CN115785449B - Side chain polymerization degree controllable modified linear polydimethylsiloxane and preparation method thereof - Google Patents
Side chain polymerization degree controllable modified linear polydimethylsiloxane and preparation method thereof Download PDFInfo
- Publication number
- CN115785449B CN115785449B CN202310087811.9A CN202310087811A CN115785449B CN 115785449 B CN115785449 B CN 115785449B CN 202310087811 A CN202310087811 A CN 202310087811A CN 115785449 B CN115785449 B CN 115785449B
- Authority
- CN
- China
- Prior art keywords
- linear polydimethylsiloxane
- side chain
- polymerization
- reaction
- modified linear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention provides modified linear polydimethylsiloxane with controllable side chain polymerization degree and a preparation method thereof, and belongs to the field of organosilicon preparation. Firstly, preparing linear polydimethylsiloxane with side chain silicon hydroxyl modified by using linear polydimethylsiloxane with side chain as hydrogen radical and water under the catalysis of metal catalyst; then carrying out chain extension reaction of the side chain to obtain side chain silicon hydroxyl end-capped linear polydimethylsiloxane with the side chain extension; and finally, adding end-capped chlorosilane and an acid binding agent for reaction to obtain the linear polydimethylsiloxane with controllable side chain polymerization degree. The polymerization degree of the branched chain is controlled by the cycle times of the reaction, and the modified linear polydimethylsiloxane with controllable side chain polymerization degree is successfully prepared. The result of 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 organosilicon preparation, and particularly relates to a 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 the 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 low rotation energy barrier. However, at around-40 ℃, the polysiloxane segments crystallize, which greatly limits the application of the polysiloxane product.
Chemical modification is a common means of improving the performance of polysiloxanes by introducing groups on both sides of the backbone of the linear polydimethylsiloxane, disrupting the crystallization of the polysiloxane chain, improving the application performance of the polysiloxane product. There are two main types of chemical modifications to linear polydimethylsiloxane products: one is to introduce other organic groups through hydrosilylation reaction, but the high temperature resistance of the introduced groups is low, so that the whole polysiloxane product has low high temperature resistance. The second is to prepare branched polydimethylsiloxane, which is mainly prepared by hydrolysis of trifunctional or tetrafunctional organosilicon monomers, but the polysiloxane prepared by the method has poor stability and can not accurately control the structure of the polysiloxane, and the performance of the product greatly fluctuates with the operation conditions.
Chinese patent CN109689734a discloses a process for the continuous production of alkoxy branched siloxanes, which is described in the patent using hydrolysis of tetrafunctional, trifunctional, difunctional and monofunctional silicone monomers. The obtained product is a partially crosslinked polysiloxane product, and the branched structure and the crosslinking degree in the product are uncontrollable. Chinese patent CN103365077a discloses a branched polysiloxane prepared by hydrosilylation of a branched polysiloxane precursor containing vinyl, alkynyl, etc. groups in Q-type and T-type with a linear polysiloxane, i.e. a 3d cross-linked network, but the chain length and cross-linking procedure prepared by this patent are still uncontrollable.
It is therefore desirable to develop a side chain controllable siloxane modified linear polydimethylsiloxane.
Disclosure of Invention
The invention provides a 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 in the prior art is uncontrollable.
A modified linear polydimethylsiloxane having a controllable degree of side chain polymerization, having the following structural formula:
wherein R is 1 And R is 2 The radicals being neutral radicals, identical or different, 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 radicals are independently hydrocarbyl radicals of 1 to 18 carbon atoms; more preferably a hydrocarbon group of 1 to 6 carbon atoms, still more preferably 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 to 5.
Preferably, R 3 、R 4 、R 5 The groups are independently hydrocarbyl or hydrocarbyloxy of 1 to 6 carbon atoms, with methyl, methoxy, phenyl, vinyl and the like being further preferred.
The invention also provides a preparation method of the modified linear polydimethylsiloxane with controllable side chain polymerization degree, which comprises the following steps:
(1) Synthesis of side chain silicon hydroxyl modified linear polydimethylsiloxane: mixing linear polydimethylsiloxane with a side chain of hydrogen group, water, an organic solvent and a metal catalyst at the temperature of 5-20 ℃ and reacting for 0.5-3 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 of hydrogen group; wherein R is 1 The radical being a neutral radical (non-acidic or non-basic), R 2 The radical being a neutral radical (non-acidic or non-basic), wherein R 1 And R is 2 PossiblyThe same, and possibly 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 growth reaction of the side chain, comprising:
carrying out water removal treatment on the reactant in the step (1), and then adding dimethyl chlorosilane and an acid binding agent for reaction;
(ii) filtering to remove precipitate after the reaction is completed, 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 linear polydimethylsiloxane reaction solution with side chain silicon hydroxyl end capped and side chain growing; 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 solution obtained in the step (2) is dehydrated, 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 hydrocarbyl or hydrocarbyloxy groups of 1 to 6 carbon atoms; methyl, methoxy, phenyl, vinyl, and the like are preferred.
