CN116425965A - Flame-retardant copolycarbonate and preparation method thereof - Google Patents
Flame-retardant copolycarbonate and preparation method thereof Download PDFInfo
- Publication number
- CN116425965A CN116425965A CN202310504681.4A CN202310504681A CN116425965A CN 116425965 A CN116425965 A CN 116425965A CN 202310504681 A CN202310504681 A CN 202310504681A CN 116425965 A CN116425965 A CN 116425965A
- Authority
- CN
- China
- Prior art keywords
- solution
- bisphenol
- sodium salt
- flame
- tubular reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003063 flame retardant Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- WGMBWDBRVAKMOO-UHFFFAOYSA-L disodium;4-[2-(4-oxidophenyl)propan-2-yl]phenolate Chemical class [Na+].[Na+].C=1C=C([O-])C=CC=1C(C)(C)C1=CC=C([O-])C=C1 WGMBWDBRVAKMOO-UHFFFAOYSA-L 0.000 claims abstract description 61
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims description 106
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 239000007788 liquid Substances 0.000 claims description 75
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 69
- 239000012266 salt solution Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 claims description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 9
- 238000010924 continuous production Methods 0.000 abstract description 7
- 238000006552 photochemical reaction Methods 0.000 abstract description 4
- 239000004417 polycarbonate Substances 0.000 abstract description 4
- 229920000515 polycarbonate Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- -1 halogenated bisphenol A acyl chloride Chemical class 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 150000001263 acyl chlorides Chemical class 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GCXUHGZBBGZTII-UHFFFAOYSA-N a828071 Chemical compound ClC(Cl)=O.ClC(Cl)=O GCXUHGZBBGZTII-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- HNDVYGDZLSXOAX-UHFFFAOYSA-N 2,6-dichloro-4-propylphenol Chemical compound CCCC1=CC(Cl)=C(O)C(Cl)=C1 HNDVYGDZLSXOAX-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to flame-retardant copolycarbonate and a preparation method thereof. The preparation method of the flame-retardant copolycarbonate provided by the invention adopts a process of pre-photochemical reaction of halogenated bisphenol A sodium salt and then blending with bisphenol A sodium salt, and combines a phase transfer catalyst and phosgene solution, thereby realizing the preparation of high-molecular-weight polycarbonate with flame-retardant effect in a continuous process.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to flame-retardant copolycarbonate and a preparation method thereof.
Background
Copolycarbonates can be classified into high molecular weight based on molecular weightAnd a low molecular weight co-oligomer. Wherein the high molecular weight copolycarbonate has excellent flame retardant property, can ensure that the product has excellent electrical property and thermal stability, has small influence on the transparency of materials (such as transparent flame retardant PC), can be widely applied to the fields of household appliances, automobiles, offices and the like, and can be prepared into a flame retardant resin for O 2 /N 2 The membrane with higher selectivity and permeability is applied to the high molecular membrane separation technology.
However, in the production process of high molecular weight copolycarbonates, halogen atoms have large steric hindrance, and side reactions occur in the synthesis process, so that the requirement of high molecular weight can only be met by adjusting the reaction time in the kettle-type batch production at present, and when the synthesis is performed by the continuous method of interfacial polycondensation, the high molecular weight flame-retardant copolycarbonates with two or more bisphenol chloroformate units with Mw of more than 15000 cannot be synthesized by the continuous production process at present because the reaction time of the continuous method is limited and the reaction time is relatively fixed.
Disclosure of Invention
Aiming at the technical problems, the invention provides flame-retardant copolycarbonate and a preparation method thereof. The preparation method provided by the invention is a method for preparing the flame-retardant copolycarbonate with two or more bisphenol chloroformate units, and realizes the preparation of the high molecular weight polycarbonate with flame-retardant effect in a continuous process.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a flame retardant copolycarbonate, the method being carried out in a tubular reactor, comprising in particular the following operations:
introducing phosgene solution and halogenated bisphenol A sodium salt solution into a first-stage tubular reactor, and reacting for 60-600 s to obtain a first feed liquid; the pH value of the halogenated bisphenol A sodium salt solution is 10.5-13.5, and the molar ratio of the halogenated bisphenol A sodium salt to phosgene is 1: (0.95-2);
uniformly mixing the first feed liquid with bisphenol A sodium salt solution, and then simultaneously introducing the mixture and phosgene solution into a two-stage tubular reactor for reaction for 45-300 s to obtain second feed liquid;
introducing the second feed liquid and the end capping reagent solution into a three-section tubular reactor simultaneously to react for 77-460s to obtain a third feed liquid;
introducing the third feed liquid and sodium hydroxide solution into a four-section tubular reactor simultaneously, and reacting for 63-355s under the condition that the pH value is 11-13.5 to obtain fourth feed liquid;
introducing the fourth feed liquid and dichloromethane into a five-section tubular reactor simultaneously to react for 102-720 seconds to obtain a fifth feed liquid;
and simultaneously introducing the fifth feed liquid and the phase transfer catalyst solution into a six-section tubular reactor to react for 45-175s, so as to obtain the solution containing the flame-retardant copolycarbonate.
The preparation method provided by the invention takes the halogenated bisphenol A sodium salt as one of the reaction raw materials, and compared with the halogenated bisphenol A, the sodium salt has higher reaction activity. On the premise of not changing the continuous reaction, firstly reacting phosgene solution and halogenated bisphenol A sodium salt solution in a one-stage tubular reactor for a specific time to obtain a pre-photochemical product halogenated bisphenol A acyl chloride monomer. If the reaction time is too short in a one-stage tubular reactor, the reaction cannot be completed, halogenated bisphenol A acyl chloride monomer cannot be generated, then in the process of continuing the subsequent reaction, halogenated bisphenol A sodium salt which does not generate halogenated bisphenol A acyl chloride monomer is affected by steric hindrance effect, the reaction efficiency with phosgene is low, a large amount of bisphenol A sodium salt can react with phosgene to generate bisphenol A acyl chloride monomer with both ends being acyl chloride end-capped, and then a polymer molecular chain cannot extend, and finally small molecular substances with molecular weight (Mw) of 2000-5000 are generated, and a large amount of halogenated bisphenol A sodium salt remains in a water phase; if the reaction time is too long, the pH value in the reaction process is reduced to below 7.5, so that the halogenated bisphenol A is separated out to generate precipitate, and the next oligomerization reaction cannot be performed. The pH value of the halogenated bisphenol A sodium salt solution and the molar ratio of the halogenated bisphenol A sodium salt to phosgene are also important conditions for ensuring the formation of halogenated bisphenol A acyl chloride monomers, on one hand, the molar ratio of the halogenated bisphenol A sodium salt to the phosgene keeps the pH value of a reaction system between 8.5 and 10 so as to ensure smooth pre-photochemical reaction, and on the other hand, too low phosgene proportion can cause insufficient phosgene addition amount, so that the halogenated bisphenol A acyl chloride monomers cannot be formed and the halogenated bisphenol A reaction rate cannot be improved; if the phosgene addition amount is too high, a halogenated bisphenol A monomer with both ends capped by acyl chloride is generated, and a long chain cannot be formed with bisphenol A in the subsequent synthesis reaction, so that high-molecular-weight flame-retardant copolycarbonate cannot be further generated.
In a two-stage tubular reactor, the halogenated bisphenol A acid chloride monomer and bisphenol A begin to form a low molecular weight copolycarbonate under the action of phosgene.
In a three-stage tubular reactor, the low molecular weight copolycarbonate is subjected to an end-capping reaction under the action of an end-capping agent.
In the blending state of the halogenated bisphenol A and bisphenol A, the steric hindrance effect of halogen atoms can cause lower reaction rate of the halogenated bisphenol A, so that the halogen content in the flame-retardant copolycarbonate with large molecular weight can not meet the requirement, and the glass transition temperature Tg of the prepared flame-retardant copolycarbonate is difficult to reach 170 ℃ or above. According to the invention, the pH value can be kept at 11-13.5 by introducing sodium hydroxide solution into the four-section tubular reactor, so that the reaction rate of halogenated bisphenol A is improved, the halogen content in the final product is improved, and the residues of bisphenol A sodium salt and tetrabromobisphenol A sodium salt in the water phase can be effectively reduced to below 50ppm. Meanwhile, the sodium hydroxide solution can consume excessive phosgene, so that the content of phosgene in the reaction waste liquid is reduced. In a four-stage tubular reactor, the formation of low molecular weight copolycarbonates is accomplished by halogenated bisphenol A and bisphenol A.
Due to the existence of halogen elements, compared with the phenolic hydroxyl groups of bisphenol A, the phenolic hydroxyl groups on the halogenated bisphenol A are more prone to oxidation reaction to generate quinone substances, so that the transmittance and yellowness index of the copolycarbonate obtained by the reaction are not easy to control. According to the invention, methylene dichloride is supplemented in the five-section tubular reactor, so that the polymerization of the low-molecular-weight copolycarbonate into the high-molecular-weight copolycarbonate is further promoted, the ratio of the organic phase to the aqueous phase in the reaction system can be adjusted, the interface ratio is increased, the reaction activity is increased, the end-capping rate of the flame-retardant copolycarbonate is greatly improved, the end-capping rate is more than 93%, and the content of free phenolic hydroxyl is greatly reduced.
In a six-section tubular reactor, the added catalyst solution enables the acyl chloride end capped chloroformate and the sodium phenolate end capped chloroformate to further undergo polycondensation reaction at the two-phase interface, thereby improving the molecular chain length and finally obtaining the high molecular weight flame retardant copolycarbonate.
In the preparation method, sodium hydroxide, methylene dichloride and a phase transfer catalyst need to be added in the strict sequence, if sodium hydroxide, methylene dichloride and triethylamine are added simultaneously, the reaction is too severe, the molecular weight distribution is uneven, the V0 flame retardant standard cannot be achieved, and the residual halogenated bisphenol A is more than 50ppm.
The preparation method provided by the invention can obtain the flame-retardant copolycarbonate with high molecular weight, and is suitable for the production of the full-series flame-retardant copolycarbonate with the melt index range of 3-50 and the halogen content range of 0.58-44.56%.
In combination with the first aspect, the phosgene solution is phosgene (phosgene) and methylene dichloride according to a mass ratio of 1: (2-20) and mixing.
In combination with the first aspect, the molar ratio of the halogenated bisphenol a sodium salt to phosgene is 1: (1.15-1.5).
With reference to the first aspect, the pH of the halogenated bisphenol a sodium salt solution is preferably 12 to 13.
With reference to the first aspect, the pH of the bisphenol a sodium salt solution is 10.5 to 13.5, preferably 12 to 13.
In combination with the first aspect, in the preparation method provided by the invention, the halogenated bisphenol A sodium salt solution and the bisphenol A sodium salt solution can be prepared by mixing halogenated bisphenol A and bisphenol A with alkali metal hydroxide solution respectively.
The halogenated bisphenol A is shown in a formula I:
wherein X is 1 ,X 2 ,X 3 ,X 4 Is halogenAn atom.
Preferably, the halogenated bisphenol a comprises: 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane. Further preferred is 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, namely tetrabromobisphenol A.
Preferably, the alkali metal hydroxide may be selected from sodium hydroxide or potassium hydroxide, and further preferably sodium hydroxide is used.
Preferably, the concentration of the alkali metal hydroxide solution is 3% to 10% by weight, more preferably 3% to 6% by weight.
The molar ratio of the halogenated bisphenol A to the alkali metal hydroxide is preferably 1: (2 to 2.5), more preferably 1: (2.03 to 2.1).
The molar ratio of bisphenol A to alkali metal hydroxide is preferably 1: (2-2.5), more preferably 1: (2.03-2.1).
In combination with the first aspect, the mass ratio of the halogenated bisphenol A to the bisphenol A is 1: (0.5 to 99), preferably 1: (0.5 to 10), and more preferably 1:0.67.
In combination with the first aspect, the molar ratio of bisphenol a sodium salt to phosgene in the phosgene solution in the one-stage tubular reactor is 1: (1.03 to 1.5), preferably control 1: (1.15-1.3).
With reference to the first aspect, the reaction time in the one-stage tubular reactor is preferably 300 to 600 seconds.
In combination with the first aspect, the capping agent may be phenol, p-tert-butylphenol or p-cumylphenol, and illustratively, the capping agent is p-tert-butylphenol and the solvent is methylene chloride. The same effect can be achieved by the end-capping agent having the same principle of action as the end-capping agent described above, which is not limited in the present invention.
Preferably, the mass ratio of the end-capping agent to dichloromethane in the end-capping agent solution is 1: (4-20).
Preferably, the ratio of the mass of the end-capping agent to the total mass of bisphenol A and halogenated bisphenol A is 1 (35-66), more preferably 1: (38-60).
In combination with the first aspect, the phase transfer catalyst is an organic tertiary amine including triethylamine, tripropylamine and tributylamine, and the solvent is dichloromethane. The same effect can be achieved by the phase transfer catalyst having the same principle of action as the above-mentioned phase transfer catalyst, and the present invention is not limited thereto.
Illustratively, the tertiary organic amine is triethylamine.
Preferably, the mass ratio of the phase transfer catalyst to dichloromethane in the phase transfer catalyst solution is 1: (10-50).
Preferably, the ratio of the amount of the substance of the organic tertiary amine to the total amount of the halogenated bisphenol A sodium salt and the bisphenol A sodium salt is 1 (9 to 32), preferably 1: (14-23).
In combination with the first aspect, the viscosity of the solution containing the flame retardant copolycarbonate is controlled to 50-200cP in a six-stage tubular reactor to ensure the efficiency of the subsequent centrifugal washing. At this viscosity, the concentration of flame retardant copolycarbonate in the solution is about 8% to 20% by weight.
With reference to the first aspect, the reaction temperature of the four-section tubular reactor is 3-40 ℃, preferably 25-33 ℃; the reaction pressure is 10 to 600KPaG, preferably 100 to 400KPaG. The reaction in the four-section tubular reactor is the end of oligomerization reaction, and the temperature and pressure of the outlet of the four-section tubular reactor are controlled, which is equivalent to the reaction of the three-section reactor in the front of the four-section tubular reactor, and plays a certain limiting role.
In combination with the first aspect, the preparation method further comprises standing a solution containing the flame-retardant copolycarbonate, removing the aqueous phase, washing the obtained organic phase with 1-5 wt% of hydrochloric acid, and washing with deoxygenated water to obtain a washed organic phase with a pH of 6.5-7.5, preferably 6.5-6.8. The pH can be regulated and controlled by adding a small amount of hydrochloric acid in the centrifugal washing process, and the oxidation reaction of free phenolic hydroxyl groups is inhibited, so that the light transmittance and the yellowness index of the flame-retardant copolycarbonate are effectively controlled.
In a second aspect, the invention provides a flame retardant copolycarbonate prepared by the above method of preparation.
The invention has the beneficial effects that: the preparation method provided by the invention can realize the production of the flame-retardant copolycarbonate on a continuous production line, the glass transition temperature Tg range of the obtained flame-retardant copolycarbonate is 147-171 ℃, the flame retardant grade can reach V0 (1.2 mm), the light transmittance range is 88-90%, the yellowness index YI range is 1.0-5.0, and the halogen content can reach 34.52% at the highest.
Drawings
FIG. 1 is a schematic of the synthesis scheme in a tubular reactor in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The high molecular weight copolycarbonate has excellent flame retardant property, has little influence on the transparency of the material, and can be prepared into a material with low impact on O 2 /N 2 The film with higher selectivity and permeability has wide application prospect. However, in the production process, the halogen atom has larger steric hindrance and side reaction occurs in the synthesis process, so that the synthesis is difficult to realize on a continuous production line at present.
The invention obtains a method for preparing the flame-retardant copolycarbonate on a continuous production line through a large amount of experimental researches. The method creatively takes halogenated bisphenol A sodium salt and bisphenol A sodium salt as reaction raw materials, adopts a process of pre-photochemical reaction of the halogenated bisphenol A sodium salt and then blending with the bisphenol A sodium salt on the premise of not changing continuous reaction, so that the halogenated bisphenol A sodium salt is used for producing halogenated bisphenol A acyl chloride groups, then utilizes high reactivity of the acyl chloride groups and combines a phase transfer catalyst and phosgene solution to carry out oligomerization reaction with the bisphenol A sodium salt, and then increases the molecular weight by introducing a pre-photochemical means, thereby preparing the high molecular weight copolycarbonate with flame retardant effect and Mw of more than 30000 in the continuous process.
The following describes the embodiments of the present invention by way of specific examples.
The advection pumps used in the following examples and comparative examples were the 2PB series advection pumps of the Shenzhou micro-department.
Example 1
The embodiment provides a preparation method of flame-retardant copolycarbonate.
1. Preparation:
mixing tetrabromobisphenol A and 4%wt sodium hydroxide solution (the molar ratio of tetrabromobisphenol A to sodium hydroxide is 1:2.10) to prepare tetrabromobisphenol A sodium salt solution with the tetrabromobisphenol A sodium salt concentration of 22.3%wt and the pH value of 12.8 for later use;
bisphenol A and 6%wt sodium hydroxide solution (the mole ratio of bisphenol A to sodium hydroxide is 1:2.10) are mixed to prepare bisphenol A sodium salt solution with bisphenol A sodium salt concentration of 16.7%wt and pH value of 13 for standby;
phosgene (phosgene) was combined with dichloromethane at 1: mixing at a mass ratio of 5.85 to obtain a phosgene solution with a phosgene concentration of 14.6 wt% for later use;
p-tert-butylphenol was reacted with methylene chloride in an amount of 1:9, mixing to obtain a capping agent solution with the concentration of the p-tert-butylphenol of 10%wt for later use;
triethylamine was mixed with methylene chloride at a mass ratio of 1:15.7 to give a phase transfer catalyst solution having a triethylamine concentration of 6% by weight for use.
2. Synthesis in a tubular reactor
Introducing tetrabromobisphenol A sodium salt solution and phosgene solution into a section of tubular reactor simultaneously by a advection pump, setting the flow rate of the tetrabromobisphenol A sodium salt solution to be 150.00g/min, setting the flow rate of the phosgene solution to be 55.46g/min, and reacting for 600s (the pH value is maintained between 8.5 and 10 in the reaction process and the pH value at the end of the reaction is 9), wherein the pre-photochemical reaction is finished at the moment to obtain a first feed liquid;
mixing the first feed liquid with bisphenol A sodium salt solution (the mass ratio of halogenated bisphenol A to bisphenol A is 1:0.67), then simultaneously introducing the mixture and phosgene solution into a two-stage tubular reactor, setting the flow rate of the mixed solution of the first feed liquid and bisphenol A sodium salt solution to 355.46g/min, setting the flow rate of the phosgene solution to 79.32g/min, and reacting for 300s to obtain a second feed liquid;
mixing the second feed liquid with a capping reagent solution (the ratio of the mass of the capping reagent to the total mass of bisphenol A and halogenated bisphenol A is 1:59), introducing the mixture into a three-section tubular reactor, setting the flow rate of the mixed solution of the second feed liquid and the capping reagent solution to 443.555g/min, and reacting for 460 seconds to obtain a third feed liquid;
mixing the third feed liquid with 32%wt concentration sodium hydroxide solution (the mass ratio of the third feed liquid to the sodium hydroxide solution is 1:0.15), and introducing the mixture into a four-section tubular reactor, wherein the flow rate of the mixture of the third feed liquid and the sodium hydroxide solution is 512.115g/min; after 355s of reaction (the pH value is maintained between 12.5 and 13 in the reaction process, and the pH value at the end of the reaction is 13), the oligomerization reaction is finished, and a fourth feed liquid is obtained;
maintaining the outlet temperature of the four-section tubular reactor at 30+/-3 ℃ and the pressure at 450+/-50 KPaG, mixing the fourth feed liquid with dichloromethane (the mass ratio of the fourth feed liquid to the dichloromethane is 1:0.43), introducing the mixture into the five-section tubular reactor, setting the flow rate of the mixed liquid of the dichloromethane and the fourth feed liquid to 730.45g/min, and reacting for 720s to obtain a fifth feed liquid;
mixing the fifth feed liquid with the phase transfer catalyst solution (the mass ratio of the fifth feed liquid to the phase transfer catalyst solution is 1:0.036), introducing the mixture into a six-section tubular reactor, setting the flow rate of the mixture of the fifth feed liquid and the phase transfer catalyst solution to 757.02g/min, and reacting for 175s to obtain the flame-retardant copolycarbonate solution with Mw of 31630.
