CN115124707A - Phosphorus-silicon-containing copolymerized polycarbonate and preparation method and application thereof - Google Patents
Phosphorus-silicon-containing copolymerized polycarbonate and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses phosphorus-silicon-containing copolymerized polycarbonate and a preparation method and application thereof. The polycarbonate comprises a polycarbonate chain segment and a phosphorus-containing polysiloxane chain segment, wherein the phosphorus-containing polysiloxane chain segment is provided by a corresponding phosphorus-containing polysiloxane monomer, and the phosphorus-containing polysiloxane monomer is prepared by performing addition reaction on polysiloxane with a double bond on a side group and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. In the invention, from the perspective of molecular structure design, a phosphorus-containing monomer is introduced into a polysiloxane side chain and then introduced into a polycarbonate molecular chain in a chemical copolymerization mode, so that the phosphorus-containing silicon copolymerized polycarbonate which is excellent in intrinsic flame retardance, and has good chemical resistance and low-temperature impact resistance can be obtained.
Description
Technical Field
The invention relates to a silicon copolymerized polycarbonate, in particular to a phosphorus-containing silicon copolymerized polycarbonate and a preparation method and application thereof.
Background
Polycarbonate (PC) is a linear thermoplastic resin derived from bisphenols and phosgene or their derivatives. Polycarbonates have many desirable properties such as light transmittance, good impact strength, and higher heat distortion temperature, and are widely used in the fields of automobiles, electronic devices, construction, computers, aerospace, and the like. The conventional PC has a flame retardant grade of V2, cannot meet the application requirements in the fields of electronic appliances, 5G communication, new energy and the like, and therefore, the polycarbonate needs to be subjected to flame retardant modification.
At present, the main modification mode is to add flame retardant into the polycarbonate matrix, and the common flame retardant for polycarbonate comprises halogens, phosphorus, silicon, sulfonate and the like. Halogen flame retardants can seriously affect the light transmittance and impact strength of PC, sulfonate flame retardants have good flame retardant effect and little influence on the light transmittance of polycarbonate, but sulfonate containing sulfur can cause harm to the environment and human bodies. The phosphorus flame retardant has low price, good flame retardant effect, no halogen and environmental protection, but the phosphorus flame retardant has poor heat resistance and can directly influence the light transmittance of the polycarbonate when too much phosphorus flame retardant is added. The organosilicon flame retardant has the characteristics of high efficiency, no toxicity, low smoke, no dripping, small influence on light transmittance, processability, mechanical property and the like, but the use of the organosilicon flame retardant in industry is limited due to high price. Therefore, according to the current research situation, the addition of a single flame retardant cannot simultaneously satisfy the performance requirements of polycarbonate.
The 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) has rich carbon source and acid source, P-H in molecules can be used as a reaction center to react with a plurality of functional groups, is an intermediate for synthesizing a series of phosphorus-containing reaction type flame retardants, has P-C bonds due to the fact that the phosphorus-containing reaction type flame retardants contain hypophosphite structures, is excellent in stability and hydrolysis resistance, and can be used as a flame retardant for polycarbonate. However, research has found that when the DOPO flame retardant is used alone and added to a polycarbonate substrate, the material has poor anti-dripping performance, and the improvement of the flame retardant performance of the material is limited.
US20210292549a1 proposes a flame retardant composition comprising a polysiloxane to which a phosphorus-containing flame retardant [ e.g. bisphenol a bis (diphenyl phosphate), triphenyl phosphate, resorcinol bis (diphenyl phosphate), tricresyl phosphate, oligomeric phosphates, etc. ] is added to a siloxane copolycarbonate in a physically blended manner, which causes problems with bleeding of the flame retardant, poor long-term stability of the material, and limited amounts of flame retardant added.
Chinese patent CN110734551B is prepared by uniformly mixing polycarbonate resin and a phosphorus-silicon flame retardant and then carrying out melt extrusion, wherein the adopted phosphorus-silicon flame retardant is prepared by modifying a DOPO flame retardant through allyl alcohol and reacting the modified structure with phenyl hydrogen-containing silicone resin. Phosphorus and silicon elements are simultaneously introduced into the flame retardant structure, and the flame retardant structure is added into polycarbonate resin to improve the flame retardant property, but the compatibility of the silicone resin and the polycarbonate in the melt extrusion blending process is poor, and the phase separation of the blended composition is easy to generate.