Preferably, R in step (1) 1 And R is 2 The groups can be hydrocarbon groups with 1-18 carbon atoms; more preferably a hydrocarbon group of 1 to 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 (the mass fraction of hydrogen element in Si-H to the polymer I) in the linear polydimethylsiloxane with the side chain of hydrogen group in the step (1) is 0.1-1.6%. 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 addition amount of the catalyst (calculated by metal elements) is 0.02-0.08% of the total mass of the reaction system.
Preferably, the organic solvent in step (1) is 1, 4-dioxane; the dosage of the organic solvent is 45-70% of the total reaction system mass. The total reaction system comprises water, a solvent and linear polydimethylsiloxane with hydrogen groups on side chains.
Preferably, the water added in the step (1) is 1.5-3.0 times of the theoretical demand. The theoretical demand of water is the amount of the substance of the silicon-hydrogen bond in the linear polydimethylsiloxane with the side chain of hydrogen radical.
Preferably, in the step (i), si-OH and dimethylchlorosilane are used for generating Si-O-Si, and the reaction temperature is 0-30 ℃.
Preferably, in step (ii), si-H bonds are catalysed to react with water to form Si-OH, and the catalyst is a palladium on carbon catalyst. The addition amount of the catalyst (calculated by metal elements) is 0.02% -0.08% of the total mass of the reaction system. The reaction system is the same as in step (1).
Preferably, in step (ii), the water is added in the same amount as the theoretical demand of water in step (i); the reaction temperature of the Si-H bond and water is 5-20 ℃.
Preferably, the water removal treatment in the step (2) and the step (3) is water removal treatment by using neutral water-absorbable inorganic salt, and further preferred inorganic salt is anhydrous sodium sulfate.
In the reaction of Si-OH and Si-Cl to form Si-O-Si, an acid-binding agent is required to be added, and 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 further preferably, the organic tertiary amine is triethylamine. The amount of the substances containing nitrogen elements in the added tertiary amine is 1.0-1.05 times of the amount of the blocked chlorosilane substances.
Preferably, the addition amount of the dimethylchlorosilane in the step (2) is 1-1.05 times of the amount of the Si-H bond substance in the polymer I.
Preferably, the blocked chlorosilane end-capping group in step (3) is a hydrocarbyl or hydrocarbyloxy group of 1 to 6 carbon atoms. The addition amount of the end-capped chlorosilane in the step (3) is 1-1.05 times of the amount of the Si-H bond substance in the polymer I.
Preferably, the reaction temperature in the step (3) is 0-30 ℃.
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 the site disappeared, confirming that the reaction has ended completely. The degree of chain growth can be determined by measuring the nuclear magnetism and the hydrogen content of the silicon-hydrogen bond-containing intermediate (the mass percentage of hydrogen element in Si-H to the total product). The low temperature resistance effect of the resulting end product can be detected by low temperature DSC.
The beneficial effects of the invention are that
The preparation method firstly prepares the stably existing silicon hydroxyl intermediate, and utilizes the activity of silicon hydroxyl to react with chlorosilane to realize the preparation of the siloxane side chain, so as to obtain the branched polydimethylsiloxane with controllable polymerization degree of the siloxane side chain, and the whole process completely avoids the characteristic that the siloxane is easy to balance under the acid or alkali condition. The result of the low-temperature DSC test of the product shows that the product has excellent low-temperature resistance.
Because Si-OH has higher reactivity, condensation is extremely easy to occur under weak acid or weak alkaline conditions, and the traditional method for preparing hydroxyl modified polysiloxane is characterized in that the prepared polysiloxane is a random polymer and cannot obtain a linear polymer due to the fact that a catalyst is acid or alkali. In the invention, linear polydimethylsiloxane with side chain as hydrogen radical is used under neutral condition to prepare the linear polydimethylsiloxane with side chain silicon hydroxyl group modified. 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 silicon hydroxyl is ensured, and the side chain silicon hydroxyl modified linear polydimethylsiloxane with stable existence is obtained. In addition, the present invention uses the immobilized catalyst to react on the surface, and the steric hindrance of the catalyst itself also inhibits the condensation of the silicon hydroxyl groups.
In the present invention, the polymerization degree of the branched chain is controlled by the number of cycles of the reaction, and although the reaction step increases as the polymerization degree increases, the solvent and the catalyst can be reused, and thus 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 chains. According to the invention, the branched chain modified polydimethylsiloxane with controllable side chain polymerization degree is synthesized for the first time, and the polysiloxane performance can be regulated and controlled through the lengths of different side chains, so that different actual demands are met.
Drawings
FIG. 1 is an infrared spectrum of product 3;
FIG. 2 shows 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 profile for product 3.
Detailed Description
The present invention will be further described with reference to 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 of hydrogen group is purchased from the organic silicon materials Co-Ltd. Common polydimethylsiloxanes (n=75) were purchased from eastern silicone materials, inc. The hydrogen content was measured using the gas flow 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 the polymer I is as follows:
step (1): 100g of Polymer I, 3.7g of water and 230g of 1, 4-dioxane were put into a flask, stirring was started, the temperature was kept to 20℃and then 2.68g of palladium carbon catalyst (loading 10 wt.%) was added for 3 hours to react, and the platinum carbon catalyst was removed by filtration to obtain filtrate A.
Step (2):
step (1): to the filtrate A, a proper amount of anhydrous sodium sulfate was added until the sodium sulfate was not recrystallized, and the sodium sulfate was removed by filtration. 14.57g of triethylamine is added into the filtrate, stirring is started, the temperature is kept to 10 ℃, 13.62g of dimethylchlorosilane is dropwise added into the flask, the temperature is controlled to be not more than 30 ℃, and stirring is continued for 2 hours after the dropwise addition is finished. Filtering to remove salt in the system to obtain filtrate B.
Step (2): 3.7g of water is added into the filtrate B, stirring is started, the temperature is kept to 20 ℃, 2.68g of palladium-carbon catalyst is added, the reaction is carried out for 3 hours at 20 ℃, and the palladium-carbon catalyst is removed by filtration, so that filtrate C is obtained.
Repeating the steps (1) and (2) four times.
Step (3): anhydrous sodium sulfate was added to the filtrate C until the anhydrous sodium sulfate was not recrystallized, and sodium sulfate was removed by filtration. 14.57g of triethylamine are then added, stirring is started, the temperature is kept to 10℃and 15.64g of trimethylchlorosilane are added dropwise to the flask, the temperature being controlled not to exceed 30 ℃. After the completion of the dropwise addition, the reaction was continued with stirring for 2 hours. Filtering to remove salt in the system, removing solvent from the obtained filtrate at-0.090 MPa and 70deg.C to obtain colorless transparent product 1 with product viscosity of 7103mm 2 And/s. The structural formula of the 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 the polymer I is as follows:
step (1): 100g of Polymer I, 8.02g of water and 108g of 1, 4-dioxane were added to a flask, stirring was started, the temperature was kept at 10℃and then 1.09g of palladium on carbon catalyst (loading 10 wt.%) was added to react for 0.5 hour, and the platinum on carbon catalyst was removed by filtration to obtain filtrate A.
Step (2):
step (1): to the filtrate A, a proper amount of anhydrous sodium sulfate was added until the sodium sulfate was not recrystallized, and the sodium sulfate was removed by filtration. 23.23g of triethylamine is added into the filtrate, stirring is started, the temperature is kept to 10 ℃, 21.72g of dimethylchlorosilane is dropwise added into the flask, the temperature is controlled to be not more than 15 ℃, and stirring is continued for 2 hours after the dropwise addition is finished. Filtering to remove salt in the system to obtain filtrate B.
Step (2): 8.02g of water is added into the filtrate B, stirring is started, the temperature is kept to 10 ℃, 1.09g of palladium-carbon catalyst is added, the reaction is carried out for 0.5 hour at 10 ℃, and the palladium-carbon catalyst is removed by filtration, so that filtrate C is obtained.
Step (3):
anhydrous sodium sulfate was added to the filtrate C until the anhydrous sodium sulfate was not recrystallized, and sodium sulfate was removed by filtration. 23.23g of triethylamine was then added, stirring was started, the temperature was kept to 10℃and 45.62g of triethoxy chlorosilane was added dropwise to the flask, the temperature was controlled to not exceed 15 ℃. After the completion of the dropwise addition, the reaction was continued with stirring for 2 hours. Filtering to remove salt in the system, removing solvent from the obtained filtrate at-0.090 MPa and 70deg.C to obtain colorless transparent product 2 with product viscosity of 120.15mm 2 And/s. The structural formula of the 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 the polymer I is as follows:
step (1): 100g of Polymer I, 25.18g of water and 102g of 1, 4-dioxane were put into a flask, stirring was started, the temperature was kept to 5℃and then 0.46g of palladium on carbon catalyst (loading 10 wt.%) was added for 3 hours to react, and the platinum on carbon catalyst was removed by filtration to obtain filtrate A.
Step (2):
step (1): to the filtrate A, a proper amount of anhydrous sodium sulfate was added until the sodium sulfate was not recrystallized, and the sodium sulfate was removed by filtration. 47.65g of triethylamine is added into the filtrate, stirring is started, the temperature is kept to 0 ℃, 44.55g of dimethylchlorosilane is dropwise added into the flask, the temperature is controlled to be not more than 5 ℃, and stirring is continued for 2 hours after the dropwise addition is finished. Filtering to remove salt in the system to obtain filtrate B
Step (2): 25.18g of water is added into the filtrate, stirring is started, the temperature is kept to 5 ℃, 0.46g of palladium-carbon catalyst is added, the reaction is carried out for 3 hours at 5 ℃, and the palladium-carbon catalyst is removed by filtration, thus obtaining filtrate C.
Repeating the steps (1) and (2) twice to obtain the final filtrate D in the step (2). When the step (1) is repeated twice and the step (2) is repeated 1 time, an intermediate 3-1 is obtained, and the structural formula is as follows:
when the steps (1) and (2) are repeated twice, an intermediate 3-2 is obtained, and the structural formula is as follows:
Step (3)
Anhydrous sodium sulfate was added to the filtrate D until the anhydrous sodium sulfate was not recrystallized, and sodium sulfate was removed by filtration. 47.65g of triethylamine was then added, stirring was started, the temperature was kept to 0℃and 51.16g of trimethylchlorosilane was added dropwise to the flask, the temperature was controlled to not exceed 5 ℃. After the completion of the dropwise addition, the reaction was continued with stirring for 2 hours. Filtering to remove salt in the system, removing solvent from the obtained filtrate at-0.090 MPa and 70deg.C to obtain colorless transparent product 3 with product viscosity of 155.32mm 2 And/s. Structure of product 3The formula is as follows:
since the final product 3 cannot be characterized by hydrogen nuclear magnetism or infrared, the structures of the products are analyzed by means of infrared test spectrograms (fig. 4 and 5) of the intermediate 3-1 and the intermediate 3-2 and infrared spectrograms (fig. 1), nuclear magnetic resonance hydrogen spectrograms (fig. 2) and nuclear magnetic resonance silicon spectrograms (fig. 3) of the final product 3.
As can be seen from the infrared spectrum of product 3 (FIG. 1), no Si-H (2200 cm -1 Nearby) and Si-OH (3600-3200 cm) -1 Nearby) and which 1 The H NMR spectrum (FIG. 2) was free of Si-H (around 4.7 ppm) and Si-OH (2.28 ppm) residues in it 29 In the Si NMR spectrum (FIG. 3), there was a very pronounced M mer (i.e., around 8ppm, (CH) 3 ）3SiO 1/2 The position of the peak of the group) D mer (i.e., around-19 ppm, (-CH) 3 ） 2 Peak position of SiO mer and T mer (i.e. -69ppm vicinity, CH) 3 SiO 1.5 The position of the peak of the group), where the occurrence of the T-mer is the most important sign of the formation of branches, each branch is formed with the occurrence of the T-mer, which fully demonstrates that our product is a branched product.
Intermediate 3-1 in the IR spectrum (FIG. 4) at 2200cm -1 Has a very obvious infrared absorption peak of silicon-hydrogen bond at 3600cm -1 ~3200cm -1 There is no infrared absorption peak of the silicon hydroxyl group. By examining the hydrogen content (H in Si-H) of the intermediate 3-1, the hydrogen content (mass ratio of hydrogen element in the Si-H bond) was 0.2288%, which was coincident with the theoretical hydrogen content (theoretical value: 0.2290%). This fully demonstrates that the degree of polymerization of our branched structure is controllable. Because if the degree of branching polymerization is not controllable, the hydrogen content value will vary greatly from the theoretical value. These are sufficient evidence that we have successfully synthesized modified linear polydimethylsiloxanes with branched chain lengths of polysiloxane and with controllable degrees of polymerization of the branches.
In addition, from the DSC plots of product 3 (FIG. 7) and conventional polydimethylsiloxane (FIG. 6), we can see that the crystallization peaks at about-49℃and about-35℃disappeared for the branched modified polydimethylsiloxane compared to the conventional linear polydimethylsiloxane. The branched chain 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 property of the polysiloxane can be adjusted by controlling the length of the branched chain, and the branched siloxane branched chain designed by the invention is a Si-O-Si chain. The branched chain of the prior 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 chain polysiloxane prepared by the invention can be used in a larger temperature range, has lower low temperature and higher high temperature, can be used in a range of-110 to 250 ℃, and better maintains the performance of the polysiloxane.
Claims (13)
1. A modified linear polydimethylsiloxane having a controllable degree of side chain polymerization, characterized by the following structural formula:
wherein R is 1 And R is 2 The radicals being neutral radicals, identical or different, 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, x is 0 to 20;
the preparation method comprises the following steps:
(1) Synthesis of side chain silicon hydroxyl modified linear polydimethylsiloxane: mixing linear polydimethylsiloxane with a side chain of hydrogen group, water, an organic solvent and a metal catalyst at the temperature of 5-20 ℃ and reacting for 0.5-3 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 growth reaction of the side chain, comprising:
carrying out water removal treatment on the reactant in the step (1), and then adding dimethyl chlorosilane and an acid binding agent for reaction;
(ii) filtering to remove precipitate after the reaction is completed, 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 linear polydimethylsiloxane reaction solution with side chain silicon hydroxyl end capping and side chain growth, wherein the repetition number is the polymerization degree of the side chain;
(3) After the final reaction solution obtained in the step (2) is dehydrated, adding end-capped chlorosilane and an acid binding agent for reaction to obtain linear polydimethylsiloxane with controllable side chain polymerization degree;
the metal catalyst in the step (1) or the step (ii) is a palladium carbon catalyst, and the organic solvent in the step (1) is 1, 4-dioxane.
2. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains as recited in claim 1, wherein R 1 、R 2 The groups are independently hydrocarbyl groups of 1 to 18 carbon atoms; m+n is 2 to 600, m is 0 to 599, n is 2 to 600; x is 0 to 5.
3. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains as recited in claim 1, wherein R 1 、R 2 The radicals independently being hydrocarbon radicals of 1 to 6 carbon atoms, R 3 、R 4 、R 5 The groups are independently hydrocarbyl or hydrocarbyloxy groups of 1 to 6 carbon atoms.
4. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains as recited in claim 1, wherein R 1 、R 2 The radicals are independently vinyl, methyl; r is R 3 、R 4 、R 5 The groups are independently methyl, methoxy, phenyl, vinyl.
5. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains according to claim 1, wherein the hydrogen content of the linear polydimethylsiloxane having a hydrogen group as a side chain in the step (1) is 0.1 to 0.5%.
6. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains according to claim 1, characterized in that the mass content of palladium in the palladium-on-carbon catalyst in step (1) or step (ii) is 10%; the addition amount of the catalyst is calculated as 0.02-0.08% of the total system mass of the reaction by metal elements.
7. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains according to claim 1, wherein the amount of the organic solvent used in the step (1) is 45 to 70% by mass of the total reaction system.
8. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains according to claim 1, wherein the amount of water added in step (1) or step (ii) is 1.5 to 3.0 times the theoretical amount.
9. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains according to claim 1, wherein in the step (i), the reaction temperature is 0 to 30 ℃; in the step (ii), the reaction temperature is 5-20 ℃.
10. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains according to claim 1, wherein the water-removing treatment in step (2) or step (3) is a water-removing treatment with anhydrous sodium sulfate;
and (3) adding an organic amine acid binding agent in the step (2) or the step (3).
11. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains as recited in claim 10, wherein said organic amine is triethylamine and the amount of nitrogen element in said organic amine is 1.0 to 1.05 times the amount of blocked chlorosilane.
12. The modified linear polydimethylsiloxane having a controllable degree of polymerization of side chains according to claim 1, characterized in that the addition amount of dimethylchlorosilane in the step (2) is 1 to 1.05 times the amount of si—h bond substance in the polymer I;
the addition amount of the end-capped chlorosilane in the step (3) is 1-1.05 times of the amount of the Si-H bond substance in the polymer I.
13. The modified linear polydimethylsiloxane having a controllable degree of side chain polymerization according to claim 1, characterized in that the blocked chlorosilane blocking group in step (3) is a hydrocarbon group or a hydrocarbyloxy group having 1 to 6 carbon atoms; the reaction temperature of the reaction in the step (3) is 0-30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310087811.9A CN115785449B (en) | 2023-02-09 | 2023-02-09 | Side chain polymerization degree controllable modified linear polydimethylsiloxane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310087811.9A CN115785449B (en) | 2023-02-09 | 2023-02-09 | Side chain polymerization degree controllable modified linear polydimethylsiloxane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115785449A CN115785449A (en) | 2023-03-14 |
| CN115785449B true CN115785449B (en) | 2023-05-12 |
Family
ID=85430642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310087811.9A Active CN115785449B (en) | 2023-02-09 | 2023-02-09 | Side chain polymerization degree controllable modified linear polydimethylsiloxane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115785449B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365416B (en) * | 2017-08-30 | 2020-04-24 | 山东大学 | Method for preparing side chain modified polysiloxane |
| CN108003348B (en) * | 2017-12-15 | 2021-02-23 | 长兴（中国）投资有限公司 | Siloxane bridged ladder-shaped polysiloxane, preparation method and application thereof |
| CN109535428B (en) * | 2018-12-04 | 2021-06-01 | 江西蓝星星火有机硅有限公司 | Polyammonium modified polyether silicone oil and preparation method and application thereof |
| CN110358094A (en) * | 2019-07-10 | 2019-10-22 | 广东德美精细化工集团股份有限公司 | A kind of polyether-modified silicon wax of chain alkyl and preparation method thereof |
-
2023
- 2023-02-09 CN CN202310087811.9A patent/CN115785449B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115785449A (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6774202B2 (en) | Polyorganosilsesquioxane and process for preparing the same | |
| CN115785449B (en) | Side chain polymerization degree controllable modified linear polydimethylsiloxane and preparation method thereof | |
| JP6430647B2 (en) | Process for producing organopolysiloxanes | |
| CN104045831A (en) | Siloxane bridged ladderlike polysiloxane and preparation method thereof | |
| CN113544195B (en) | Polyorganosiloxane having poly (meth) acrylate groups, method for the production and use thereof | |
| JP2002212294A (en) | Multibranched polycarbosilane, polycarbosiloxane, polycarbosilazene and copolymer thereof | |
| JP2000044687A (en) | Ultra-branched polymer containing silicon atom | |
| CN102884109B (en) | Reactive amine-functional silicone-polyether block copolymers | |
| KR101474283B1 (en) | Hydrogen oligosiloxane resin and preparing method thereof | |
| Itoh et al. | Characterization and some insights into the reaction chemistry of polymethylsilsesquioxane or methyl silicone resins | |
| CN101899156B (en) | Preparation method of multichain trapezoidal polyalkyl silsesquioxane | |
| CN107400238A (en) | A kind of multi-arm siloxanes abutting ladder poly-siloxane copolymer and its preparation method and application | |
| CN103131011A (en) | Organosiloxane containing anhydride groups and manufacturing method thereof | |
| Fuchise et al. | Precise synthesis of linear polysiloxanes with a polar side-chain structure by organocatalytic controlled/living ring-opening polymerization of (3-cyanopropyl) pentamethylcyclotrisiloxane | |
| CN108299645A (en) | Can directly heat cure organosiloxane preparation and application | |
| JP2005517749A (en) | Aminomethylene functional siloxane | |
| CN112175574A (en) | Fire-resistant mica tape adhesive and preparation method thereof | |
| Gunji et al. | Preparation and properties of organic–inorganic hybrid gel films based on polyvinylpolysilsesquioxane synthesized from trimethoxy (vinyl) silane | |
| CN113549219A (en) | Preparation method of polydimethylsiloxane | |
| JP2008266301A (en) | New silicone compound, and raw material thereof and method for producing the silicone compound | |
| CN112646187A (en) | Self-crosslinking trapezoidal polysilsesquioxane polymer and preparation method and application thereof | |
| JP4906207B2 (en) | Method for producing polyorganosiloxane using solid acidic zirconia oxide catalyst | |
| Flipsen et al. | Densely crosslinked polycarbosiloxanes. I. Synthesis | |
| KR100481911B1 (en) | Polyorganosilsesquioxane and process for preparing the same | |
| CN115386087B (en) | Hydrosilylation self-crosslinking self-chain-extension linear polysiloxane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |