CN115124707B - Phosphorus-silicon-containing copolycarbonate and preparation method and application thereof - Google Patents
Phosphorus-silicon-containing copolycarbonate and preparation method and application thereof Download PDFInfo
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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Abstract
The invention discloses phosphorus-containing silicon copolycarbonate and a preparation method and application thereof. The polycarbonate comprises a polycarbonate segment and a phosphorus-containing polysiloxane segment, wherein the phosphorus-containing polysiloxane segment is provided by a corresponding phosphorus-containing polysiloxane monomer, and the phosphorus-containing polysiloxane monomer is prepared by an addition reaction of polysiloxane with side group containing double bonds and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. In the invention, from the aspect of molecular structure design, phosphorus-containing monomers are introduced into polysiloxane side chains, and then introduced into polycarbonate molecular chains in a chemical copolymerization mode, so that phosphorus-containing silicon copolycarbonate with excellent intrinsic flame retardance, good chemical resistance and low-temperature impact resistance can be obtained.
Description
Technical Field
The invention relates to silicon copolycarbonate, in particular to phosphorus-containing silicon copolycarbonate and a preparation method and application thereof.
Background
Polycarbonates (PC) are linear thermoplastic resins derived from bisphenols and phosgene or their derivatives. Polycarbonates have many desirable properties such as light transmittance, good impact strength, and high heat distortion temperature, and have wide applications in the automotive, electronic, construction, computer, aerospace, and other fields. The conventional PC has a flame retardant grade of V2, and cannot meet the application of the PC in the fields of electronic appliances, 5G communication, new energy and the like, so that the polycarbonate needs to be subjected to flame retardant modification.
The main modification mode at present is to add flame retardant into polycarbonate matrix, and the common flame retardant for polycarbonate comprises halogen, phosphorus, silicon, sulfonate and the like. The halogen flame retardant can seriously influence the light transmittance and impact strength of PC, and the sulfonate flame retardant has good flame retardant effect and smaller influence on the light transmittance of polycarbonate, but the sulfonate contains sulfur element, which can cause harm to environment and human body. The phosphorus flame retardant has low price, good flame retardant effect and no halogen and environmental protection, but the phosphorus flame retardant has poor heat resistance and excessive addition amount can directly influence the light transmittance of the polycarbonate. The organic silicon flame retardant has the characteristics of high efficiency, no toxicity, low smoke, drip resistance, small influence on light transmittance, processability and mechanical properties, and the like, but is limited in industrial use due to high price. Therefore, according to the current research situation, the addition of a single flame retardant cannot simultaneously meet 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 the molecule 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 reactive flame retardants, has excellent stability and good hydrolysis resistance due to the existence of P-C bonds and can be used as a flame retardant for polycarbonate. However, it has been found that DOPO flame retardants, when used alone and added to polycarbonate substrates, provide materials that have poor melt drip resistance and limited improvement in flame retardant properties.
U.S. patent No. 20210292549A1 proposes a flame retardant composition comprising a polysiloxane, wherein a phosphorus-containing flame retardant [ e.g., bisphenol a bis (diphenyl phosphate), triphenyl phosphate, resorcinol bis (diphenyl phosphate), tricresyl phosphate, oligomeric phosphate, etc. ] is added to a silicone copolycarbonate in a physically blended manner, which causes problems of migration of the flame retardant, poor long-term stability of the material, and a limited amount of flame retardant to be added.
Chinese patent CN110734551B is prepared by uniformly mixing polycarbonate resin and phosphorus-silicon flame retardant, and then carrying out melt extrusion, wherein the adopted phosphorus-silicon flame retardant is prepared by modifying DOPO flame retardant through propenol, and reacting the modified structure with phenyl hydrogen-containing silicon resin. Phosphorus and silicon elements are simultaneously introduced into the flame retardant structure and added into the polycarbonate resin to improve the flame retardant performance, but the silicon resin and the polycarbonate have the problem of poor compatibility in the melt extrusion blending process, and the blended composition is easy to generate phase separation.
Chinese patent CN101838538B discloses a polyphosphate flame retardant containing a DOPO side chain structure, which is prepared by reacting intermediate I containing a DOPO structure with phosphorus oxychloride to obtain intermediate II containing phosphorus oxychloride, and melt polymerizing the intermediate II with bisphenol compound to obtain the polyphosphate flame retardant containing a DOPO side chain structure. The patent adopts phosphorus oxychloride with strong corrosiveness and strong irritation as a raw material, and has high melting reaction temperature, great process control difficulty and difficult application in industrialization.
