CN115676785A - Preparation method of phosphonitrile chloride catalyst and application of phosphonitrile chloride catalyst in preparation of hydrogen-containing silicone oil - Google Patents
Preparation method of phosphonitrile chloride catalyst and application of phosphonitrile chloride catalyst in preparation of hydrogen-containing silicone oil Download PDFInfo
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- CN115676785A CN115676785A CN202211104495.3A CN202211104495A CN115676785A CN 115676785 A CN115676785 A CN 115676785A CN 202211104495 A CN202211104495 A CN 202211104495A CN 115676785 A CN115676785 A CN 115676785A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 28
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims abstract description 62
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 31
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 30
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 30
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000007689 inspection Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 2
- AGISYFFNQWEPMW-UHFFFAOYSA-N n-ethylethanamine;toluene Chemical compound CCNCC.CC1=CC=CC=C1 AGISYFFNQWEPMW-UHFFFAOYSA-N 0.000 description 9
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention discloses a preparation method of a phosphonitrile chloride catalyst and application thereof in preparation of hydrogen-containing silicone oil, wherein tetrachloroethane and ammonium chloride are mixed and stirred uniformly to prepare a tetrachloroethane solution of ammonium chloride for later use; adding phosphorus pentachloride into a reaction device, slowly heating to 140-160 ℃ under the protection of nitrogen, then dropwise adding the prepared tetrachloroethane solution of ammonium chloride, heating to 170-175 ℃ after dropwise adding, and cooling to room temperature after the reaction is finished to obtain a reaction solution; and adding anisole into the reaction liquid, and stirring and mixing uniformly under a vacuum condition to obtain the phosphonitrile chloride catalyst. The preparation method of the phosphonitrile chloride catalyst and the application of the phosphonitrile chloride catalyst in preparation of hydrogen-containing silicone oil are adopted, and the prepared phosphonitrile chloride catalyst is used for preparing vinyl-terminated polydimethylsiloxane, so that the production efficiency is improved, the product quality is improved, and the storage stability is also improved.
Description
Technical Field
The invention relates to the technical field of preparation methods of organic silicon oil, in particular to a preparation method of a phosphonitrile chloride catalyst and application of the phosphonitrile chloride catalyst in preparation of hydrogen-containing silicone oil.
Background
In the traditional method for preparing the terminal vinyl silicone oil by using the tetramethylammonium hydroxide, residual substances such as trimethylamine and the like still exist after the catalyst is heated and decomposed in the reaction process, and a certain peculiar smell exists in the materials. Affecting the production and use of downstream products. In addition, the catalyst has low end-capping efficiency, contains a certain amount of hydroxyl, and can influence the addition of powder in the later period, even the rubber material has serious structurization and seriously influences the quality of the rubber material. Therefore, it is desirable to provide a new catalyst and a method for preparing the same.
Disclosure of Invention
The invention aims to provide a preparation method of a phosphonitrile chloride catalyst and application of the phosphonitrile chloride catalyst in preparation of hydrogen-containing silicone oil.
In order to realize the purpose, the invention provides a preparation method of a phosphonitrile chloride catalyst and application thereof in preparation of hydrogen-containing silicone oil, which comprises the following steps:
(1) Purging the reaction device by adopting nitrogen, carrying out preheating treatment, opening condensed water in the reaction device, and infiltrating the reaction device by using dichloromethane and tetrachloroethane in sequence;
(2) Uniformly mixing and stirring tetrachloroethane and ammonium chloride to prepare a tetrachloroethane solution of ammonium chloride for later use;
(3) Adding phosphorus pentachloride into a reaction device, slowly heating to 140-160 ℃ under the protection of nitrogen, then dropwise adding the prepared tetrachloroethane solution of ammonium chloride, performing reflux reaction after dropwise adding, heating to 170-175 ℃, continuing the reflux reaction, and cooling to room temperature after the reaction is finished to obtain a reaction solution;
(4) Adding anisole into the reaction liquid, wherein the mass ratio of the anisole to the reaction liquid is 2.
Preferably, in the step (3), the mass ratio of tetrachloroethane to ammonium chloride is 160: (10 to 11).
