obtain filtrate C.
Repeating the steps (1) and (2) for two times to obtain the final filtrate D of the step (2). When step (1) is repeated twice and step (2) is repeated 1 time, intermediate 3-1 is obtained, and the structural formula is as follows:
when the steps (1) and (2) are repeated twice respectively, an intermediate 3-2 is obtained, and the structural formula of the intermediate is as follows:
Step (3)
To the filtrate D was added anhydrous sodium sulfate until crystallization of anhydrous sodium sulfate did not occur, and sodium sulfate was removed by filtration. Then 47.65g of triethylamine is added, stirring is started, the temperature is kept to 0 ℃, 51.16g of trimethylchlorosilane is dropwise added into the flask, and the temperature is controlled not to exceed 5 ℃. After the completion of the dropwise addition, the reaction was continued with stirring for 2 hours. Filtering, removing salt in the system, removing solvent from the obtained filtrate at-0.090MPa and 70 deg.C to obtain colorless transparent product 3 with product viscosity of 155.32mm 2 And s. The structural formula of product 3 is as follows:
since the final product 3 cannot be characterized by hydrogen nuclear magnetism or infrared, the structure of the product is analyzed by means of infrared test spectrograms (figure 4 and figure 5) of the intermediate 3-1 and the intermediate 3-2 and an infrared spectrogram (figure 1), a nuclear magnetic resonance hydrogen spectrum (figure 2) and a nuclear magnetic resonance silicon spectrum (figure 3) of the final product 3.
As can be seen from the infrared spectrum of product 3 (FIG. 1), si-H (2200 cm) was absent -1 Nearby) and Si-OH (3600-3200 cm) -1 Near) and which has an infrared absorption peak, and 1 the H NMR spectrum (FIG. 2) was free of Si-H (around 4.7 ppm) and Si-OH (2.28 ppm) residues, in which 29 In the Si NMR spectrum (FIG. 3), the M segment (i.e., around 8ppm, (CH) is very significant 3 ）3SiO 1/2 Peak position of group), D mer (i.e., (-CH) around-19 ppm 3 ） 2 The peak position of SiO segment) and T segment (i.e., -69ppm or so, CH) 3 SiO 1.5 The position of the peak of the radical), the occurrence of the T chain link being the most important for the formation of the branchIt is indicated that T-mer is present for each branch formed, which is a good indication that our product is a branched product.
Infrared Spectrum (FIG. 4) of intermediate 3-1 at 2200cm -1 Has a very obvious infrared absorption peak of a silicon-hydrogen bond at 3600cm -1 ~3200cm -1 No infrared absorption peak of silicon hydroxyl. By detecting the hydrogen content (H in Si-H) of the intermediate 3-1, the hydrogen content (mass ratio of hydrogen in the silicon-hydrogen bond in the product) is 0.2288%, which is consistent with the theoretical hydrogen content (theoretical value of 0.2290%). This is a good indication that the degree of polymerization of our branched structure is controllable. Because the hydrogen content value is very different from the theoretical value if the branched chain polymerization degree is not controllable. These are sufficient evidence that we have succeeded in synthesizing a modified linear polydimethylsiloxane whose branch length is polysiloxane and whose degree of polymerization of the branches is controlled.
In addition, from DSC images of product 3 (FIG. 7) and ordinary polydimethylsiloxane (FIG. 6), we can see that the crystallization peaks of the branched modified polydimethylsiloxane at around-49 ℃ and around-35 ℃ disappear as compared with the conventional linear polydimethylsiloxane. The branched modified polysiloxane prepared by the invention can keep the flowing state at low temperature and has more excellent low-temperature resistance. The length of the polysiloxane branched chain in the invention is controllable, the performance of the polysiloxane can be adjusted by controlling the length of the branched chain, and meanwhile, the branched siloxane branched chain designed by the invention is a Si-O-Si chain link. The branched chain of the existing dimethyl siloxane is a Si-C-C chain link, and the thermal stability and the flexibility of Si-O-Si are better, so that the branched polysiloxane prepared by the invention has a wider usable temperature range, a lower low temperature and a higher high temperature, can be used within a temperature range of-110-250 ℃, and better maintains the performance of the polysiloxane.
Claims (14)
1. A modified linear polydimethylsiloxane with controllable side chain polymerization degree is characterized by having the following structural formula:
wherein R is 1 And R 2 The radicals are each identical or different neutral radicals, R 3 、R 4 、R 5 The group is any group; m + n is 2 to 1500, m is 0 to 1499, n is 2 to 1500, and x is 0 to 20.