The flow chart of the synthesis process is shown in fig. 1.
Standing the obtained flame-retardant copolycarbonate solution, removing a water phase, and simultaneously measuring that the total sum of bisphenol A sodium salt and tetrabromobisphenol A sodium salt residues in the water phase of the solution is 38ppm; the obtained organic phase is firstly washed with 2 percent by weight of hydrochloric acid, then is washed with deoxidized water, the pH value of the washed organic phase is 6.8, and the organic phase is dried, thus obtaining the flame-retardant copolycarbonate. Through detection, the bromine content in the obtained flame-retardant copolycarbonate reaches 30%, and the flame-retardant grade is V0.
Examples 2 to 6
Examples 2 to 6 provide a method for preparing flame retardant copolycarbonates, respectively, and a method for synthesizing the same in a tubular reactor as in example 1, except for the concentration of the solution and the flow rate and pH during the synthesis.
The formulation parameters for each solution in each example are shown in tables 1-3.
Table 1 formulation parameters of tetrabromobisphenol a sodium salt solution in examples 2 to 6
Table 2 formulation parameters of bisphenol a sodium salt solution in examples 2 to 6
TABLE 3 concentration of other solutions in examples 2-6
The process parameters for the synthesis in the tubular reactor in each example are shown in tables 4 to 9.
Table 4 process parameters for the synthesis in a one-stage tubular reactor in examples 2 to 6
Table 5 process parameters for the synthesis in the two-stage tubular reactor in examples 2 to 6
Table 6 process parameters for the synthesis in three-stage tubular reactors in examples 2 to 6
Table 7 process parameters for the synthesis in the fourth tubular reactor in examples 2 to 6
Table 8 process parameters for the synthesis in five-stage tubular reactors in examples 2 to 6
Table 9 process parameters for the synthesis in six-stage tubular reactor in examples 2 to 6
Standing the obtained flame-retardant copolycarbonate solution, removing a water phase, and simultaneously measuring the residual sum of bisphenol A sodium salt and tetrabromobisphenol A sodium salt in the water phase of the solution; the obtained organic phase is firstly washed with 2 percent by weight of hydrochloric acid, then washed with deoxidized water and dried, thus obtaining the flame-retardant copolycarbonate. The molecular weight of the flame-retardant copolycarbonate in the flame-retardant copolycarbonate solution obtained in each example, the sum of bisphenol A sodium salt and tetrabromobisphenol A sodium salt residues in the aqueous phase, the pH value of the organic phase after washing, and the bromine content in the flame-retardant copolycarbonate after drying are shown in Table 10.
Table 10 data of examples 2 to 6 before and after treatment of the resulting flame-retardant copolycarbonate solution
Comparative example 1
The comparative example provides a method for preparing flame-retardant copolycarbonate.
1. Preparation: as in example 1.
2. Synthesis in a tubular reactor
Mixing tetrabromobisphenol A sodium salt solution and bisphenol A sodium salt solution by a advection pump, then simultaneously introducing the mixture and phosgene solution into a two-stage tubular reactor, setting the flow rate of the tetrabromobisphenol A sodium salt solution to be 150.00g/min, setting the flow rate of the bisphenol A sodium salt solution to be 150.00g/min (the flow rate of the mixed solution of the tetrabromobisphenol A sodium salt solution and the bisphenol A sodium salt solution to be 300.00 g/min), setting the flow rate of the phosgene solution to be 134.78g/min, and obtaining the outlet product of the two-stage tubular reactor after 300s of reaction;
mixing the end capping agent solution with the outlet product of the two-stage tubular reactor (the mass ratio of the end capping agent solution to the outlet product of the two-stage tubular reactor is 1:0.02), introducing the mixture into the three-stage tubular reactor, setting the flow rate of the mixture of the end capping agent solution and the outlet product of the two-stage tubular reactor to 443.555g/min, and reacting for 460 seconds to obtain the outlet product of the three-stage tubular reactor;
mixing 32% wt concentration sodium hydroxide solution with a three-section tubular reactor outlet product (the mass ratio of the three-section tubular reactor outlet product to the sodium hydroxide solution is 1:0.15), introducing the mixture into a four-section tubular reactor, setting the flow rate of the mixture of the three-section tubular reactor outlet product and the sodium hydroxide solution to 512.115g/min, maintaining the pH value between 12.5 and 13, and reacting 355s to obtain the four-section tubular reactor outlet product;
maintaining the outlet temperature of the four-section tubular reactor at 27-33 ℃ and the pressure at 300-550 KPaG, mixing dichloromethane and the outlet product of the four-section tubular reactor (the mass ratio of the outlet product of the four-section tubular reactor to dichloromethane is 1:0.43), introducing the mixture into a five-section tubular reactor, setting the flow rate of the mixture of the two to 730.45g/min, and reacting for 720s to obtain the outlet product of the five-section tubular reactor;
mixing the phase transfer catalyst solution with the outlet product of the five-section tubular reactor (the mass ratio of the outlet product of the five-section tubular reactor to the phase transfer catalyst solution is 1:0.036), introducing the mixture into the six-section tubular reactor, setting the flow rate of the mixture of the two to 757.02g/min, and after 175s of reaction, completing the reaction to obtain the copolymerized polycarbonate solution with Mw of 12750.
Comparative example 2
The comparative example provides a method for preparing flame-retardant copolycarbonate.
1. Preparation: as in example 1.
2. Synthesis in a tubular reactor
Introducing tetrabromobisphenol A sodium salt solution and phosgene solution into a section of tubular reactor simultaneously by a advection pump, setting the flow rate of the tetrabromobisphenol A sodium salt solution to be 150.00g/min, setting the flow rate of the phosgene solution to be 55.46g/min, and reacting for 600s to obtain a first feed liquid;
mixing the first feed liquid with bisphenol A sodium salt solution (the mass ratio of halogenated bisphenol A to bisphenol A is 1:0.67), then simultaneously introducing the mixture and phosgene solution into a two-stage tubular reactor, setting the flow rate of the mixed solution of the first feed liquid and bisphenol A sodium salt solution to 355.46g/min, setting the flow rate of the phosgene solution to 79.32g/min, and reacting for 300s to obtain a second feed liquid;
mixing the second feed liquid with a capping reagent solution (the ratio of the mass of the capping reagent to the total mass of bisphenol A and halogenated bisphenol A is 1:59), introducing the mixture into a three-section tubular reactor, setting the flow rate of the mixed solution of the second feed liquid and the capping reagent solution to 443.555g/min, and reacting for 460 seconds to obtain a third feed liquid;
mixing the third feed liquid with 32%wt concentration sodium hydroxide solution, methylene dichloride and phase transfer catalyst solution (the mass ratio of the third feed liquid to the sodium hydroxide solution, the methylene dichloride and the phase transfer catalyst is 1:0.15:0.43:0.036), introducing the mixture into a four-section tubular reactor, setting the flow rate of the mixture of the third feed liquid, the sodium hydroxide solution, the methylene dichloride and the phase transfer catalyst solution to 757.02g/min, and reacting for 1250s to obtain the fourth feed liquid.
Standing the obtained fourth feed liquid, removing the water phase, and simultaneously measuring that the sum of bisphenol A sodium salt and tetrabromobisphenol A sodium salt residues in the water phase of the solution is 425ppm; the organic phase obtained was washed with 2% by weight of hydrochloric acid and then with deoxygenated water, so that the pH of the washed organic phase was 6.8, and dried. The flame retardant grade of the obtained product is V2 grade after detection.
Comparative example 3
The comparative example provides a method for preparing flame-retardant copolycarbonate.
1. Preparation: as in example 1.
2. Synthesis in a tubular reactor
Introducing tetrabromobisphenol A sodium salt solution and phosgene solution into a section of tubular reactor simultaneously by a advection pump, setting the flow rate of the tetrabromobisphenol A sodium salt solution to be 150.00g/min, setting the flow rate of the phosgene solution to be 55.46g/min, and reacting for 1200s (the pH value of the reaction end point is 7) to obtain a first feed liquid;
after the first feed liquid and bisphenol A sodium salt solution are mixed (the mass ratio of halogenated bisphenol A to bisphenol A is 1:0.67), the mixture and phosgene solution are simultaneously introduced into a two-stage tubular reactor, the flow rate of the mixed liquid of the first feed liquid and bisphenol A sodium salt solution is 355.46g/min, the flow rate of the phosgene solution is 79.32g/min, and precipitation is carried out after 300s of reaction. The subsequent reaction was stopped.
Comparative example 4
The comparative example provides a method for preparing flame-retardant copolycarbonate.
1. Preparation:
mixing tetrabromobisphenol A and 3% wt sodium hydroxide solution to prepare tetrabromobisphenol A sodium salt solution with tetrabromobisphenol A sodium salt concentration of 17.64% wt and pH value of 12 for later use;
bisphenol A sodium salt solution, phosgene solution, capping agent solution, and phase transfer catalyst solution were the same as in example 1.
2. Synthesis in a tubular reactor
Introducing tetrabromobisphenol A sodium salt solution and phosgene solution into a section of tubular reactor simultaneously by a advection pump, setting the flow rate of the tetrabromobisphenol A sodium salt solution to 189.63g/min, setting the flow rate of the phosgene solution to 55.46g/min, and reacting for 30s (the pH of the reaction end point is 11) to obtain a first feed liquid;
mixing the first feed liquid with bisphenol A sodium salt solution (the mass ratio of halogenated bisphenol A to bisphenol A is 1:0.67), then simultaneously introducing the mixture and phosgene solution into a two-stage tubular reactor, setting the flow rate of the mixed solution of the first feed liquid and bisphenol A sodium salt solution to 395.09g/min, setting the flow rate of the phosgene solution to 79.32g/min, and reacting for 300s to obtain a second feed liquid;
mixing the second feed liquid with a capping reagent solution (the ratio of the mass of the capping reagent to the total mass of bisphenol A and halogenated bisphenol A is 1:59), introducing the mixture into a three-section tubular reactor, setting the flow rate of the mixed solution of the second feed liquid and the capping reagent solution to 483.19g/min, and reacting for 460 seconds to obtain a third feed liquid;
mixing the third feed liquid with 32%wt concentration sodium hydroxide solution (the mass ratio of the third feed liquid to the sodium hydroxide solution is 1:0.14), and introducing the mixture into a four-section tubular reactor, wherein the flow rate of the mixture of the third feed liquid and the sodium hydroxide solution is 551.75g/min; after 355s of reaction (the pH of the reaction end point is 13.5), a fourth feed liquid is obtained;
maintaining the outlet temperature of the four-section tubular reactor at 30+/-3 ℃ and the pressure at 450+/-50 KPaG, mixing the fourth feed liquid with dichloromethane (the mass ratio of the fourth feed liquid to the dichloromethane is 1:0.40), introducing the mixture into the five-section tubular reactor, setting the flow rate of the mixed liquid of the dichloromethane and the fourth feed liquid to 770.08g/min, and reacting for 720s to obtain a fifth feed liquid;
mixing the fifth feed liquid with the phase transfer catalyst solution (the mass ratio of the fifth feed liquid to the phase transfer catalyst solution is 1:0.035), introducing the mixture into a six-section tubular reactor, setting the flow rate of the mixture of the fifth feed liquid and the phase transfer catalyst solution to 796.65g/min, and reacting for 175s to obtain the flame-retardant copolycarbonate solution with Mw of 4520.
Standing the obtained flame-retardant copolycarbonate solution, removing a water phase, and simultaneously measuring 3500ppm of bisphenol A sodium salt and tetrabromobisphenol A sodium salt residues in the water phase of the solution; the obtained organic phase is firstly washed with 2 percent by weight of hydrochloric acid, then is washed with deoxidized water, the pH value of the washed organic phase is 6.8, and the organic phase is dried, thus obtaining the flame-retardant copolycarbonate. Through detection, the halogen content of the obtained flame-retardant copolycarbonate reaches 30.3 percent. Detected.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. A method for preparing flame-retardant copolycarbonate, which is characterized in that the preparation method is carried out in a tubular reactor and comprises the following operations:
introducing phosgene solution and halogenated bisphenol A sodium salt solution into a first-stage tubular reactor, and reacting for 60-600 s to obtain a first feed liquid; the pH value of the halogenated bisphenol A sodium salt solution is 10.5-13.5, and the molar ratio of the halogenated bisphenol A sodium salt to phosgene is 1: (0.95-2);
uniformly mixing the first feed liquid with bisphenol A sodium salt solution, and then simultaneously introducing the mixture and phosgene solution into a two-stage tubular reactor for reaction for 45-300 s to obtain second feed liquid;
introducing the second feed liquid and the end capping reagent solution into a three-section tubular reactor simultaneously to react for 77-460s to obtain a third feed liquid;
introducing the third feed liquid and sodium hydroxide solution into a four-section tubular reactor simultaneously, and reacting for 63-355s under the condition that the pH value is 11-13.5 to obtain fourth feed liquid;
introducing the fourth feed liquid and dichloromethane into a five-section tubular reactor simultaneously to react for 102-720 seconds to obtain a fifth feed liquid;
and simultaneously introducing the fifth feed liquid and the phase transfer catalyst solution into a six-section tubular reactor to react for 45-175s, so as to obtain the solution containing the flame-retardant copolycarbonate.
2. The method for preparing the flame-retardant copolycarbonate according to claim 1, wherein the phosgene solution is prepared from phosgene and methylene dichloride according to a mass ratio of 1: (2-20) mixing; and/or
The molar ratio of the halogenated bisphenol A sodium salt to phosgene is 1: (1.15-1.5); and/or
The pH value of the halogenated bisphenol A sodium salt solution is 12-13; and/or
The pH value of the bisphenol A sodium salt solution is 10.5-13.5.
3. The method for preparing the flame-retardant copolycarbonate according to claim 1, wherein the halogenated bisphenol a sodium salt solution is prepared by mixing halogenated bisphenol a with an alkali metal hydroxide solution; the bisphenol A sodium salt solution is prepared by mixing bisphenol A with alkali metal hydroxide solution.
5. The method for producing a flame-retardant copolycarbonate according to claim 4, wherein the mass ratio of halogenated bisphenol A to bisphenol A is 1: (0.5 to 99); and/or
The molar ratio of bisphenol a sodium salt to phosgene in the phosgene solution in the one-stage tubular reactor was 1: (1.03-1.5); and/or
The reaction time in the one-stage tubular reactor is 300 to 600 seconds.
6. The method for preparing flame-retardant copolycarbonate according to claim 3, wherein the end-capping agent is selected from phenol, p-tert-butylphenol and p-cumylphenol, and the solvent is methylene chloride.
7. The method for preparing the flame-retardant copolycarbonate according to claim 6, wherein the mass ratio of the end-capping agent to methylene dichloride in the end-capping agent solution is 1: (4-20); and/or
The ratio of the mass of the end-capping agent to the total mass of the bisphenol A and the halogenated bisphenol A is 1 (35-66).
8. The method for preparing flame-retardant copolycarbonate according to claim 1, wherein the phase transfer catalyst is an organic tertiary amine and the solvent is methylene chloride.
9. The method for producing a flame-retardant copolycarbonate according to claim 8, wherein the mass ratio of the phase transfer catalyst to methylene chloride in the phase transfer catalyst solution is 1: (10-50); and/or
The ratio of the amount of the organic tertiary amine to the total amount of the halogenated bisphenol A sodium salt and bisphenol A sodium salt is 1 (9-32).
10. A flame retardant copolycarbonate prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310504681.4A CN116425965B (en) | 2023-05-06 | 2023-05-06 | Flame-retardant copolycarbonate and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310504681.4A CN116425965B (en) | 2023-05-06 | 2023-05-06 | Flame-retardant copolycarbonate and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116425965A true CN116425965A (en) | 2023-07-14 |
CN116425965B CN116425965B (en) | 2024-02-13 |
Family
ID=87090780
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310504681.4A Active CN116425965B (en) | 2023-05-06 | 2023-05-06 | Flame-retardant copolycarbonate and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116425965B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05279467A (en) * | 1992-03-31 | 1993-10-26 | Idemitsu Petrochem Co Ltd | Polycarbonate copolymer and its production |
CN101037501A (en) * | 2007-04-19 | 2007-09-19 | 临海市兴华化学厂 | Method for preparing polyether carbonate tetrahalo biphenol A ester |
CN102030895A (en) * | 2010-11-05 | 2011-04-27 | 烟台万华聚氨酯股份有限公司 | Method for preparing polycarbonate with continuous two-phase interface phosgene method |
CN102775592A (en) * | 2012-03-12 | 2012-11-14 | 甘肃银光聚银化工有限公司 | Method for continuously preparing makrolon by phosgene interface polycondensation |
CN105482091A (en) * | 2015-12-28 | 2016-04-13 | 甘肃银光聚银化工有限公司 | Preparation method of low-molecular-weight halogen flame-retardant polycarbonate |
-
2023
- 2023-05-06 CN CN202310504681.4A patent/CN116425965B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05279467A (en) * | 1992-03-31 | 1993-10-26 | Idemitsu Petrochem Co Ltd | Polycarbonate copolymer and its production |
CN101037501A (en) * | 2007-04-19 | 2007-09-19 | 临海市兴华化学厂 | Method for preparing polyether carbonate tetrahalo biphenol A ester |
CN102030895A (en) * | 2010-11-05 | 2011-04-27 | 烟台万华聚氨酯股份有限公司 | Method for preparing polycarbonate with continuous two-phase interface phosgene method |
CN102775592A (en) * | 2012-03-12 | 2012-11-14 | 甘肃银光聚银化工有限公司 | Method for continuously preparing makrolon by phosgene interface polycondensation |
CN105482091A (en) * | 2015-12-28 | 2016-04-13 | 甘肃银光聚银化工有限公司 | Preparation method of low-molecular-weight halogen flame-retardant polycarbonate |
Also Published As
Publication number | Publication date |
---|---|
CN116425965B (en) | 2024-02-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI557153B (en) | And a branched aromatic polycarbonate resin having a desired degree of branching | |
JPH04213323A (en) | Process | |
CN114230779B (en) | Polycarbonate and preparation method and application thereof | |
JP2634756B2 (en) | Method for producing polymer | |
CN116425965B (en) | Flame-retardant copolycarbonate and preparation method thereof | |
KR100322264B1 (en) | A continuous process for the preparation of copolycarbonate resins | |
WO2012019424A1 (en) | A method of melt transesterification for preparing a polycarbonate | |
EP0093914B2 (en) | Process for the production of polycarbonate | |
CN111187403A (en) | Siloxane copolycarbonate and preparation method thereof | |
CN114763407A (en) | Copolycarbonate with high transmittance and low-temperature impact resistance, and preparation method and application thereof | |
CN107001607A (en) | Method for producing polycarbonate-polyorganosiloxane copolymer | |
CN111196874A (en) | Polyester block copolycarbonate and preparation method thereof | |
US4767840A (en) | Cyclic monocarbonate bishaloformates, method for their preparation, and uses thereof | |
CN101613468B (en) | Aromatic polycarbonate polymer | |
KR20070052820A (en) | Polycarbonate resin composition having high melting flow property and process for preparing thereof | |
TWI675863B (en) | Branched polycarbonate manufacturing method | |
CN108884221B (en) | Copolycarbonate and composition containing same | |
JPS6256895B2 (en) | ||
JP4644442B2 (en) | Method for producing branched polycarbonate resin | |
JP2877415B2 (en) | Polyether resin, its production method and optical material comprising it | |
CN103739836A (en) | Aromatic polycarbonate and preparation method thereof | |
US4921975A (en) | Cyclic monocarbonate bishaloformates | |
WO2016104532A1 (en) | Process for producing polycarbonate | |
KR100358657B1 (en) | A Continuous Process for the preparation of Copolycarbonate resins | |
JPH05222182A (en) | Branched polycarbonate resin and its production |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |