CN115028823A - Preparation method of copolycarbonate, copolycarbonate and application thereof - Google Patents
Preparation method of copolycarbonate, copolycarbonate and application thereof Download PDFInfo
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- CN115028823A CN115028823A CN202210784071.XA CN202210784071A CN115028823A CN 115028823 A CN115028823 A CN 115028823A CN 202210784071 A CN202210784071 A CN 202210784071A CN 115028823 A CN115028823 A CN 115028823A
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- 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
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- 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
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
The invention relates to a preparation method of copolycarbonate, the copolycarbonate and application thereof, wherein the copolycarbonate is prepared from diphenol compounds shown in a general formula (I) and a general formula (II), raw materials and phosgene are added twice in the polymerization reaction process, meanwhile, a reaction solution is emulsified by an emulsifying machine in the reaction process, and a small amount of 2-naphthol is added as a second end-capping reagent. The copolycarbonate prepared by the method can improve the disorder of the whole chain segment, reduce the reaction time and realize the optimization of the mechanical, thermal and optical properties of the polycarbonate by controlling the reaction process.
Description
Technical Field
The invention belongs to the technical field of polycarbonate copolymers, and particularly relates to a preparation method of copolycarbonate with improved performance, the copolycarbonate and application of the copolycarbonate.
Background
The copolycarbonate obtained by taking 1, 1-bis- (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (BPTMC) and bisphenol A (BPA) as comonomers is mainly applied to some high-temperature fields, such as automobile lamps and the like. As a comonomer, the activity difference of BPTMC and BPA is large, and a block copolymer is easily formed in the polymerization reaction process to influence the product performance. Therefore, it is necessary to improve the disorder of the chain segment and further improve the overall performance of the product by improving the preparation method.
Chinese patent CN113614148A describes an improved process for the preparation of bisphenol TMC and bisphenol a type polycarbonates, which facilitates the obtaining of polycarbonates with low oligomer and low proportion of di-chain terminator carbonates by adding the chain terminator to the reaction system at a specific point in time, but does not mention the effect of improving polymer properties.
Chinese patent CN113614147A describes an improved process for the preparation of bisphenol TMC and bisphenol a type polycarbonates, which, given the energy input for the dispersion of the aqueous and organic phases, makes it possible to achieve a reduction in the amount of phosgene and advantageously a reduction in the oligomer proportion of the polycarbonate, and which likewise does not mention an improved effect on the properties of the polymer.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention aims to provide a method for preparing copolycarbonates, wherein the comprehensive properties of such polycarbonates can be improved by synergistically controlling the manner of adding raw materials, the manner of adding phosgene, the manner of emulsifying the reaction solution, and the manner of adding a second end-capping reagent during the polymerization process.
It is a further object of the present invention to provide such copolycarbonates with improved properties.
It is a further object of the present invention to provide the use of copolycarbonates having improved properties.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of copolycarbonate, which comprises the following steps:
1) mixing part of the diphenol compound with the structure shown in the formula (I) and part of the diphenol compound with the structure shown in the formula (II) with alkali, a deoxidant and water in a nitrogen environment, adding an organic solvent immiscible with water, and introducing phosgene and alkali liquor to perform an interfacial polycondensation reaction, wherein the phosgene is 5-20% excessive relative to the total molar weight of the diphenol compound with the structure shown in the formula (I) and the diphenol compound with the structure shown in the formula (II) in the system in the step 1), so as to obtain a prepolymer;
2) adding an end-capping reagent, the rest of diphenol compound with the structure of the formula (I) and the rest of diphenol compound with the structure of the formula (II) into the prepolymer obtained in the step 1) in a nitrogen environment, and introducing phosgene and alkali liquor to carry out polymerization reaction, wherein the phosgene is 5-20% in excess relative to the total molar weight of the diphenol compound with the structure of the formula (I) and the diphenol compound with the structure of the formula (II) in the system obtained in the step 2), so as to obtain a polymer reaction solution;
3) emulsifying the polymer reaction solution obtained in the step 2) by an emulsifying machine, and simultaneously adding a catalyst and 2-naphthol to carry out end capping reaction to obtain copolycarbonate;
wherein, the diphenol compound with the structure of formula (I) and the diphenol compound with the structure of formula (II) respectively have the following structural general formulas:
in the formulae (I) and (II), R 1 、R 2 、R 3 、R 4 Each independently selected from H, halogen, C 1 ～C 10 Alkyl of (C) 5 ～C 6 Cycloalkyl or C 6 ～C 10 Aryl of (a);
in the formula (I), R 5 、R 6 、R 7 Each independently selected from H or C 1 ～C 10 Alkyl group of (1).
In a preferred embodiment, the diphenol compound of formula (I) is a compound of formula (III), i.e., BPTMC:
in a preferred embodiment, the diphenol compound of formula (II) is a compound of formula (IV), i.e., bisphenol A:
in a preferred embodiment, the raw materials of the diphenol compound with the structure of formula (I) and the diphenol compound with the structure of formula (II) are added in two times in step 1) and step 2), wherein the molar ratio of the diphenol compound with the structure of formula (I) added in two times is 10: 90-40: 60, and the molar ratio of the diphenol compound with the structure of formula (II) added in two times is 60: 40-90: 10.
In a preferred embodiment, the molar ratio of the total amount of diphenol compounds with a structure of formula (I) to the total amount of diphenol compounds with a structure of formula (II) is 1:99 to 99:1, preferably 10:90 to 70:30, and more preferably 30:70 to 40: 60.
In a preferred embodiment, in step 1), the base is an inorganic base selected from any one of NaOH, KOH, LiOH, CsOH, or a combination of at least two thereof;
preferably, the addition amount of the base is 200-240% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in two times in step 1) and step 2).
The oxygen scavenger is selected from sodium hydrosulfite and/or potassium hydrosulfite;
preferably, the addition amount of the oxygen scavenger is 0.1-0.3% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in the steps 1) and 2).
The organic solvent which is not mutually soluble with water is selected from any one or the combination of at least two of dichloromethane, chloroform, tetrachloromethane, dichloroethane, toluene and chlorobenzene;
preferably, the addition amount of the water-immiscible organic solvent is 1500-2500% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in two times in step 1) and step 2).
The adding amount of the water is 5000-9500% of the sum of the total molar amount of the diphenol compound with the structure of the formula (I) and the total molar amount of the diphenol compound with the structure of the formula (II) added in the step 1) and the step 2).
In a preferred embodiment, in the step 1), phosgene is continuously added, phosgene is continuously introduced during the reaction process, and the molar excess of phosgene in the system is kept to be 5-20% relative to the molar excess of the diphenol compound with the structure of formula (I) and the diphenol compound with the structure of formula (II) in the system in the step 1);
preferably, the time for introducing the phosgene is 10-50 min, and preferably 30-40 min.
In a preferred embodiment, in the step 1), the alkali liquor and the phosgene are simultaneously introduced into the system, a continuous feeding mode, preferably a dropping mode is adopted, the alkali liquor is continuously dropped in the reaction process, and the total molar amount of the alkali in the system in the step 1) is kept at least 300% of the molar amount of the excess phosgene, preferably 300-600%;
the alkali liquor is an alkali water solution, the concentration is 5-50 wt%, preferably 5-32 wt%, and the alkali is an inorganic alkali selected from any one or a combination of at least two of NaOH, KOH, LiOH and CsOH;
preferably, the introduction time of the alkali liquor is 10-50 min, preferably 30-40 min.
In a preferred embodiment, in the step 1), the interfacial polycondensation reaction is carried out at a reaction temperature of 18 to 30 ℃, preferably 25 to 27 ℃, and a reaction time of 10 to 50min, preferably 20 to 40 min.
In a preferred embodiment, in step 2), the end-capping agent is selected from any one of phenol, p-tert-butylphenol, cumylphenol, or a combination of at least two thereof;
preferably, the addition amount of the end capping agent is 1 to 10 percent, preferably 2 to 5 percent of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in two times in step 1) and step 2).
In a preferred embodiment, in the step 2), phosgene is continuously added, phosgene is continuously introduced during the reaction process, and the molar excess of phosgene in the system is kept to be 5-20% relative to the molar excess of the diphenol compound with the structure of formula (I) and the diphenol compound with the structure of formula (II) in the system in the step 2);
preferably, the time for introducing the phosgene is 30-120min, and preferably 60-80 min.
In a preferred embodiment, in the step 2), the alkali liquor and the phosgene are simultaneously introduced into the system, a continuous feeding mode, preferably a dropping mode is adopted, the alkali liquor is continuously dropped in the reaction process, and the total molar weight of the alkali in the system in the step 2) is kept at least 300% of the molar weight of the excess phosgene, preferably 300-600%;
the alkali liquor is an alkali water solution, the concentration is 5-50 wt%, preferably 5-32 wt%, wherein the alkali is inorganic alkali selected from any one or a combination of at least two of NaOH, KOH, LiOH and CsOH;
preferably, the time for introducing the alkali liquor is 30-120min, preferably 60-80 min.
In a preferred embodiment, in the step 2), the polymerization reaction is carried out at a reaction temperature of 25 to 37 ℃, preferably 33 to 35 ℃, and for a reaction time of 30 to 120min, preferably 60 to 90 min.
In a preferred embodiment, in the step 3), the reaction liquid is emulsified by an emulsifying machine, and the rotating speed of the emulsifying machine is controlled to be 10000-19000 r/min, preferably 10000-16000 r/min, so that the reaction liquid can achieve the required emulsified state. In the synthesis process of BPA type polycarbonate, the emulsification is avoided as much as possible by the existing method, but the invention finds that the reaction rate can be obviously accelerated by controlling the rotating speed of an emulsifying machine to emulsify reaction liquid in a proper range in experiments.
In a preferred embodiment, in the step 3), the 2-naphthol is used as a blocking agent, and the addition amount of the 2-naphthol is 1 to 3mol per thousand of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in the step 1) and the step 2);
preferably, the 2-naphthol is dissolved in alkali liquor for use, and the concentration is 0.001-0.1 g/mL;
more preferably, the alkali liquor is an alkali water solution with the concentration of 5-50 wt%, wherein the alkali is selected from NaOH and/or KOH.