Chinese patent CN101838538B discloses a polyphosphate flame retardant containing a DOPO side chain structure, which is prepared by reacting an intermediate I containing the DOPO structure with phosphorus oxychloride to obtain an intermediate II containing phosphorus oxychloride, and carrying out melt polymerization on the intermediate II and a bisphenol compound to obtain the polyphosphate flame retardant containing the DOPO side chain structure. The patent adopts phosphorus oxychloride with strong corrosivity and strong irritability as a raw material, and has the advantages of high melting reaction temperature, large process control difficulty and difficult application in industrialization.
In conclusion, the existing modification method has limited improvement on the flame retardant property of the polymer, has the problems of easy migration of the flame retardant, low compatibility with resin base materials, reduced mechanical properties and the like, cannot meet the requirements of materials in high-end application fields, and still has wide requirements for further developing polycarbonate products with improved flame retardant property.
Disclosure of Invention
In order to solve the technical problems, the invention provides phosphorus-silicon-containing copolymerized polycarbonate and a preparation method and application thereof. In the invention, from the perspective of molecular structure design, a phosphorus-containing monomer is introduced into a polysiloxane side chain and then introduced into a polycarbonate molecular chain in a chemical copolymerization mode, so that the phosphorus-containing silicon copolymerized polycarbonate which is excellent in intrinsic flame retardance, and has good chemical resistance and low-temperature impact resistance can be obtained.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a phosphorus-silicon-containing copolycarbonate comprising:
1) a polycarbonate segment of the formula I,
2) a phosphorus-containing polysiloxane segment represented by formula II,
in the formula II, m and n are integers, wherein m is selected from 20-150, preferably 40-90, and n is selected from 1-50, preferably 5-40.
In a preferred embodiment of the invention, the weight percentage of segments of formula I in the polycarbonate is 70-99%, preferably 80-95% (e.g.70%, 75%, 80%, 85%, 90%, 95%, 99%, etc.), and the weight percentage of segments of formula II is 1-30%, preferably 5-20% (e.g.1%, 5%, 9%, 11%, 13%, 16%, 20%, 30%, etc.).
In a preferred embodiment of the present invention, the weight average molecular weight of the polycarbonate is 19000-56000g/mol, preferably 22000-35000 g/mol.
In a preferred embodiment of the present invention, the polycarbonate is prepared from bisphenol A and a phosphorus-containing polysiloxane monomer of formula III by interfacial phosgene polycondensation;
in the formula III, m and n are defined as in the formula II.
In a preferred embodiment of the invention, the phosphorus-containing polysiloxane monomer is prepared by an addition reaction of polysiloxane shown in a formula IV and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, wherein the polysiloxane contains double bonds in side groups;
in the formula IV, m and n are the same as those in the formula II.
Specific preparation methods of the phosphorus-containing polysiloxane monomer are as follows:
dissolving DOPO and polysiloxane with double bonds on the side group shown in the formula IV into an inert solvent, adding an aqueous solution of sodium hydroxide into the system, refluxing for 2-6 hours at the temperature of 100-150 ℃, and removing the inert solvent from the obtained reaction solution by flash evaporation to obtain the phosphorus-containing polysiloxane monomer shown in the formula III.
In the above method, the dosage ratio of the DOPO to the polysiloxane having a side group containing a double bond represented by formula iv, in terms of the molar ratio of DOPO to the double bond unit, is (1-10): 1, preferably (1-8): 1.
The mass concentration of the sodium hydroxide aqueous solution is 5-40%, preferably 20-35%; the amount of the aqueous sodium hydroxide solution added is (0.005-0.1):1, preferably (0.01-0.05):1, in terms of the molar ratio of sodium hydroxide to DOPO.
The inert solvent is, for example, a halogenated hydrocarbon, and chloroform, chlorobenzene, or the like is more preferable.
The polysiloxane having a pendant double bond represented by formula IV can be purchased commercially or synthesized according to known published patents and literature procedures, for example, referring to CN106928439B for the preparation of eugenol-terminated polysiloxane in the preliminary examples, except that a portion of the starting octamethylcyclotetrasiloxane is adjusted to a vinyl-containing siloxane monomer, such as tetramethyltetravinylcyclotetrasiloxane.