Preferably, in the step (4), the dropping rate of tetrachloroethane of ammonium chloride is 0.45 to 0.55L/h.
Preferably, in the step (4), the mass ratio of the phosphorus pentachloride to the ammonium chloride is 20: (2-5).
The phosphonitrile chloride catalyst prepared by the preparation method of the phosphonitrile chloride catalyst is applied to preparation of vinyl polydimethylsiloxane.
The preparation method of the phosphonitrile chloride catalyst applied to vinyl polydimethylsiloxane comprises the following steps:
(a) Carrying out air tightness inspection on the reaction device, and carrying out drying treatment;
(b) Adding a linear body and potassium hydroxide into a reaction device according to a certain proportion, mixing and stirring uniformly, reacting for 1-2 h at 140-160 ℃, adding phosphate into a reaction system after the reaction is finished, neutralizing, continuously stirring for 0.5h, removing the solvent, and preparing hydroxyl-terminated polydimethylsiloxane with the viscosity of 6-10 ten thousand;
(c) Cooling the prepared hydroxyl-terminated polydimethylsiloxane to 55-65 ℃, adding a functional material and a phosphonitrile chloride catalyst, stirring and mixing uniformly under the condition of 700-900 rpm, continuously cooling to below 40 ℃, dropwise adding a toluene solution of diethylamine with the concentration of 0.5-1.5 wt% into a reaction system, vacuumizing to-0.95 bar, controlling the temperature of the reaction system to be less than 60 ℃, stirring, continuously stirring for 2-4 h under vacuum after dropwise adding is finished, then heating to 100-120 ℃, and stirring for reaction for 0.5-1.5 h; and after the reaction is finished, cooling to below 40 ℃, and discharging to obtain the vinyl-terminated polydimethylsiloxane.
Preferably, in step (b), potassium hydroxide is used in an amount of 1ppm based on the total amount; the amount of phosphate was 3ppm based on the total amount.
Preferably, in the step (c), the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the functional material is 100: (0.5-6.0), wherein the functional material is one or more of hexamethyldisiloxane, 1, 3-tetramethyl dihydrodisiloxane and high hydrogen silicone oil.
Preferably, in step (c), the phosphazene chloride catalyst is used in an amount of 2 to 10ppm based on the total amount.
Preferably, in the step (c), the dropping rate of the toluene solution of diethylamine is 0.4 to 0.6L/h, and the dropping amount of the toluene solution of diethylamine is 1.0% of that of the hydroxy-terminated polydimethylsiloxane.
The invention has the beneficial effects that:
under the action of phosphonitrile chloride catalyst, polydimethylsiloxane is modified and terminated to prepare polydimethylsiloxane containing hydrogen methyl terminated, the amount of the catalyst used in the preparation of silicone oil is small, the residual amount is small, and the production and application of downstream products are not affected.
The polydimethylsiloxane containing hydrogen methyl end capping prepared by the phosphazene catalyst improves the production efficiency, has less catalyst consumption and has more stable storage in the later period of the product. In addition, the phosphazene is used as a catalyst, the low-viscosity to high-viscosity hydrogen-containing methyl terminated polydimethylsiloxane can be prepared, the production process is flexible and simple, and the production efficiency is greatly improved.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
The present invention will be further described with reference to examples, in which various chemicals and reagents are commercially available unless otherwise specified.
Example 1
Purging the reaction device by adopting nitrogen, carrying out preheating treatment, opening condensed water in the reaction device, and infiltrating the reaction device by using dichloromethane and tetrachloroethane in sequence. Uniformly mixing and stirring tetrachloroethane and ammonium chloride to prepare a tetrachloroethane solution of ammonium chloride for later use; the mass ratio of tetrachloroethane to ammonium chloride is 160:10. adding phosphorus pentachloride into a reaction device, wherein the mass ratio of the phosphorus pentachloride to the ammonium chloride is 20:2, slowly heating to 160 ℃ under the protection of nitrogen, and then dropwise adding the prepared tetrachloroethane solution of ammonium chloride, wherein the dropwise adding speed of the tetrachloroethane of the ammonium chloride is 0.5L/h. After the dropwise addition is finished, carrying out reflux reaction, then heating to 170 ℃, continuing the reflux reaction, and cooling to room temperature after the reaction is finished to obtain a reaction solution; adding anisole into the reaction liquid, stirring and mixing uniformly under vacuum condition to obtain target crystal, namely the phosphonitrile chloride catalyst.
Checking the air tightness of the reaction device, drying, adding the linear body and potassium hydroxide into the reaction device according to a certain proportion, and uniformly mixing and stirring, wherein the consumption of the potassium hydroxide accounts for 1ppm of the total amount. Reacting for 2 hours at 140 ℃, adding a phosphate terminating agent into the reaction system after the reaction is finished, neutralizing, continuously stirring for 0.5 hour, and removing the solvent to obtain the hydroxyl-terminated polydimethylsiloxane with the viscosity of 6-10 ten thousand, wherein the phosphate accounts for 3ppm of the total amount. Cooling the prepared hydroxyl-terminated polydimethylsiloxane to 55 ℃, adding hexamethyldisiloxane, high-hydrogen-content silicone oil and phosphonitrile chloride catalyst, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the hexamethyldisiloxane to the high-hydrogen-content silicone oil is 100:3:30, the phosphonitrile chloride catalyst is used in an amount of 2ppm based on the total amount, and the mixture is stirred and mixed uniformly at 700 rpm. Continuously cooling to below 40 ℃, dropwise adding a diethylamine toluene solution with the concentration of 0.5wt% into the reaction system, wherein the dropwise adding speed of the diethylamine toluene solution is 0.4L/h, the dropwise adding amount of the diethylamine toluene solution is 1.0% of that of the hydroxy-terminated polydimethylsiloxane, vacuumizing to-0.95 bar, controlling the temperature of the reaction system to be less than 60 ℃, stirring, continuously stirring for 2h under vacuum after the dropwise adding is finished, then heating to 120 ℃, and stirring for reaction for 0.5h; and after the reaction is finished, cooling to below 40 ℃, and discharging to obtain the hydrogen-containing methyl terminated polydimethylsiloxane.
Example 2
Purging the reaction device by adopting nitrogen, carrying out preheating treatment, opening condensed water in the reaction device, and infiltrating the reaction device by using dichloromethane and tetrachloroethane in sequence. Mixing tetrachloroethane and ammonium chloride, and stirring uniformly to obtain a tetrachloroethane solution of ammonium chloride for later use; the mass ratio of tetrachloroethane to ammonium chloride is 160:11. adding phosphorus pentachloride into a reaction device, wherein the mass ratio of the phosphorus pentachloride to the ammonium chloride is 20: and 3, slowly heating to 160 ℃ under the protection of nitrogen, and then dropwise adding the prepared tetrachloroethane solution of ammonium chloride at the dropping speed of 0.5L/h. After the dropwise addition is finished, carrying out reflux reaction, then heating to 170 ℃, continuing the reflux reaction, and cooling to room temperature after the reaction is finished to obtain a reaction solution; and adding anisole into the reaction solution, and stirring and mixing uniformly under a vacuum condition to obtain a target crystal, namely the phosphonitrile chloride catalyst.
Checking the air tightness of the reaction device, drying, adding the linear body and potassium hydroxide into the reaction device according to a certain proportion, and uniformly mixing and stirring, wherein the consumption of the potassium hydroxide accounts for 1ppm of the total amount. Reacting for 2 hours at 150 ℃, adding a phosphate terminating agent into the reaction system after the reaction is finished, neutralizing, continuously stirring for 0.5 hour, and removing the solvent to obtain the hydroxyl-terminated polydimethylsiloxane with the viscosity of 6-10 ten thousand, wherein the phosphate accounts for 3ppm of the total amount. Cooling the obtained hydroxyl-terminated polydimethylsiloxane to 60 ℃, adding 1, 3-tetramethyl dihydrodisiloxane, high hydrogen-containing silicone oil and phosphonitrile chloride catalyst, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the 1, 3-tetramethyl dihydrodisiloxane to the high hydrogen-containing silicone oil is 100:0.5:50, the phosphazene chloride catalyst was used in an amount of 6ppm of the total amount, and the mixture was stirred and mixed uniformly at 800 rpm. Continuously cooling to below 40 ℃, dropwise adding a 1.0wt% diethylamine toluene solution into the reaction system, wherein the dropwise adding speed of the diethylamine toluene solution is 0.5L/h, the dropwise adding amount of the diethylamine toluene solution is 1.0% of that of the hydroxy-terminated polydimethylsiloxane, vacuumizing to-0.95 bar, controlling the temperature of the reaction system to be less than 60 ℃, stirring, continuously stirring for 2-4 h under vacuum after the dropwise adding is finished, then heating to 120 ℃, and stirring for reaction for 1.0h; and after the reaction is finished, cooling to below 40 ℃, discharging, and preparing the end-side hydrogen-terminated polydimethylsiloxane.
Example 3
Purging the reaction device by adopting nitrogen, carrying out preheating treatment, opening condensed water in the reaction device, and infiltrating the reaction device by using dichloromethane and tetrachloroethane in sequence. Mixing tetrachloroethane and ammonium chloride, and stirring uniformly to obtain a tetrachloroethane solution of ammonium chloride for later use; the mass ratio of tetrachloroethane to ammonium chloride is 160:11. adding phosphorus pentachloride into a reaction device, wherein the mass ratio of the phosphorus pentachloride to the ammonium chloride is 20: and 5, slowly heating to 160 ℃ under the protection of nitrogen, and then dropwise adding the prepared tetrachloroethane solution of ammonium chloride at the dropping speed of 0.55L/h. After the dropwise addition is finished, carrying out reflux reaction, then heating to 175 ℃, continuing the reflux reaction, and cooling to room temperature after the reaction is finished to obtain reaction liquid; adding anisole into the reaction liquid, stirring and mixing uniformly under vacuum condition to obtain target crystal, namely the phosphonitrile chloride catalyst.
Checking the air tightness of the reaction device, drying, adding the linear body and potassium hydroxide into the reaction device according to a certain proportion, and uniformly mixing and stirring, wherein the dosage of the potassium hydroxide accounts for 1ppm of the total amount. Reacting for 2 hours at 160 ℃, adding a phosphate terminator into the reaction system after the reaction is finished, neutralizing, continuing stirring for 0.5 hour, and removing the solvent to obtain the hydroxyl-terminated polydimethylsiloxane with the viscosity of 6-10 ten thousand, wherein the phosphate accounts for 3ppm of the total amount. Cooling the hydroxyl-terminated polydimethylsiloxane prepared in the above way to 65 ℃, adding 1, 3-tetramethyl dihydrodisiloxane and phosphonitrile chloride catalyst, wherein the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the 1, 3-tetramethyl dihydrodisiloxane is 100:2, the usage amount of the phosphonitrile chloride catalyst is 10ppm of the total amount, and the mixture is stirred and mixed evenly under the condition of 900 rpm. Continuously cooling to below 40 ℃, dropwise adding a 1.5wt% diethylamine toluene solution into the reaction system, wherein the dropwise adding speed of the diethylamine toluene solution is 0.6L/h, the dropwise adding amount of the diethylamine toluene solution is 1.0% of that of the hydroxy-terminated polydimethylsiloxane, vacuumizing to-0.95 bar, controlling the temperature of the reaction system to be less than 60 ℃, stirring, continuously stirring for 4h under vacuum after the dropwise adding is finished, then heating to 120 ℃, and stirring for reaction for 1.5h; and after the reaction is finished, cooling to below 40 ℃, discharging, and preparing the hydrogen-terminated polydimethylsiloxane.
Comparative example
Comparative example is hydrogen-containing silicone oil prepared by a conventional process, and differs from examples 1 to 3 in that the catalyst is sulfuric acid.
The hydrogen-containing silicone oils obtained in examples 1 to 3 and comparative example were subjected to property testing, and the results are shown in Table 1.
TABLE 1 Performance test results for Hydrogen-containing Silicone oils
In conclusion, the method for preparing the hydrogen-containing silicone oil by using the phosphonitrile chloride catalyst has the advantages of high conversion rate, short conversion time, no need of filtering the prepared hydrogen-containing silicone oil, small catalyst dosage, good stability and wide viscosity range of the prepared hydrogen-containing silicone oil.
Finally, it should be noted that: the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of phosphonitrile chloride catalyst is characterized in that: the method comprises the following steps:
(1) Purging the reaction device by adopting nitrogen, carrying out preheating treatment, opening condensed water in the reaction device, and infiltrating the reaction device by using dichloromethane and tetrachloroethane in sequence;
(2) Uniformly mixing and stirring tetrachloroethane and ammonium chloride to prepare a tetrachloroethane solution of ammonium chloride for later use;
(3) Adding phosphorus pentachloride into a reaction device, slowly heating to 140-160 ℃ under the protection of nitrogen, then dropwise adding the prepared tetrachloroethane solution of ammonium chloride, performing reflux reaction after dropwise adding is finished, heating to 170-175 ℃, continuing the reflux reaction, and cooling to room temperature after the reaction is finished to obtain a reaction solution;
(4) Adding anisole into the reaction liquid, wherein the mass ratio of the anisole to the reaction liquid is 2.
2. A method of preparing a phosphonitrile chloride catalyst as claimed in claim 1, wherein: in the step (3), the mass ratio of tetrachloroethane to ammonium chloride is 160: (10 to 11).
3. A method of preparing a phosphonitrile chloride catalyst as claimed in claim 1, wherein: in the step (4), the dropping speed of tetrachloroethane of ammonium chloride is 0.45-0.55L/h.
4. A method of preparing a phosphonitrile chloride catalyst as claimed in claim 1, wherein: in the step (4), the mass ratio of the phosphorus pentachloride to the ammonium chloride is 20: (2-5).
5. The phosphonitrile chloride catalyst prepared by the method for preparing a phosphonitrile chloride catalyst according to any one of claims 1 to 4 is applied to the preparation of hydrogen-containing silicone oil.
6. The method for producing hydrogen-containing silicone oil according to claim 5, characterized by comprising the steps of:
(a) Carrying out air tightness inspection on the reaction device, and carrying out drying treatment;
(b) Adding a linear body and potassium hydroxide into a reaction device according to a certain proportion, mixing and stirring uniformly, reacting for 1-2 h at 140-160 ℃, adding phosphate into a reaction system after the reaction is finished, neutralizing, continuously stirring for 0.5h, removing the solvent, and preparing hydroxyl-terminated polydimethylsiloxane with the viscosity of 6-10 ten thousand;
(c) Cooling the prepared hydroxyl-terminated polydimethylsiloxane to 55-65 ℃, adding a functional material and a phosphonitrile chloride catalyst, stirring and mixing uniformly under the condition of 700-900 rpm, continuously cooling to below 40 ℃, dropwise adding a toluene solution of diethylamine with the concentration of 0.5-1.5 wt% into a reaction system, vacuumizing to-0.95 bar, controlling the temperature of the reaction system to be less than 60 ℃, stirring, continuously stirring for 2-4 h under vacuum after dropwise adding is finished, heating to 100-120 ℃, and stirring for reaction for 0.5-1.5 h; after the reaction is finished, the temperature is reduced to be below 40 ℃, and the hydrogen-containing silicone oil is obtained after discharging.
7. The method for producing hydrogen-containing silicone oil according to claim 6, characterized in that: in the step (b), the dosage of the potassium hydroxide accounts for 1ppm of the total amount; the amount of phosphate was 3ppm based on the total amount.
8. The method for producing hydrogen-containing silicone oil according to claim 6, characterized in that: in the step (c), the functional material is one or more of hexamethyldisiloxane, 1, 3-tetramethyl dihydrodisiloxane and high hydrogen silicone oil.
9. The method for producing hydrogen-containing silicone oil according to claim 6, characterized in that: in the step (c), the usage amount of the phosphonitrile chloride catalyst accounts for 2-10 ppm of the total amount.
10. The method for producing hydrogen-containing silicone oil according to claim 6, characterized in that: in the step (c), the dropping speed of the toluene solution of diethylamine is 0.4-0.6L/h, and the dropping amount of the toluene solution of diethylamine is 1.0% of that of the hydroxy-terminated polydimethylsiloxane.
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| CN116535652A (en) * | 2023-05-11 | 2023-08-04 | 东南大学 | Modified organic silicon polymer flame retardant and preparation method and application thereof |
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