In a preferred embodiment, in step 3), the catalyst is selected from any one of tertiary amines, organic phosphorus species or a combination of at least two thereof, preferably triethylamine and/or trimethylamine.
Preferably, the adding amount of the catalyst is 0.1-1 mol% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in two times in the step 1) and the step 2);
preferably, the catalyst is continuously added, preferably dropwise added, into the reaction system in the reaction process, wherein the adding time is 40-100 min, preferably 60-80 min;
more preferably, the catalyst is prepared into a solution with the concentration of 1-6 wt% and then added into the system, and the solvent is selected from any one or a combination of at least two of dichloromethane, chloroform and toluene.
In a preferred embodiment, in the step 3), the end-capping reaction is carried out at a reaction temperature of 30 to 37 ℃, preferably 33 to 35 ℃, and for a reaction time of 40 to 100min, preferably 60 to 80 min.
In a preferred embodiment, in step 3), after the reaction is finished, a post-treatment process such as separation, washing, desolvation, drying and the like is further included, which is a routine operation in the art, and there is no particular requirement, for example, in some specific examples, a post-treatment method such as: separating the reaction liquid, collecting an oil phase, sequentially washing with hydrochloric acid and deionized water until the conductivity is less than 100 mu s/cm, removing the solvent from the oil phase, and drying to obtain the copolycarbonate.
In another aspect, the present invention provides a copolycarbonate obtained by the above-mentioned production method, wherein the weight average molecular weight of the copolycarbonate is 15000 to 50000, preferably 15000 to 35000.
In a specific embodiment, the copolycarbonate further optionally comprises 0 to 5 wt%, preferably 0 to 2.5 wt%, more preferably 0 to 2 wt%, of an additive, wherein the additive is selected from any one of or a combination of at least two of a mold release agent, a flow aid, a heat stabilizer, a hydrolysis stabilizer, an antioxidant, a UV absorber, a flame retardant, an antistatic agent, a pigment, and a reinforcing filler, and the additive can be further introduced during extrusion after the copolycarbonate is prepared.
On the other hand, the invention also provides application of the copolycarbonate in the fields of car lamps, lamp bead lenses and medical instruments.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the copolycarbonate of the invention is advantageous to improve the disorder of the whole chain segment and reduce the proportion of the block part by controlling the polymerization process, adding the raw materials and supplementing phosgene twice. Meanwhile, the reaction liquid is emulsified by the emulsifying machine, so that the contact area of interfacial polymerization is increased, and the reaction rate is improved. In addition, the addition of the end capping agent 2-naphthol is beneficial to increasing the end group volume of the chain segment and improving the heat resistance, and the preparation method can realize the comprehensive improvement of the mechanical, thermal, optical and other properties of the polycarbonate.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
The following examples and comparative examples of the present invention were prepared from the following starting materials, which were otherwise common commercial materials unless otherwise specified:
BPTMC (diphenol compound of formula III), Michelin Biochemical technology Ltd, purity > 99%;
bisphenol a (diphenolic compound of formula IV), livyiweifar chemical ltd, purity > 99%;
p-tert-butylphenol, Allantin reagent Limited, purity > 99%;
2-naphthol, Aladdin reagent, Inc., purity > 98%;
triethylamine, Aladdin reagent, Inc., purity > 99%;
dichloromethane, Wanhua chemical group, Inc., purity > 99%;
NaOH, Aladdin reagent, Inc., purity > 99%;
sodium dithionite, alatin reagent limited, purity > 99%;
phosgene, Vanhua chemical group, Inc., purity > 99%.
The copolycarbonate resins prepared in the following examples and comparative examples according to the present invention were subjected to performance testing using the following methods:
tensile modulus, tensile strength according to ISO527, Vicat softening point according to ISO30-B120, heat distortion temperature according to ISO75-1/2, light transmittance and haze according to ISO13468-2, ISO14782, respectively.
Weight average molecular weight, determined by volume exclusion gel chromatography after pre-calibration with PS or polycarbonate calibration substances.
Example 1
Preparation of copolycarbonates from BPTMC, bisphenol a: the molar ratio of the total amount of BPTMC to the total amount of bisphenol A was 30: 70.
Wherein the total amount of BPTMC 93g (0.3mol) is put in twice, the mol ratio is 10:90, and the corresponding mass is respectively 9.3g (0.03mol) and 83.7g (0.27 mol);
159.6g (0.7mol) of total bisphenol A were charged in two portions at a molar ratio of 90:10, corresponding to masses of 143.64g (0.63mol) and 15.96g (0.07mol), respectively;
0.144g (0.001mol) of 2-naphthol was dissolved in 20ml of a5 wt% aqueous NaOH solution to prepare an alkali solution of 2-naphthol.
1) Taking a 3L reaction kettle with a stirring paddle, starting stirring, introducing nitrogen for protection, introducing 30 ℃ constant temperature water into a jacket, adding 83g (2.08mol) of NaOH solid, 0.348g (0.002mol) of sodium hydrosulfite and 1348g (74.89mol) of deionized water, after the solid is completely dissolved, adding 9.3g (0.03mol) of BPTMC and 143.64g (0.63mol) of bisphenol A, adding 1595.3g (18.77mol) of dichloromethane after the powder is completely dissolved, then phosgene is continuously introduced to carry out interfacial polycondensation reaction, the reaction temperature is 26 ℃, the reaction time is 30min, the phosgene amount in the system is controlled to be 12 percent in excess relative to the total molar amount of BPTMC and bisphenol A in the system in the step, the gas is continuously introduced for 30min, and simultaneously, dropwise adding 32 wt% of NaOH aqueous solution into the reaction kettle, wherein the total molar amount of NaOH in the dropwise adding process control system is 450% of the total molar amount of excess phosgene, and continuously dropwise adding for 30min to obtain the prepolymer.
2) Adding 83.7g (0.27mol) of BPTMC and 15.96g (0.07mol) of bisphenol A into the prepolymer in the step 1) in a nitrogen environment, then adding 3.79g (0.025mol) of p-tert-butylphenol, continuously introducing phosgene after complete dissolution for polymerization reaction at the reaction temperature of 33 ℃ for 60min, controlling the phosgene in the system to be 15% in excess relative to the total molar amount of the BPTMC and the bisphenol A in the system in the step, continuously introducing for 60min, simultaneously dropwise adding a NaOH aqueous solution with the concentration of 32 wt% into a reaction kettle, controlling the total molar amount of NaOH in the system to be 450% of the total molar amount of the excess phosgene in the dropwise adding process, and continuously dropwise adding for 60min to obtain a polymer reaction liquid.
3) Emulsifying the polymer reaction liquid obtained in the step 2) by an emulsifying machine, controlling the rotating speed of the emulsifying machine to be 10000r/min, then dropwise adding 60g of 1 wt% triethylamine solution (0.006 mol of triethylamine and dichloromethane as a solvent) into the reaction kettle for 60min, and then adding 20ml of 2-naphthol (0.001mol) alkali solution for end capping reaction at 35 ℃ for 60 min.
After the reaction is finished, separating and collecting the oil phase, adding 2L of 0.4mol/L hydrochloric acid for washing, after the acid washing is finished, collecting the oil phase, and adding 5L of deionized water for washing until the conductivity is less than 100 mus/cm. The oil phase was then desolventized and dried to provide a copolycarbonate resin (No. A1), weight average molecular weight 32514, performance test results are shown in Table 1.
Example 2
Preparation of copolycarbonates from BPTMC, bisphenol a: the molar ratio of the total amount of BPTMC to the total amount of bisphenol A is 40: 60.
Wherein 124g (0.4mol) of total BPTMC is added in two times, the molar ratio is 20:80, and the corresponding masses are respectively 24.8g (0.08mol) and 99.2g (0.32 mol);
136.8g (0.6mol) of total bisphenol A were charged in two portions at a molar ratio of 80:20, corresponding to masses of 109.44g (0.48mol) and 27.36g (0.12mol), respectively;
0.288g (0.002mol) of 2-naphthol was dissolved in 20ml of a5 wt% aqueous NaOH solution to prepare an alkali solution of 2-naphthol.
1) Taking a 3L reaction kettle with a stirring paddle, starting stirring, introducing nitrogen for protection, introducing 30 ℃ constant temperature water into a jacket, adding 84.8g (2.12mol) of NaOH solid, 0.522g (0.003mol) of sodium hydrosulfite and 1478g (82.10mol) of deionized water, after the solid is completely dissolved, adding 24.8g (0.08mol) of BPTMC and 109.44g (0.48mol) of bisphenol A, adding 1643.2g (19.33mol) of dichloromethane after the powder is completely dissolved, then phosgene is continuously introduced to carry out interfacial polycondensation reaction, the reaction temperature is 20 ℃, the reaction time is 40min, the phosgene amount in the system is controlled to be excessive by 18 percent relative to the total molar amount of BPTMC and bisphenol A in the system in the step, the introduction is continuously carried out for 40min, and simultaneously, dropwise adding 32 wt% of NaOH aqueous solution into the reaction kettle, wherein the total molar amount of NaOH in the dropwise adding process control system is 500% of the total molar amount of excess phosgene, and continuously dropwise adding for 40min to obtain the prepolymer.
2) Adding 99.2g (0.32mol) of BPTMC and 27.36g (0.12mol) of bisphenol A into the prepolymer in the step 1) in a nitrogen environment, then adding 3.91g (0.026mol) of p-tert-butylphenol, after completely dissolving, continuously introducing phosgene for polymerization at a reaction temperature of 27 ℃ for 60min, controlling the phosgene in the system to be in excess of 15 percent relative to the total molar amount of the BPTMC and the bisphenol A in the system in the step, continuously introducing the phosgene for 60min, simultaneously dropwise adding a NaOH aqueous solution with the concentration of 32wt percent into a reaction kettle, controlling the total molar amount of NaOH in the system to be 500 percent of the total molar amount of the excess phosgene in the dropwise adding process, and continuously dropwise adding the NaOH aqueous solution for 60min to obtain a polymer reaction solution.
3) Emulsifying the polymer reaction liquid obtained in the step 2) by an emulsifying machine, controlling the rotating speed of the emulsifying machine to be 12000r/min, then dropwise adding 60g of 1 wt% triethylamine solution (0.006 mol of triethylamine and dichloromethane as a solvent) into the reaction kettle for 40min, and then adding 20ml of 2-naphthol (0.002mol) aqueous alkali for end capping reaction at the reaction temperature of 30 ℃ for 40 min.
After the reaction is finished, separating and collecting the oil phase, adding 2L of 0.4mol/L hydrochloric acid for washing, after the acid washing is finished, collecting the oil phase, and adding 5L of deionized water for washing until the conductivity is less than 100 mus/cm. The oil phase was then desolventized and dried to give a copolycarbonate resin (No. A2) having a weight average molecular weight of 32874 and the results of the performance test are shown in Table 1.
Example 3
Preparation of copolycarbonates from BPTMC, bisphenol a: the molar ratio of the total amount of BPTMC to the total amount of bisphenol A was 50: 50.
Wherein 155g (0.5mol) of total BPTMC is added in two times, the molar ratio is 30:70, and the corresponding masses are 46.5g (0.15mol) and 108.5g (0.35mol), respectively;
114g (0.5mol) of total bisphenol A were charged in two portions at a molar ratio of 70:30, corresponding to masses of 79.8g (0.35mol) and 34.2g (0.15mol), respectively;
0.432g (0.003mol) of 2-naphthol was dissolved in 20ml of a5 wt% NaOH aqueous solution to prepare a 2-naphthol alkaline solution.
1) Taking a 3L reaction kettle with a stirring paddle, starting stirring, introducing nitrogen for protection, introducing 30 ℃ constant temperature water into a jacket, adding 84g (2.10mol) of NaOH solid, 0.174g (0.001mol) of sodium hydrosulfite and 1524g (84.69mol) of deionized water, after the solid is completely dissolved, adding 46.5g (0.15mol) of BPTMC and 79.8g (0.35mol) of bisphenol A, adding 1691.5g (19.90mol) of dichloromethane after the powder is completely dissolved, then phosgene is continuously introduced to carry out interfacial polycondensation reaction, the reaction temperature is 30 ℃, the reaction time is 20min, the phosgene amount in the system is controlled to be 8 percent excess relative to the total molar amount of BPTMC and bisphenol A in the system in the step, the introduction is continuously carried out for 20min, and simultaneously, dropwise adding 32 wt% of NaOH aqueous solution into the reaction kettle, wherein the total molar amount of NaOH in the dropwise adding process control system is 450% of the total molar amount of excess phosgene, and continuously dropwise adding for 20min to obtain the prepolymer.
2) Adding 108.5g (0.35mol) of BPTMC and 34.2g (0.15mol) of bisphenol A into the prepolymer in the step 1) in a nitrogen environment, then adding 4.06g (0.027mol) of p-tert-butylphenol, continuously introducing phosgene after complete dissolution for polymerization reaction at 37 ℃ for 40min, controlling the phosgene in the system to be 8% in excess relative to the total molar amount of the BPTMC and the bisphenol A in the system in the step, continuously introducing 40min, simultaneously dropwise adding a NaOH aqueous solution with the concentration of 32 wt% into the reaction kettle, controlling the total molar amount of NaOH in the system to be 450% of the total molar amount of the excess phosgene in the dropwise adding process, and continuously dropwise adding 40min to obtain a polymer reaction solution.
3) Emulsifying the polymer reaction liquid obtained in the step 2) by an emulsifying machine, controlling the rotating speed of the emulsifying machine to be 14000r/min, then dropwise adding 60g of triethylamine solution (0.006 mol of triethylamine and dichloromethane as a solvent) with the concentration of 1 wt% into the reaction kettle for 40min, and then adding 20ml of 2-naphthol (0.003mol) alkali solution for end capping reaction at 37 ℃ for 40 min.
After the reaction is finished, separating and collecting the oil phase, adding 2L of 0.4mol/L hydrochloric acid for washing, after the acid washing is finished, collecting the oil phase, and adding 5L of deionized water for washing until the conductivity is less than 100 mu s/cm. The oil phase was then freed of solvent and dried to give a copolycarbonate resin (No. A3) having a weight average molecular weight of 33201 and the results of the property tests are shown in Table 1.
Example 4
Preparation of copolycarbonates from BPTMC, bisphenol a: the molar ratio of the total amount of BPTMC to the total amount of bisphenol A was 10: 90.
Wherein 31g (0.1mol) of total BPTMC is added in two times, the molar ratio is 40:60, and the corresponding masses are 12.4g (0.04mol) and 18.6g (0.06mol), respectively;
205.2g (0.9mol) of total bisphenol A were charged in two portions at a molar ratio of 60:40, corresponding to masses of 123.12g (0.54mol) and 82.08g (0.36mol), respectively;
0.432g (0.003mol) of 2-naphthol was dissolved in 20ml of a5 wt% NaOH aqueous solution to prepare a 2-naphthol alkaline solution.
Synthesis procedure referring to example 1, the reaction mixture was emulsified by an emulsifier, and the rotation speed of the emulsifier was controlled to 16000r/min, to obtain a copolycarbonate resin (No. A4), weight average molecular weight 33579, and the results of the performance test are shown in Table 1.
Example 5
Preparation of copolycarbonates from BPTMC, bisphenol a: the molar ratio of the total amount of BPTMC to the total amount of bisphenol A was 20: 80.
Wherein, the total amount of BPTMC is 62g (0.2mol) and is put in twice, the mol ratio is 15:85, and the corresponding mass is 9.3g (0.03mol) and 52.7g (0.17mol) respectively;
182.4g (0.8mol) of total bisphenol A were charged in two portions at a molar ratio of 85:15, corresponding to masses of 155.04g (0.68mol) and 27.36g (0.12mol), respectively;
0.432g (0.003mol) of 2-naphthol was dissolved in 20ml of a5 wt% NaOH aqueous solution to prepare a 2-naphthol alkaline solution.
Synthesis procedure referring to example 1, the reaction mixture was emulsified by an emulsifier, and the rotation speed of the emulsifier was controlled at 18000r/min, to obtain a copolycarbonate resin (No. A5), weight average molecular weight 32147, and the results of the performance test are shown in Table 1.
Example 6
Preparation of copolycarbonates from BPTMC, bisphenol a: the molar ratio of the total amount of BPTMC to the total amount of bisphenol A is 60: 40.
Wherein, the total amount of BPTMC is 186g (0.6mol) which is put in twice, the mol ratio is 25:75, and the corresponding mass is 46.5g (0.15mol) and 139.5g (0.45 mol);
91.2g (0.4mol) of total bisphenol A were charged in two portions at a molar ratio of 75:25, corresponding to masses of 68.4g (0.3mol) and 22.8g (0.1mol), respectively;
0.432g (0.003mol) of 2-naphthol was dissolved in 20ml of a5 wt% NaOH aqueous solution to prepare a 2-naphthol alkaline solution.
Synthesis procedure referring to example 1, the reaction mixture was emulsified by an emulsifier, and the rotation speed of the emulsifier was controlled to 19000r/min, to obtain a copolycarbonate resin (No. A6), which had a weight-average molecular weight of 31953, and the results of the performance test thereof are shown in Table 1.
Example 7
Preparation of copolycarbonates from BPTMC, bisphenol a: the molar ratio of the total amount of BPTMC to the total amount of bisphenol A was 70: 30.
Wherein 217g (0.7mol) of total BPTMC is added in two times, the mol ratio is 35:65, and the corresponding masses are 75.95g (0.245mol) and 141.05g (0.455 mol);
68.4g (0.3mol) of total bisphenol A were charged in two portions at a molar ratio of 65:35, corresponding to masses of 44.46g (0.195mol) and 23.94g (0.105mol), respectively;
0.432g (0.003mol) of 2-naphthol was dissolved in 20ml of a5 wt% NaOH aqueous solution to prepare a 2-naphthol alkaline solution.
Synthesis procedure referring to example 1, the reaction mixture was emulsified by an emulsifier, and the rotation speed of the emulsifier was controlled to 12000r/min, to obtain a copolycarbonate resin (No. A7), weight average molecular weight 32567, and the results of the performance test are shown in Table 1.
Comparative example 1
A copolycarbonate was prepared according to the method of example 1, except that: BPTMC and BPA raw materials are added at one time in the step 1), other operations are not changed, the copolycarbonate resin (number 1) is prepared, the weight average molecular weight is 32278, and the performance test results are shown in Table 1.
Comparative example 2
A copolycarbonate was prepared according to the method of example 1, except that: BPTMC raw materials are added at one time in the step 1), BPA raw materials are added at one time in the step 2), other operations are not changed, and the copolycarbonate resin (number 2) is prepared, wherein the weight average molecular weight is 32587, and the performance test results are shown in the table 1.
Comparative example 3
A copolycarbonate was prepared according to the method of example 1, except that: BPA raw materials are added in one step in the step 1), BPTMC raw materials are added in one step in the step 2), and other operations are not changed, so that the copolycarbonate resin (number 3) with the weight-average molecular weight of 31689 is prepared.
Comparative example 4
Copolycarbonates were prepared according to the method of example 1, with the following exceptions: BPTMC raw materials are added in one step in the step 1), BPA raw materials are added in two steps in the steps 1) and 2), other operations are not changed, the copolycarbonate resin (number 4) is prepared, the weight average molecular weight is 32119, and the performance test results are shown in the table 1.
Comparative example 5
Copolycarbonates were prepared according to the method of example 1, with the following exceptions: BPA raw materials are added in one step in the step 1), BPTMC raw materials are added in two steps in the steps 1) and 2), other operations are not changed, the copolycarbonate resin (number 5) is prepared, the weight average molecular weight is 32299, and the performance test results are shown in the table 1.
Comparative example 6
A copolycarbonate was prepared according to the method of example 1, except that: in the step 3), emulsification was performed without using an emulsifying machine, and the other operations were not changed, thereby obtaining a copolycarbonate resin (No. 6) having a weight-average molecular weight of 32625, and the results of the performance test are shown in Table 1.
Comparative example 7
A copolycarbonate was prepared according to the method of example 1, except that: no 2-naphthol was added in step 3), and the other operations were not changed to prepare a copolycarbonate resin (No. 7) having a weight average molecular weight of 32875, the results of the performance tests being shown in Table 1.
TABLE 1 results of property testing of copolycarbonates prepared in examples and comparative examples
As shown in Table 1, by adding the raw materials in two steps during the polymerization, it is advantageous to increase the light transmittance, tensile modulus, tensile strength, Vicat softening point and heat distortion temperature of the polymer and to reduce the haze. When the addition ratio of the raw materials is beyond the range, the corresponding performance is reduced. In addition, the reaction liquid is emulsified by the emulsifying machine, which is beneficial to shortening the reaction time, but the rotating speed of the emulsifying machine needs to be controlled within a certain range. Meanwhile, the addition of the end-capping reagent 2-naphthol is beneficial to improving the heat resistance of the polymer.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A method for preparing a copolycarbonate, comprising the steps of:
1) mixing part of the diphenol compound with the structure shown in the formula (I) and part of the diphenol compound with the structure shown in the formula (II) with alkali, a deoxidant and water in a nitrogen environment, adding an organic solvent immiscible with water, and introducing phosgene and alkali liquor to perform an interfacial polycondensation reaction, wherein the phosgene is 5-20% excessive relative to the total molar weight of the diphenol compound with the structure shown in the formula (I) and the diphenol compound with the structure shown in the formula (II) in the system in the step 1), so as to obtain a prepolymer;
2) adding an end-capping agent, the rest of diphenol compound with the structure of the formula (I) and the rest of diphenol compound with the structure of the formula (II) into the prepolymer obtained in the step 1) in a nitrogen environment, and introducing phosgene and alkali liquor to carry out polymerization reaction, wherein the phosgene is excessive by 5-20% relative to the total molar amount of the diphenol compound with the structure of the formula (I) and the diphenol compound with the structure of the formula (II) in the system obtained in the step 2), so as to obtain a polymer reaction solution;
3) emulsifying the polymer reaction solution obtained in the step 2) by an emulsifying machine, and simultaneously adding a catalyst and 2-naphthol to carry out end capping reaction to obtain copolycarbonate;
wherein, the diphenol compound with the structure of formula (I) and the diphenol compound with the structure of formula (II) respectively have the following structural general formulas:
in the formulae (I) and (II), R 1 、R 2 、R 3 、R 4 Each independently selected from H, halogen, C 1 ～C 10 Alkyl of (C) 5 ～C 6 Cycloalkyl or C 6 ～C 10 Aryl of (a);
in the formula (I), R 5 、R 6 、R 7 Each independently selected from H or C 1 ～C 10 Alkyl group of (1).
2. The process of claim 1, wherein the diphenol compound of formula (I) is a compound of formula (III), BPTMC:
the diphenol compound with the structure of the formula (II) is a compound shown as a formula (IV), namely bisphenol A:
3. the preparation method of claim 1 or 2, wherein the raw materials of the diphenol compound with the structure of formula (I) and the diphenol compound with the structure of formula (II) are added in two times in step 1) and step 2), wherein the molar ratio of the diphenol compound with the structure of formula (I) added in two times is 10: 90-40: 60, and the molar ratio of the diphenol compound with the structure of formula (II) added in two times is 60: 40-90: 10;
the molar ratio of the total diphenol compound with the structure of the formula (I) to the total diphenol compound with the structure of the formula (II) is 1: 99-99: 1, preferably 10: 90-70: 30, and more preferably 30: 70-40: 60.
4. The method according to any one of claims 1 to 3, wherein in the step 1), the base is an inorganic base selected from any one or a combination of at least two of NaOH, KOH, LiOH and CsOH;
preferably, the adding amount of the base is 200-240% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in two times in step 1) and step 2); and/or
The oxygen scavenger is selected from sodium hydrosulfite and/or potassium hydrosulfite;
preferably, the addition amount of the oxygen scavenger is 0.1-0.3% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in the step 1) and the step 2); and/or
The organic solvent which is not mutually soluble with water is selected from any one or the combination of at least two of dichloromethane, chloroform, tetrachloromethane, dichloroethane, toluene and chlorobenzene;
preferably, the adding amount of the organic solvent immiscible with water is 1500-2500% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in two times in the step 1) and the step 2); and/or
The adding amount of the water is 5000-9500% of the sum of the total molar amount of the diphenol compound with the structure of the formula (I) and the total molar amount of the diphenol compound with the structure of the formula (II) added in the step 1) and the step 2); and/or
In the step 1), phosgene is continuously added, phosgene is continuously introduced in the reaction process, and the excessive rate of the total molar amount of phosgene in a system is kept to be 5-20% relative to the total molar amount of the diphenol compound with the structure of formula (I) and the diphenol compound with the structure of formula (II) in the system in the step 1);
preferably, the time for introducing the phosgene is 10-50 min, preferably 30-40 min; and/or
In the step 1), continuously adding alkali liquor in a continuous feeding mode, preferably in a dropping mode, continuously dropping alkali liquor in the reaction process, and keeping the total molar weight of alkali in the system in the step 1) at least 300% of the molar weight of excess phosgene, preferably 300-600%;
the alkali liquor is an alkali water solution, the concentration is 5-50 wt%, preferably 5-32 wt%, wherein the alkali is inorganic alkali selected from any one or a combination of at least two of NaOH, KOH, LiOH and CsOH;
preferably, the introduction time of the alkali liquor is 10-50 min, preferably 30-40 min.
5. The production method according to any one of claims 1 to 4, wherein in the step 2), the end-capping agent is selected from any one of phenol, p-tert-butylphenol, cumylphenol, or a combination of at least two thereof;
preferably, the addition amount of the end capping agent is 1-10%, preferably 2-5% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in two times in step 1) and step 2); and/or
In the step 2), phosgene is continuously added, phosgene is continuously introduced in the reaction process, and the excessive rate of the total molar amount of phosgene in the system is kept to be 5-20% relative to the total molar amount of the diphenol compound with the structure of formula (I) and the diphenol compound with the structure of formula (II) in the system in the step 2);
preferably, the time for introducing the phosgene is 30-120min, preferably 60-80 min; and/or
In the step 2), introducing the alkali liquor and phosgene into the system at the same time, adopting a continuous feeding mode, preferably a dripping mode, continuously dripping the alkali liquor in the reaction process, and keeping the total molar weight of alkali in the system in the step 2) at least 300% of the molar weight of excess phosgene, preferably 300-600%;
the alkali liquor is an alkali water solution, the concentration is 5-50 wt%, preferably 5-32 wt%, wherein the alkali is inorganic alkali selected from any one or a combination of at least two of NaOH, KOH, LiOH and CsOH;
preferably, the introduction time of the alkali liquor is 30-120min, preferably 60-80 min.
6. The method according to any one of claims 1 to 5, wherein in step 3), the rotation speed of the emulsifying machine is 10000 to 19000r/min, preferably 10000 to 16000 r/min; and/or
In the step 3), the 2-naphthol is used as a blocking agent, and the addition amount of the 2-naphthol is 1-3 mol per thousand of the sum of the total molar amount of the diphenol compound with the structure shown in the formula (I) and the total molar amount of the diphenol compound with the structure shown in the formula (II) added in the step 1) and the step 2);
preferably, the 2-naphthol is dissolved in alkali liquor for use, and the concentration is 0.001-0.1 g/mL;
more preferably, the alkali liquor is an alkali water solution with the concentration of 5-50 wt%, wherein the alkali is selected from NaOH and/or KOH; and/or
In the step 3), the catalyst is selected from any one or a combination of at least two of tertiary amines and organic phosphorus, and is preferably triethylamine and/or trimethylamine;
preferably, the adding amount of the catalyst is 0.1-1 mol% of the sum of the total molar amount of the diphenol compound with the structure of formula (I) and the total molar amount of the diphenol compound with the structure of formula (II) added in two times in the step 1) and the step 2);
preferably, the catalyst is continuously added, preferably dropwise added, into the reaction system in the reaction process, wherein the adding time is 40-100 min, preferably 60-80 min;
more preferably, the catalyst is prepared into a solution with the concentration of 1-6 wt% and then added into the system, and the solvent is selected from any one or a combination of at least two of dichloromethane, chloroform and toluene.
7. The method according to any one of claims 1 to 6, wherein in the step 1), the interfacial polycondensation reaction is carried out at a reaction temperature of 18 to 30 ℃, preferably 25 to 27 ℃, for a reaction time of 10 to 50min, preferably 20 to 40 min; and/or
In the step 2), the polymerization reaction is carried out at the reaction temperature of 25-37 ℃, preferably 33-35 ℃, and the reaction time is 30-120min, preferably 60-90 min; and/or
In the step 3), the end capping reaction is carried out at the reaction temperature of 30-37 ℃, preferably 33-35 ℃, and the reaction time is 40-100 min, preferably 60-80 min.
8. A copolycarbonate prepared according to any of claims 1 to 8, wherein the weight average molecular weight of the copolycarbonate is between 15000 and 50000, preferably between 15000 and 35000.
9. The copolycarbonate according to claim 8, further optionally comprising 0 to 5 wt%, preferably 0 to 2.5 wt%, more preferably 0 to 2 wt% of an additive selected from any one or a combination of at least two of a mold release agent, a flow aid, a heat stabilizer, a hydrolysis stabilizer, an antioxidant, a UV absorber, a flame retardant, an antistatic agent, a pigment, and a reinforcing filler, based on the total weight of the copolycarbonate.
10. Use of the copolycarbonate prepared by the method of any one of claims 1 to 8 or the copolycarbonate of claim 9 in the field of automotive lamps, lamp bead lenses, medical devices.
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