A method of making a phosphorus-silicon-containing copolycarbonate as described above, comprising the steps of:
1) preparing a water phase: uniformly mixing bisphenol A, a blocking agent and alkali metal hydroxide in water, adding a catalyst after the bisphenol A is completely dissolved, and preparing to obtain a water phase;
2) preparing an oil phase: mixing liquid phosgene with an inert solvent in a mixer to prepare phosgene solution; in another mixer, mixing phosphorus-containing polysiloxane monomer shown in formula III with inert solvent to obtain comonomer solution;
in the formula III, m and n are defined as the formula II;
3) polymerization reaction: under the condition of stirring, dropwise adding the prepared phosgene solution and the prepared comonomer solution into the water phase, and carrying out polymerization reaction to obtain copolymer emulsion, wherein the reaction temperature is 30-35 ℃, and the reaction time is 2-4 hours;
4) and (3) post-treatment: purifying the copolymer emulsion, removing the inert solvent, and collecting to obtain the phosphorus-silicon-containing copolymerized polycarbonate.
In a preferred embodiment of the invention, in step 1), the molar ratio of bisphenol A, blocking agent, alkali metal hydroxide, water is 1 (0.01-0.03): 2.0-3.0): 25-50, preferably 1 (0.012-0.027): 2.2-3.0): 30-50;
in the step 1), the addition amount of the catalyst is 0.0001-0.006:1 according to the molar ratio of the catalyst to bisphenol A; more preferably 0.001-0.005: 1; the catalyst is preferably one or more of triethylamine, tetrabutylammonium bromide and tetrabutylammonium chloride, and more preferably tetrabutylammonium chloride;
preferably, the end-capping agent is one or more of phenol, p-tert-butylphenol, p-cumylphenol and p-cyanophenol, preferably p-tert-butylphenol;
preferably, the alkali metal hydroxide is one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, preferably sodium hydroxide.
In a preferred embodiment of the present invention, the concentration of the phosgene solution prepared in step 2) is 1 (5-40), preferably 1 (10-30), in terms of the weight ratio of phosgene to inert solvent; the concentration of the comonomer solution is 1 (3-6), preferably 1 (4-5) based on the weight ratio of the phosphorus-containing polysiloxane monomer shown in the formula III to the inert solvent.
In a preferred embodiment of the present invention, in step 3), the phosgene solution is added dropwise in the aqueous phase in a molar ratio of phosgene to bisphenol A of (1.05-1.4):1, preferably (1.1-1.3): 1;
in step 3), the comonomer solution is added dropwise in the aqueous phase in an amount of 0.01 to 0.5, preferably 0.05 to 0.3, based on the weight ratio of the phosphorus-containing polysiloxane monomer represented by formula III to bisphenol A.
In a preferred embodiment of the present invention, the inert solvent is one or more of dichloromethane, trichloromethane, dichloroethane, trichloroethane;
preferably, the pH of the reaction system is maintained at 11 to 12 by adjusting the pH of the reaction system with an aqueous alkali metal hydroxide solution during the polymerization reaction in step 3).
Preferably, the stirring rate of the polymerization reaction is 500-800rpm, more preferably 600-800 rpm.
In step 4), the post-treatment may be performed by a method conventional in the art, for example: the copolymer emulsion is first oil-water separated, and the oil phase is washed successively with alkali, acid and water for several times to eliminate solvent, crushed and dried to obtain qualified copolymer powder.
An application of the phosphorus-silicon-containing copolycarbonate or the phosphorus-silicon-containing copolycarbonate prepared by the method is disclosed, for example, the application in the fields of electronic appliances, 5G communication, new energy sources and the like.
In view of molecular structure design, the phosphorus-containing monomer is introduced into a polysiloxane side chain and then introduced into a polycarbonate molecular chain in a chemical copolymerization mode, so that the obtained phosphorus-silicon-containing copolymerized polycarbonate increases the content of chemically bonded phosphorus and silicon in a PC material, improves the intrinsic flame retardance of a product through a silicon-phosphorus synergistic effect, and has good chemical resistance and low-temperature impact resistance and widens the application field of the polycarbonate material. In addition, the preparation method has simple and easy operation steps and mild conditions, and is beneficial to reducing the production cost and improving the production efficiency.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The raw material sources in the following examples and comparative examples of the present invention were obtained commercially, unless otherwise specified. Among them, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was purchased from Yarui chemical Co., Ltd, Zhang harbor.
The analytical evaluation methods involved in the examples of the present invention or the comparative examples are as follows:
(1) the molecular weight was measured by Gel Permeation Chromatography (GPC), specifically using Agilent Technologies 1260 limits, dichloromethane as mobile phase, polystyrene as standard, flow rate of 1mL/min, column temperature and box temperature both 30 ℃.
(2) Notched Izod impact Strength at-40 ℃ was measured according to the standard test method for Izod impact testing of plastics as specified in ASTM D256-1997.
(3) Flame retardant properties
Flammability was evaluated according to the Underwriter's Laboratory Bulletin 94 protocol entitled "Tests for flexibility of Plastic Materials for Parts in Devices and applications" (ISBN 0-7629-. Several ratings may be available based on the rate of burning, the extinguishing time, the ability to resist dripping, and whether the drips are burning. Following this protocol, materials can be classified as UL94 HB, V0, V1, V2, 5VA, 5 VB; the invention respectively carries out flame retardance detection on samples with the thickness of 1.5mm and 3.2 mm.
(4) Test for solvent resistance
After a sunscreen (Banana Boat) was applied to a test piece (test piece thickness 3.2mm) for tensile strength test in a 1.0% strain jig according to ASTM D543, the change in appearance was observed and classified into four grades, A (no crack), B (crack), C (severe crack) and D (break) according to the weight of crack occurrence.
[ preparative examples ]
(1) < preparation of polysiloxane having pendant double bond >
Adding octamethylcyclotetrasiloxane (710g, 2.40mol), tetramethyltetravinylcyclotetrasiloxane (828g, 2.4mol), tetramethyldisiloxane (40.2g, 0.3mol) and clay catalyst Filtrol 20(23.4g, 1.6 wt%) into a reaction kettle equipped with a stirrer and a thermometer and stirring for 40 minutes to homogenize the material mixture, then raising the temperature of the reaction system to 50 ℃ at a rate of 5 ℃/min and stirring at that temperature for 3 hours, subsequently continuing raising the temperature of the reaction system to 120 ℃ at a rate of 5 ℃/min and stirring vigorously at that temperature for 5 hours, and then filtering to remove the clay catalyst. Then, the material after removing the clay catalyst was put into a reaction kettle equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2g, 1.02mol) and karstedt's catalyst (0.67g) was added dropwise with stirring, followed by stirring reaction at a temperature of 80 ℃ for 13 hours. Unreacted raw materials were then distilled off at 200 ℃ under reduced pressure to 0.2kPa to obtain polysiloxane having a double bond in a pendant group in a yield of 99%, and the total degree of polymerization of the product was 50 as measured by nuclear magnetism, wherein the degree of polymerization of the polydimethylsiloxane segment was 25 and the degree of polymerization of the polysiloxane segment having a double bond was 25, and for convenience, the polysiloxane having a double bond in a pendant group prepared in this example was defined as PDMS-25-25.
② octamethylcyclotetrasiloxane (789g, 2.66mol), tetramethyltetravinylcyclotetrasiloxane (736g, 2.13mol), tetramethyldisiloxane (20.1g, 0.3mol) and clay catalyst Filtrol 20(23.4g, 1.6 wt%) were added to a reaction vessel equipped with a stirrer and a thermometer and stirred for 40 minutes to homogenize the material mixture, then the reaction system was heated up to 50 ℃ at a rate of 5 ℃/min and stirred at this temperature for 3 hours, then the temperature of the reaction system was continuously heated up to 120 ℃ at a rate of 5 ℃/min and stirred vigorously at this temperature for 5 hours, after which the clay catalyst was removed by filtration. Then, the material after the removal of the clay catalyst was put into a reaction tank equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2g, 1.02mol) and karstedt's catalyst (0.67g) was added dropwise with stirring, followed by stirring at a temperature of 80 ℃ for a reaction of 13 hours. Unreacted raw materials were then distilled off at 200 ℃ under reduced pressure to 0.2kPa to obtain a polysiloxane having a double bond in a pendant group in a yield of 99%, and the total degree of polymerization of the product was 91 as determined by nuclear magnetic resonance, wherein the degree of polymerization of the polydimethylsiloxane segment was 51 and the degree of polymerization of the polysiloxane segment having a double bond was 40, and for convenience, the polysiloxane having a double bond in a pendant group prepared in this example was defined as PDMS-51-40.
(2) < preparation of phosphorus-containing polysiloxane monomer >
Adding DOPO (2073.0g,9.6mol), PDMS-25-25(1538g, containing 9.60mol of double bond units) prepared in the previous step, 6L chlorobenzene and 32% sodium hydroxide solution (12g, 0.096mol) into a reactor, mechanically stirring, heating to 120 ℃, keeping reflux for 4h, and distilling under reduced pressure to remove unreacted raw materials and solvent. Maintaining the reaction temperature of the reaction system, vacuumizing and decompressing for 6 hours, and finally obtaining a viscous transparent product at normal temperature, namely a phosphorus-containing polysiloxane monomer which is defined as PDMS-25-25-P;
② adding DOPO (1840.0g,8.52mol), PDMS-51-40(1525g, containing 8.52mol of double bond unit), 6L chlorobenzene and 32% sodium hydroxide solution (10.6g, 0.085mol) into a reactor, mechanically stirring, heating to 120 ℃, keeping reflux reaction for 4h, and removing unreacted raw materials and solvent by reduced pressure distillation. And keeping the reaction system at the reaction temperature, vacuumizing and decompressing for 6 hours to finally obtain a viscous transparent product at normal temperature, namely the phosphorus-containing polysiloxane monomer, which is defined as PDMS-51-40-P.
(2) < preparation of Dimethicone monomer >
Octamethylcyclotetrasiloxane (1420g, 4.80mol), tetramethyldisiloxane (40.2g, 0.3mol) and clay catalyst Filtrol 20(23.4g, 1.6 wt%) were added to a reaction vessel equipped with a stirrer and a thermometer and stirred for 40 minutes to homogenize the material mixture, then the reaction system was heated up to 50 ℃ at a rate of 5 ℃/min and stirred at that temperature for 3 hours, and then the temperature of the reaction system was continuously heated up to 120 ℃ at a rate of 5 ℃/min and stirred vigorously at that temperature for 5 hours, after which the clay catalyst was removed by filtration. The material after removal of the clay catalyst was then put into a reaction tank equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2g, 1.02mol) and karstedt's platinum catalyst (0.67g) was added dropwise at a rate of 20 g/min with stirring, after which the reaction was stirred at a temperature of 80 ℃ for 13 hours. Followed by distillation at 200 ℃ under reduced pressure to 0.2kPa to remove unreacted starting materials, to give eugenol-terminated polysiloxane in a yield of 99%, with a degree of polymerization of PDMS 55 as determined by nuclear magnetic detection, herein defined for convenience as PDMS-55;
other conditions were unchanged, and by varying the amount of tetramethyldisiloxane, a monomer having a degree of siloxane polymerization of 89 (corresponding to an amount of tetramethyldisiloxane of 20.1g), defined herein as PDMS-89, was prepared separately.
[ example 1 ]
The method comprises the following steps: 2280g of bisphenol A (BPA), 1000g of sodium hydroxide, 59g of p-tert-butylphenol and 7200g of water are added into a mixer protected by nitrogen and are uniformly mixed; after complete dissolution, 12.9g of tetrabutylammonium bromide catalyst is added to prepare an aqueous phase solution of the sodium phenolate;
step two: adding 1139g of liquid phosgene and 22770g of dichloromethane into another mixer, and uniformly mixing to form a phosgene solution with the mass concentration of 4.76%; adding 640g of PDMS-25-25-P and 2562g of dichloromethane into a mixer, and uniformly mixing to form a comonomer solution with the mass concentration of 20%;
step three: putting the water phase solution of the phenol sodium salt into a polymerization reactor, respectively adding the prepared phosgene solution and the comonomer solution into the polymerization reactor at the stirring speed of 550rpm, and simultaneously dropwise adding a sodium hydroxide water solution with the mass concentration of 32% into a reaction system to keep the pH value of the reaction system at 11.4; and (3) maintaining the temperature of the reaction system at 35 ℃, separating and purifying the reaction system and removing the solvent after reacting for 2 hours to prepare the phosphorus-silicon-containing copolymerized polycarbonate.
[ examples 2 to 14 and comparative examples 1 to 3 ]
A polycarbonate was produced in substantially the same manner as in example 1, except that the amount of the raw materials was changed, as shown in Table 1. In each of the examples and comparative examples, if a phosgene solution and a phosphorus-containing polysiloxane monomer solution were added, the mass concentrations of the prepared solutions were maintained at 4.76% and 20%, respectively.
In addition, the physical and chemical properties of the polycarbonates prepared in the examples and comparative examples were measured to obtain a Wanhua chemical polycarbonate
2100 was used as a blank control and the results are shown in Table 3.