In summary, the existing modification method has limited improvement of the flame retardant property of the polymer, has the problems of easy migration of the flame retardant, low mechanical property reduction caused by poor compatibility with the resin base material and the like, cannot meet the requirement of the material in the high-end application field, and has wide requirements for further developing the polycarbonate product with the improved flame retardant property.
Disclosure of Invention
In order to solve the technical problems, the invention provides phosphorus-containing silicon copolycarbonate and a preparation method and application thereof. In the invention, from the aspect of molecular structure design, phosphorus-containing monomers are introduced into polysiloxane side chains, and then introduced into polycarbonate molecular chains in a chemical copolymerization mode, so that phosphorus-containing silicon copolycarbonate with excellent intrinsic flame retardance, good chemical resistance and low-temperature impact resistance can be obtained.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a phosphorus-containing silicon copolycarbonate, the polycarbonate comprising:
1) A polycarbonate chain segment represented by 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 polycarbonate has a weight percent of the segment of formula I of 70 to 99%, preferably 80 to 95% (e.g., 70%, 75%, 80%, 85%, 90%, 95%, 99%, etc.), and a weight percent of the segment of formula II of 1 to 30%, preferably 5 to 20% (e.g., 1%, 5%, 9%, 11%, 13%, 16%, 20%, 30%, etc.).
In a preferred embodiment of the invention, the polycarbonates have weight average molecular weights of 19000 to 56000g/mol, preferably 22000 to 35000g/mol.
In a preferred embodiment of the invention, the polycarbonate is prepared from bisphenol A and a phosphorus-containing polysiloxane monomer of formula III by an interfacial phosgene polycondensation process;
in the formula III, m and n are defined as the formula II.
In a preferred embodiment of the invention, the phosphorus-containing polysiloxane monomer is prepared by an addition reaction of polysiloxane with double bonds on side groups of formula IV and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
in the formula IV, m and n are defined as the formula II.
The specific preparation method of the phosphorus-containing polysiloxane monomer is as follows:
dissolving DOPO and polysiloxane with double bonds on side groups shown in formula IV into an inert solvent, adding sodium hydroxide aqueous solution into the system, refluxing for 2-6 hours at 100-150 ℃, and removing the inert solvent by flash evaporation of the obtained reaction solution to obtain the phosphorus-containing polysiloxane monomer shown in formula III.
In the method, the dosage ratio of DOPO to polysiloxane with double bonds on the side group shown in the formula IV is (1-10) based on the molar ratio of DOPO to double bond units: 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 to be 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, and the like are further preferable.
The polysiloxanes having double bonds in the side groups of formula IV can be purchased commercially or synthesized according to known published patents and literature methods, for example by the preparation of eugenol-blocked polysiloxanes in the preparatory examples of patent CN106928439B, with the only difference that part of the starting octamethyltetrasiloxane is modified to vinyl-containing siloxane monomers, such as tetramethyl-tetravinyl-cyclotetrasiloxane.
A method for preparing a phosphorus-containing silicon copolycarbonate as described above, comprising the steps of:
1) Preparing an aqueous 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 obtain a phosgene solution; mixing a phosphorus-containing polysiloxane monomer shown in a formula III with an inert solvent in another mixer to prepare a comonomer solution;
in the formula III, m and n are defined as the formula II;
3) Polymerization reaction: dropwise adding the prepared phosgene solution and comonomer solution into the water phase under the stirring condition, and carrying out polymerization reaction to obtain copolymer emulsion, wherein the reaction temperature is 30-35 ℃ and the reaction time is 2-4h;
4) Post-treatment: and purifying the copolymer emulsion, removing the inert solvent, and collecting to obtain the phosphorus-containing silicon copolycarbonate.
In a preferred embodiment of the invention, in step 1), the molar ratio of bisphenol A, capping 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 mol 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, more preferably tetrabutylammonium chloride;
preferably, the end-capping agent is one or more of phenol, p-tert-butylphenol, p-cumylphenol, 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 invention, the concentration of the phosgene solution obtained in step 2) is configured to be 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 of formula III to the inert solvent.
In a preferred embodiment of the invention, in step 3), the phosgene solution is added dropwise in the aqueous phase in an amount of (1.05-1.4): 1, preferably (1.1-1.3): 1, based on the molar ratio of phosgene to bisphenol-A;
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 of formula III to bisphenol A.