2. The modified linear polydimethylsiloxane of claim 1, wherein R is selected from the group consisting of 1 、R 2 The groups are independently alkyl with 1 to 18 carbon atoms; m + n is 2 to 600, m is 0 to 599, n is 2 to 600; x is 0~5.
3. The modified linear polydimethylsiloxane of claim 1, wherein R is selected from the group consisting of 1 、R 2 The radicals are independently a hydrocarbon radical of 1~6 carbon atoms, R 3 、R 4 、R 5 The groups are independently hydrocarbyl or hydrocarbyloxy groups of 1~6 carbon atoms.
4. The modified linear polydimethylsiloxane of claim 1, wherein R is selected from the group consisting of 1 、R 2 The groups are independently vinyl, methyl; r 3 、R 4 、R 5 The groups are independently methyl, methoxy, phenyl, vinyl.
5. The method of preparing a modified linear polydimethylsiloxane of controllable degree of polymerization of its side chains of any of claims 1~4 comprising the steps of:
(1) Synthesizing linear polydimethylsiloxane modified by side chain silicon hydroxyl: mixing linear polydimethylsiloxane with a side chain being a hydrogen group, water, an organic solvent and a metal catalyst at the temperature of 5 to 20 ℃, and reacting for 0.5 to 3 hours to obtain a reaction solution; filtering the reaction solution, and removing water to obtain a side chain silicon hydroxyl modified linear polydimethylsiloxane product;
(2) The second step is a chain extension reaction of the side chain, comprising:
carrying out water removal treatment on the reactant in the step (1), and then adding dimethylchlorosilane and an acid-binding agent for reaction;
(ii) filtering to remove precipitate after the reaction is finished, mixing the filtrate with water and a metal catalyst, and reacting to obtain a reaction solution;
repeating the step (1) and the step (2) to obtain a side chain silicon hydroxyl end-capped linear polydimethylsiloxane reaction solution containing side chain growth, wherein the repetition times are the polymerization degree of the side chain;
(3) And (3) after the final reaction liquid obtained in the step (2) is subjected to water removal treatment, adding end-capped chlorosilane and an acid-binding agent for reaction to obtain the linear polydimethylsiloxane with controllable side chain polymerization degree.
6. The method according to claim 5, wherein the linear polydimethylsiloxane having a hydrogen group in a side chain in the step (1) has a hydrogen content of 0.1 to 0.5%.
7. The method according to claim 5, wherein the metal catalyst in step (1) or (ii) is a palladium-on-carbon catalyst, and the palladium content of the palladium-on-carbon catalyst is 10% by mass; the adding amount of the catalyst is 0.02 to 0.08 percent of the total mass of the reaction system calculated by the metal elements.
8. The method according to claim 5, wherein the organic solvent in the step (1) is 1,4-dioxane; the dosage of the organic solvent is 45 to 70 percent of the total mass of the reaction system.
9. The method according to claim 5, wherein the water is added in an amount of 1.5 to 3.0 times the theoretical requirement in step (1) or step (ii).
10. The process according to claim 5, wherein in the step (i), the reaction temperature is from 0 to 30 ℃; in the step (ii), the reaction temperature is 5 to 20 ℃.
11. The method according to claim 5, wherein the water removal treatment in step (2) or step (3) is water removal treatment with anhydrous sodium sulfate;
and (3) adding an organic amine acid-binding agent into the step (2) or the step (3).
12. The preparation method according to claim 11, wherein the organic amine is triethylamine, and the amount of the substance of nitrogen element in the organic amine is 1.0 to 1.05 times of the amount of the blocked chlorosilane substance.
13. The preparation method according to claim 5, wherein the addition amount of dimethylchlorosilane in the step (2) is 1 to 1.05 times of the amount of substances with Si-H bonds in the polymer I;
the addition amount of the end-capped chlorosilane in the step (3) is 1 to 1.05 times of the amount of substances with Si-H bonds in the polymer I.
14. The preparation method of claim 5, wherein the end-capped chlorosilane end-capping group in step (3) is a hydrocarbyl or hydrocarbyloxy group of 1~6 carbon atoms; and (3) controlling the reaction temperature to be 0-30 ℃.
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| CN116179149A (en) * | 2023-03-29 | 2023-05-30 | 广州盛泰诺新材料科技有限公司 | High-strength 107 glue and preparation method and application thereof |
| CN116179149B (en) * | 2023-03-29 | 2023-08-01 | 广州盛泰诺新材料科技有限公司 | High-strength 107 glue and preparation method and application thereof |
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