As can be seen from the comparison of the data in Table 3, compared with the conventional PC, the polycarbonate provided by the invention has the advantages that the intrinsic flame retardant property, the chemical resistance and the low-temperature impact resistance are superior to those of the conventional PC, the phosphorus-containing chain segment with excellent performance is introduced into the polycarbonate chain segment, the performance of the polycarbonate is effectively improved, and the application field of the material is widened.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
TABLE 2 feeding parameters for the examples and comparative examples
TABLE 3 Performance test results
Claims (10)
1. A phosphorus-silicon-containing copolymeric polycarbonate, comprising:
1) a polycarbonate segment of the formula I,
2) a phosphorus-containing polysiloxane segment represented by formula II,
in the formula II, m and n are integers, wherein m is selected from 20-150, preferably 40-90, and n is selected from 1-50, preferably 5-40.
2. The phosphorus-silicon-containing copolycarbonate according to claim 1, wherein the weight percentage of the segment represented by formula I in the polycarbonate is 70 to 99%, preferably 80 to 95%, and the weight percentage of the segment represented by formula ii is 1 to 30%, preferably 5 to 20%.
3. The phosphorus-silicon-containing copolymeric polycarbonate of claim 2, wherein the weight average molecular weight of the polycarbonate is 19000-56000g/mol, preferably 22000-35000 g/mol.
4. The phosphorus-silicon-containing copolycarbonate according to any one of claims 1 to 3, wherein the polycarbonate is prepared from bisphenol A and a phosphorus-containing polysiloxane monomer represented by formula III by interfacial phosgene polycondensation;
in the formula III, m and n are defined as in the formula II.
5. The phosphorus-silicon-containing copolycarbonate according to claim 4, wherein the phosphorus-containing polysiloxane monomer is prepared by an addition reaction of polysiloxane having a double bond in a pendant group represented by formula IV and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
in the formula IV, m and n are the same as those in the formula II.
6. A method for preparing the phosphorus-silicon-containing copolycarbonate according to any one of claims 1 to 5, comprising the steps of:
1) preparing a water phase: uniformly mixing bisphenol A, a blocking agent and alkali metal hydroxide in water, adding a catalyst after the bisphenol A is completely dissolved, and preparing to obtain a water phase;
2) preparing an oil phase: mixing liquid phosgene with an inert solvent in a mixer to prepare phosgene solution; in another mixer, mixing phosphorus-containing polysiloxane monomer shown in formula III with inert solvent to obtain comonomer solution;
in the formula III, m and n are defined as the formula II;
3) polymerization reaction: under the condition of stirring, dropwise adding the prepared phosgene solution and the prepared comonomer solution into the water phase, and carrying out polymerization reaction to obtain copolymer emulsion, wherein the reaction temperature is 30-35 ℃, and the reaction time is 2-4 hours;
4) and (3) post-treatment: purifying the copolymer emulsion, removing the inert solvent, and collecting to obtain the phosphorus-silicon-containing copolymerized polycarbonate.
7. The method of claim 6, wherein in step 1), the molar ratio of bisphenol A, the end-capping reagent, the alkali metal hydroxide and water is 1 (0.01-0.03): 2.0-3.0): 25-50, preferably 1 (0.012-0.027): 2.2-3.0): 30-50;
in the step 1), the addition amount of the catalyst is 0.0001-0.006:1 according to the molar ratio of the catalyst to bisphenol A; more preferably 0.001-0.005: 1; the catalyst is preferably one or more of triethylamine, tetrabutylammonium bromide and tetrabutylammonium chloride, and more preferably tetrabutylammonium chloride;
preferably, the end-capping agent is one or more of phenol, p-tert-butylphenol, p-cumylphenol and p-cyanophenol, preferably p-tert-butylphenol;
preferably, the alkali metal hydroxide is one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, preferably sodium hydroxide.
8. The method according to claim 7, wherein the phosgene solution is added dropwise to the aqueous phase in the amount of (1.05-1.4):1, preferably (1.1-1.3): 1;
in step 3), the comonomer solution is added dropwise in the aqueous phase in an amount of 0.01 to 0.5, preferably 0.05 to 0.3, based on the weight ratio of the phosphorus-containing polysiloxane monomer represented by formula III to bisphenol A.
9. The method of any of claims 6-8, wherein the inert solvent is one or more of dichloromethane, trichloromethane, dichloroethane, trichloroethane;
preferably, the pH of the reaction system is maintained at 11 to 12 by adjusting the pH of the reaction system with an aqueous alkali metal hydroxide solution during the polymerization reaction in step 3).
10. Use of the phosphorus-containing silicon copolycarbonate according to any one of claims 1 to 5 or the phosphorus-containing silicon copolycarbonate produced by the method according to any one of claims 6 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115124707B (en) | 2023-10-13 |
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