In a preferred embodiment of the present invention, the inert solvent is one or more of dichloromethane, chloroform, dichloroethane, trichloroethane;
preferably, during the polymerization of step 3), 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.
Preferably, the stirring rate of the polymerization reaction is 500 to 800rpm, more preferably 600 to 800rpm.
In step 4), the post-treatment may be performed by methods conventional in the art, such as: the copolymer emulsion is firstly subjected to oil-water separation, the oil phase is sequentially subjected to alkali washing, acid washing and multiple water washing to remove the solvent in the oil phase, and qualified copolymer powder is obtained after crushing and drying.
The use of the phosphorus-containing silicon copolycarbonate as described above or the phosphorus-containing silicon copolycarbonate produced by the method described above, for example in the fields of electronics, 5G communications, new energy sources, etc.
In the invention, from the aspect 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 obtained phosphorus-containing silicon copolycarbonate increases the contents of chemically bonded phosphorus elements and silicon elements in a PC material, and improves the intrinsic flame retardance of a product through the synergistic effect of silicon and phosphorus, and on the other hand, the polymer has good chemical resistance and low-temperature impact resistance, so that the application field of the polycarbonate material is widened. 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 invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The raw material source information in the following examples and comparative examples of the present invention are commercially available, unless otherwise specified. Wherein 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was purchased from Zhangjia Korea chemical Co.
The analytical evaluation methods involved in the examples or comparative examples of the present invention are as follows:
(1) The molecular weight was measured by Gel Permeation Chromatography (GPC), specifically using Agilent Technologies 1260 inch, methylene chloride as the mobile phase, polystyrene as the standard, flow rate of 1mL/min, column temperature and box temperature of 30 ℃.
(2) The notched Izod impact strength at-40℃is determined according to the standard test method for the detection of the Izod impact properties of plastics specified in ASTM D256-1997.
(3) Flame retardant Properties
Flammability was assessed according to the procedure of Underwriter's Laboratory Bulletin 94, titled "Tests for Flammability of Plastic Materials for Parts in Devices and Appliances" (ISBN 0-7629-0082-2), version 5, 10/29/1996, plus all revisions and including revisions at 12/2003. Several grades may be applicable based on burn rate, extinguishing time, drip resistance, and whether or not drips burn. Materials can be classified as UL94 HB, V0, V1, V2, 5VA, 5VB according to this protocol; the invention respectively detects the flame retardance of samples with the thickness of 1.5mm and 3.2 mm.
(4) Solvent resistance test
According to ASTM D543, a test piece for tensile strength test (test piece thickness 3.2 mm) was coated with a sunscreen cream (Banana coat) by a 1.0% strain clamp, and appearance change was observed, and the test piece was classified into four classes, A (no crack), B (crack), C (severe crack) and D (break) according to the weight of occurrence of cracks.
[ preparation example ]
(1) < preparation of polysiloxanes having double bonds in the side groups >
(1) Octamethyltetrasiloxane (710 g,2.40 mol), tetramethyltetravinyl cyclotetrasiloxane (828 g,2.4 mol), tetramethyldisiloxane (40.2 g,0.3 mol) and clay catalyst Filtrol 20 (23.4 g,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 warmed to 50℃at a rate of 5℃per minute and stirred at this temperature for 3 hours, then the temperature of the reaction system was continued to be warmed to 120℃at a rate of 5℃per minute and stirred vigorously at this temperature for 5 hours, and then the clay catalyst was removed by filtration. The material after the removal of the clay catalyst was then put into a reaction kettle equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2 g,1.02 mol) and karstedt catalyst (0.67 g) was added dropwise with stirring, followed by stirring at a temperature of 80℃for 13 hours. The unreacted starting materials were then distilled off under reduced pressure to 0.2kPa at 200 c to give a polysiloxane having double bonds in pendant groups in a yield of 99% and a total degree of polymerization of the product by nuclear magnetic resonance detection of 50, wherein the degree of polymerization of the polydimethylsiloxane segment was 25 and the degree of polymerization of the double bond-containing polysiloxane segment was 25, and the polysiloxane having double bonds in pendant groups prepared in this example was defined as PDMS-25-25 for convenience.
(2) Octamethyltetrasiloxane (789 g,2.66 mol), tetramethyltetravinyl cyclotetrasiloxane (356 g,2.13 mol), tetramethyldisiloxane (20.1 g,0.3 mol) and clay catalyst Filtrol 20 (23.4 g,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 warmed to 50℃at a rate of 5℃per minute and stirred at this temperature for 3 hours, then the temperature of the reaction system was continued to be warmed to 120℃at a rate of 5℃per minute and stirred vigorously at this temperature for 5 hours, and then the clay catalyst was removed by filtration. The material after the removal of the clay catalyst was then put into a reaction kettle equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2 g,1.02 mol) and karstedt catalyst (0.67 g) was added dropwise with stirring, followed by stirring at a temperature of 80℃for 13 hours. The unreacted starting materials were then distilled off under reduced pressure to 0.2kPa at 200 c to give a polysiloxane having double bonds in pendant groups in a yield of 99% and a total degree of polymerization of the product detected by nuclear magnetism of 91, wherein the degree of polymerization of the polydimethylsiloxane segment was 51 and the degree of polymerization of the double bond-containing polysiloxane segment was 40, and the polysiloxane having double bonds in pendant groups prepared in this example was defined as PDMS-51-40 for convenience.
(2) < preparation of phosphorus-containing polysiloxane monomer >
(1) DOPO (2073.0 g,9.6 mol), PDMS-25-25 (1538 g, 9.60mol double bond unit), 6L chlorobenzene, 32% sodium hydroxide solution (12 g,0.096 mol) prepared by the previous steps, were added to the reactor, mechanically stirred, warmed to 120 ℃, kept to reflux for 4 hours, and unreacted raw materials and solvents were distilled off under reduced pressure. Vacuum pumping and decompression are carried out on the reaction system for 6 hours at the reaction temperature, and finally, a viscous transparent product at normal temperature, namely a phosphorus-containing polysiloxane monomer, is obtained, which is defined as PDMS-25-25-P;
(2) DOPO (1840.0 g,8.52 mol), PDMS-51-40 (1525 g, containing 8.52mol of double bond unit) prepared in the previous step, 6L chlorobenzene, 32% sodium hydroxide solution (10.6 g,0.085 mol) were added into the reactor, mechanically stirred, heated to 120 ℃, kept to reflux for 4 hours, and distilled under reduced pressure to remove unreacted raw materials and solvent. Vacuum pumping and decompression are carried out on the reaction system for 6 hours at the reaction temperature, and finally, a viscous transparent product at normal temperature, namely a phosphorus-containing polysiloxane monomer, is obtained, which is defined as PDMS-51-40-P.
(2) < preparation of polydimethylsiloxane monomer >
Octamethyl cyclotetrasiloxane (1420 g,4.80 mol), tetramethyl disiloxane (40.2 g,0.3 mol) and clay catalyst filter 20 (23.4 g,1.6 wt%) were added to a reaction kettle equipped with a stirrer and a thermometer and stirred for 40 minutes to homogenize the material mixture, then the reaction system was warmed 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 warmed to 120 ℃ at a rate of 5 ℃/min and reacted vigorously at this temperature for 5 hours, after which the clay catalyst was removed by filtration. The mass after removal of the clay catalyst was then placed in a reaction kettle equipped with a stirrer and a thermometer and a mixed solution of eugenol (167.2 g,1.02 mol) and karstedt platinum catalyst (0.67 g) was added dropwise with stirring at a rate of 20 g/min, followed by stirring at a temperature of 80℃for 13 hours. Unreacted starting material was then distilled off under reduced pressure to 0.2kPa at 200 ℃ to give eugenol-terminated polysiloxane in 99% yield and a degree of polymerization of PDMS, as measured by nuclear magnetism, of 55, defined herein as PDMS-55 for convenience;
other conditions were unchanged, and monomers having a siloxane polymerization degree of 89 (corresponding to an amount of 20.1g of tetramethyldisiloxane) were prepared by varying the amount of tetramethyldisiloxane, respectively, and were defined herein as PDMS-89.
[ example 1 ]
Step one: 2280g bisphenol A (BPA), 1000g sodium hydroxide, 59g p-tert-butylphenol, 7200g water were added to a nitrogen-protected mixer and mixed well; after complete dissolution, 12.9g of tetrabutylammonium bromide catalyst is added to prepare aqueous solution of sodium phenolate;
step two: 1139g of liquid phosgene and 22770g of methylene dichloride are added into another mixer and mixed uniformly to form phosgene solution with the mass concentration of 4.76%; then 640g of PDMS-25-25-P and 2562g of methylene dichloride are added into a mixer and mixed uniformly to form a comonomer solution with the mass concentration of 20%;
step three: placing aqueous phase solution of sodium phenolate into a polymerization reactor, respectively adding the prepared phosgene solution and comonomer solution into the polymerization reactor at a stirring speed of 550rpm, and simultaneously, dropwise adding 32% sodium hydroxide aqueous solution with mass concentration into a reaction system to keep the pH value of the reaction system to be 11.4; the temperature of the reaction system is maintained at 35 ℃, after the reaction is carried out for 2 hours, the reaction system is separated and purified, and the solvent is removed, so that the phosphorus-containing silicon copolycarbonate is prepared.
Examples 2 to 14 and comparative examples 1 to 3
Polycarbonates were prepared in substantially the same manner as in example 1, except that the amounts of the materials fed were changed, with reference to Table 1. Examples and comparative examples include, for example, a phosgene solution and a phosphorus-containing polysiloxane monomer solution, and the mass concentrations of the solutions prepared by these methods were maintained at 4.76% and 20%, respectively.
In addition, various physical and chemical property tests were carried out on the polycarbonates prepared in each example and comparative example to obtain a chemical polycarbonate2100 served as a blank and the test results are shown in table 3.
As can be seen from the comparison of the data in the table 3, compared with the conventional PC, the polycarbonate provided by the invention has better intrinsic flame retardant property, chemical resistance and low-temperature impact resistance than the conventional PC, and the phosphorus-containing chain segment with excellent performance is introduced into the polycarbonate chain segment, so that the performance of the polycarbonate is effectively improved, and the application field of the material is widened.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Table 2, feeding parameters of each example and comparative example
TABLE 3 Performance test results
Claims (23)
1. A phosphorus-containing silicon copolycarbonate, the polycarbonate comprising:
1) A polycarbonate chain segment represented by 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, and n is selected from 1-50;
in the polycarbonate, the weight percentage of the chain segment shown in the formula I is 70-99%, and the weight percentage of the chain segment shown in the formula II is 1-30%.
2. The phosphorus-containing silicon copolycarbonate of claim 1, wherein m and n are integers in formula ii, wherein m is selected from 40 to 90 and n is selected from 5 to 40.
3. The phosphorus-containing silicon copolycarbonate of claim 1, wherein the polycarbonate comprises 80-95 wt.% of the segments of formula I and 5-20 wt.% of the segments of formula ii.
4. The phosphorus-containing silicon copolycarbonate of claim 1, wherein the weight average molecular weight of the polycarbonate is 19000-56000g/mol.
5. The phosphorus-containing silicon copolycarbonate of claim 4, wherein the weight average molecular weight of the polycarbonate is 22000-35000g/mol.
6. The phosphorus-containing silicon copolycarbonate according to any one of claims 1-5, wherein the polycarbonate is prepared from bisphenol a and a phosphorus-containing polysiloxane monomer of formula iii by an interfacial phosgene polycondensation process;
in the formula III, m and n are defined as the formula II.
7. The phosphorus-containing silicon copolycarbonate according to claim 6, wherein the phosphorus-containing polysiloxane monomer is prepared by an addition reaction of polysiloxane having double bonds on side groups represented by formula iv and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
in the formula IV, m and n are defined as the formula II.
8. A method for producing the phosphorus-containing silicon copolycarbonate as defined in any one of claims 1 to 7, comprising the steps of:
1) Preparing an aqueous 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 obtain a phosgene solution; mixing a phosphorus-containing polysiloxane monomer shown in a formula III with an inert solvent in another mixer to prepare a comonomer solution;
in the formula III, m and n are defined as the formula II;
3) Polymerization reaction: dropwise adding the prepared phosgene solution and comonomer solution into the water phase under the stirring condition, and carrying out polymerization reaction to obtain copolymer emulsion, wherein the reaction temperature is 30-35 ℃ and the reaction time is 2-4h;
4) Post-treatment: and purifying the copolymer emulsion, removing the inert solvent, and collecting to obtain the phosphorus-containing silicon copolycarbonate.
9. The method for producing a phosphorus-containing silicon copolycarbonate according to claim 8, wherein in step 1), the molar ratio of bisphenol a, the end-capping agent, the alkali metal hydroxide, and water is 1 (0.01-0.03): 2.0-3.0): 25-50;
in the step 1), the addition amount of the catalyst is 0.0001-0.006:1 according to the mol ratio of the catalyst to bisphenol A.
10. The method for producing a phosphorus-containing silicon copolycarbonate as claimed in claim 9, wherein in step 1), the molar ratio of bisphenol A, the end-capping agent, the alkali metal hydroxide, and water is 1 (0.012-0.027): 2.2-3.0): 30-50.
11. The method for producing a phosphorus-containing silicon copolycarbonate as claimed in claim 9, wherein in step 1), the catalyst is added in an amount of 0.001 to 0.005:1 in terms of a molar ratio thereof to bisphenol a.
12. The method for producing a phosphorus-containing silicon copolycarbonate according to claim 9, wherein the catalyst is one or more of triethylamine, tetrabutylammonium bromide, and tetrabutylammonium chloride.
13. The method for producing a phosphorus-containing silicon copolycarbonate as defined in claim 12, wherein the catalyst is tetrabutylammonium chloride.
14. The method for producing a phosphorus-containing silicon copolycarbonate according to claim 9, wherein the end-capping agent is one or more of phenol, p-tert-butylphenol, p-cumylphenol, and p-cyanophenol.
15. The method for producing a phosphorus-containing silicon copolycarbonate according to claim 14, wherein the end-capping agent is p-tert-butylphenol.
16. The method for producing a phosphorus-containing silicon copolycarbonate according to claim 9, wherein the alkali metal hydroxide is one or more of potassium hydroxide, sodium hydroxide, lithium hydroxide, and cesium hydroxide.
17. The method for producing a phosphorus-containing silicon copolycarbonate as defined in claim 16, wherein the alkali metal hydroxide is sodium hydroxide.
18. The method for producing a phosphorus-containing silicon copolycarbonate as defined in claim 9, wherein in step 3), the phosgene solution is added dropwise in an amount of (1.05-1.4) 1 in terms of the molar ratio of phosgene to bisphenol a;
in the step 3), the dropping amount of the comonomer solution in the water phase is 0.01 to 0.5 based on the weight ratio of the phosphorus-containing polysiloxane monomer shown in the formula III to bisphenol A.
19. The method for producing a phosphorus-containing silicon copolycarbonate as claimed in claim 18, wherein in step 3), the phosgene solution is added dropwise in an amount of (1.1-1.3) 1 in terms of a molar ratio of phosgene to bisphenol A.
20. The method for producing a phosphorus-containing silicon copolycarbonate as claimed in claim 18, wherein in step 3), the amount of the comonomer solution added dropwise in the aqueous phase is 0.05 to 0.3 in terms of the weight ratio of the phosphorus-containing polysiloxane monomer represented by formula iii to bisphenol a.
21. The method for producing a phosphorus-containing silicon copolycarbonate according to any one of claims 8 to 20, wherein the inert solvent is one or more of dichloromethane, chloroform, dichloroethane, and trichloroethane.
22. The method for producing a phosphorus-containing silicon copolycarbonate as claimed in claim 21, wherein the pH of the reaction system is maintained at 11 to 12 by adjusting the aqueous alkali metal hydroxide solution during the polymerization in step 3).
23. Use of a phosphorus-silicon copolycarbonate as defined in any one of claims 1 to 7 or as defined in any one of claims 8 to 22.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN107022071A (en) * | 2017-03-17 | 2017-08-08 | 中山市通彩化工科技有限公司 | A kind of specificity end-blocking Copolycarbonate of polysiloxane block and preparation method thereof |
| CN112280027A (en) * | 2020-10-28 | 2021-01-29 | 东莞市华盈新材料有限公司 | Phosphorus-silicon-containing copolymerized polycarbonate, preparation method and composition thereof, and preparation method and application of composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928439A (en) * | 2017-03-17 | 2017-07-07 | 中山市通彩化工科技有限公司 | A kind of low temperature resistant nontransparent HI high impact random copolymerization makrolon and its production and use |
| CN107022071A (en) * | 2017-03-17 | 2017-08-08 | 中山市通彩化工科技有限公司 | A kind of specificity end-blocking Copolycarbonate of polysiloxane block and preparation method thereof |
| CN112280027A (en) * | 2020-10-28 | 2021-01-29 | 东莞市华盈新材料有限公司 | Phosphorus-silicon-containing copolymerized polycarbonate, preparation method and composition thereof, and preparation method and application of composition |
| CN112409585A (en) * | 2020-12-07 | 2021-02-26 | 万华化学(四川)有限公司 | Copolycarbonate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 含磷氮丙烯酸酯核壳粒子的制备;李青芳;闫莉;王策;桑晓明;;精细化工(第01期);全文 * |
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