CN115651182A - Copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance, and preparation method and application thereof - Google Patents
Copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance, and preparation method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- -1 polyphenol compound Chemical class 0.000 claims abstract description 21
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 18
- 229920000515 polycarbonate Polymers 0.000 claims description 23
- 239000004417 polycarbonate Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 claims description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 2
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 150000007514 bases Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims description 2
- 239000011265 semifinished product Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 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 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229960001553 phloroglucinol Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 125000002444 phloroglucinyl group Chemical group [H]OC1=C([H])C(O[H])=C(*)C(O[H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Abstract
The invention relates to a copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance, a preparation method and an application thereof, wherein the copolycarbonate comprises the following structure: 1) A structural unit derived from a dihydroxy compound represented by formula (I):2) A structural unit derived from a polyphenol compound represented by formula (II):3) A structural unit derived from a dihydroxy compound represented by formula (III):
Description
Technical Field
The invention relates to a copolycarbonate, in particular to a copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance, a preparation method and application thereof.
Background
In the automotive field, polycarbonate plastics can be used as parts such as headlamp lampshades, headlamp bushings and reflectors, fog lamp housings and the like, and are required to be used under outdoor conditions, so that the environmental temperature difference tolerance is large. The automobile lamp has the advantages that the automobile lamp has certain strength in a low-temperature environment, can tolerate heat emitted by halogen lamps and LED lamps, and meanwhile, as for automobile illumination, the water vapor content in the lamp shade should be reduced as much as possible, so that the influence on the driving safety is avoided, and therefore, the automobile lamp also needs to have low water absorption.
At present, general-purpose polycarbonates on the market mainly comprise bisphenol a type polycarbonates, and have poor impact resistance at low temperatures, and also cannot withstand heat emitted from halogen lamps for a long period of time in terms of high temperature resistance. The polycarbonate chain segment contains a carbonate bond, so that the water absorption is high, water mist is easily generated in the lampshade forming shell, and the lighting effect is influenced.
In order to improve the overall properties of polycarbonates, the prior art has attempted to:
chinese patent CN109776783B, which uses bisphenol a, hydroquinone, m-benzene/terephthaloyl chloride and polyorganosiloxane to prepare polyester-polyorganosiloxane-polycarbonate copolymer, can improve the impact resistance of the copolymer at low temperature, but the process is an intermittent process, the preparation process is complicated, and is not beneficial to industrial amplification, and meanwhile, the polycarbonate copolymer does not mention improvement of heat resistance and water absorption.
Chinese patent CN105209543B blends and extrudes a high-temperature-resistant polycarbonate and amino-terminated siloxane to prepare a polycarbonate blend, which can obviously improve the temperature resistance and the flow property of the material, but in the blending process, the delamination phenomenon of siloxane and polycarbonate is easy to occur, which is not beneficial to product molding.
Chinese patent CN1772811A can prepare a blend with low water absorption by blending polycarbonate with polyformal, which is significantly lower than pure polycarbonate, but still cannot meet the requirements of the automotive lamp field.
Therefore, there is a need in the art to develop a polycarbonate having a combination of temperature resistance, high heat resistance and low water absorption.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a copolycarbonate having low water absorption, low temperature impact resistance, and high heat resistance. The copolycarbonate prepared by the invention can be applied to special fields, particularly outdoor environments, the influence of environmental temperature difference change on material performance is reduced, and meanwhile, the copolycarbonate can be used as an automobile lamp, and the influence of water vapor on lighting effect can be avoided.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance, which comprises the following structure:
1) A structural unit derived from a dihydroxy compound represented by formula (I):
wherein, X 1 、X 2 Independently represent C1-C10 alkylene, C6-C20 arylene, or represent a chemical bond only, preferably C1-C4 alkylene, C6-C10 arylene, or represent a chemical bond only, more preferably aryleneMethyl, ethylene, phenylene or represent only a chemical bond;
2) A structural unit derived from a polyphenol compound represented by formula (II):
3) A structural unit derived from a dihydroxy compound represented by formula (III):
preferably, the dihydroxy compound represented by formula (I) has the structural formula represented by formula (IV):
in the sources of the structural units of the copolycarbonate according to the present invention, the molar ratio of the dihydroxy compound represented by formula (I) to the dihydroxy compound represented by formula (III) is 1 to 99 to 20, preferably 10 to 15;
preferably, the ratio of the polyphenol compound represented by the formula (II) to the total amount of the dihydroxy compounds represented by the formula (I) and the formula (III) is 1 to 5% by mol, preferably 3 to 4% by mol.
The copolycarbonates according to the invention have a weight average molecular weight of 10000 to 50000 (weight average molecular weight, determined by volume exclusion gel chromatography after calibration with PS or polycarbonate calibration substances in advance), preferably 25000 to 40000, more preferably 30000 to 35000.
For the terpolymerization systems of the present invention comprising formula (I), formula (II) and formula (III), preferably formula (IV), formula (II) and formula (III), the copolycarbonates of the present invention have a transmission of 88 to 90% and the corresponding copolymers have a Vicat temperature of 150 to 210 ℃ depending on the monomer ratio.
The copolycarbonate of the invention can lead the impact strength of the copolymer to be 750-850J/m at 23 ℃ and 400-700J/m at-40 ℃ by adjusting the monomer proportion.
The water absorption of the copolycarbonate is 0.05-0.25%.
The invention also provides a preparation method of the copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance, and the copolycarbonate can be prepared by a melt transesterification method known by the technical personnel in the field;
the melt transesterification method is to prepare polycarbonate by reacting a dihydroxy compound represented by formula (I) or formula (III), a polyphenol compound represented by formula (II) and a carbonic diester by a melt transesterification polycondensation method in the presence of a basic compound catalyst, an ester exchange catalyst or a mixed catalyst composed of the two; among them, the carbonic acid diester, the catalyst, the reaction conditions, and the like can be selected by those skilled in the art according to the actual needs based on the prior art, and the present invention is not particularly limited, and for example, the description in CN103257376A can be adopted, and as a preferable embodiment, the molar ratio of the carbonic acid diester to the dihydroxy compound represented by formula (I) or formula (III) in the present invention is 0.99 to 1.20:1.
the copolycarbonates according to the invention may additionally contain various conventional additives which are customarily added to thermoplastic resins, in proportions of 0 to 5 wt.%, preferably 0 to 2.5 wt.%, particularly preferably 0 to 2 wt.%, relative to the total weight of the copolycarbonate;
the conventional additives are selected from one or more of mold release agents, flow aids, heat stabilizers, hydrolysis stabilizers, antioxidants, UV absorbers, flame retardants, antistatic agents, pigments, reinforcing fillers.
The copolycarbonates of the invention may be formulated with the above-described additives to produce compositions, and may be produced by: the components are mixed in a known manner and melt-compounded and melt-extruded at a temperature of from 250 to 330 ℃ in customary apparatuses such as internal mixers, extruders and twin-screw kneaders, and granulated by means of a granulator.
In addition, the invention also provides a molded part prepared from the copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance or a composition thereof, and a solution prepared from the copolycarbonate.
The copolycarbonate or the composition thereof can be used for preparing any type of formed parts, has good designability, can adapt to forming processes such as injection molding, extrusion, blow molding and the like, and can meet the design requirements of molds.
Preferred applications of the copolycarbonates according to the invention or the compositions thereof are transparent/translucent or colored injection-molded parts, extrudates, such as sheets, film laminates, profiles, semi-finished products, and cast films made of high molecular weight polycarbonates; preferably, the copolycarbonate or the composition thereof is more suitable for shell materials of car lamps, street lamps, searchlights and the like, or some outdoor application scenes such as lamp bead lenses of LED lamps and the like.
The copolycarbonates according to the invention or their compositions can optionally be blended with other thermoplastic polymers and/or conventional additives for processing into any shaped parts/extrudates, all where known polycarbonates, polyester carbonates and polyesters are used.
The polycarbonate sold in the market at present is mainly bisphenol A polycarbonate, the low-temperature impact resistance and the high-temperature resistance of the polycarbonate are poor, and meanwhile, the carbonate structure is a hydrophilic structure, so that water mist is generated in the automobile lamp after long-term use. The invention increases steric hindrance effect and improves heat resistance by introducing the monomer with the structure of formula (I) on a polymer chain segment, and simultaneously, the introduction of the monomer with the structure of formula (II) can form a cross-linked network structure and improve low-temperature impact resistance. Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
according to the invention, by selecting the compounds of the formula (I), the formula (II) and the formula (III) for combined design, preferably selecting the compounds of the formula (IV), (II) and the formula (III), the copolycarbonate with low-temperature impact resistance and high heat resistance can be obtained, and meanwhile, the copolycarbonate of the invention also has low water absorption rate and can be applied to special use environments.
Detailed Description
The following examples are intended to illustrate the present invention, and the present invention is not limited to the scope of the examples, but includes any other changes within the scope of the claims of the present invention.
Some of the raw materials of the reagents used in the examples and comparative examples of the present invention are obtained as follows, and the rest of the raw materials of the reagents are all commercially available products unless otherwise specified:
a monomer represented by the formula (IV): the preparation method is adopted in CN 104370712A;
a monomer of formula (II): the preparation method is adopted in CN 10189898968B;
formula (III) (bisphenol a): purchased from Aladdin reagent company, the purity is more than 98 percent;
diphenyl carbonate: purchased by Aladdin reagent company, with purity more than 98%;
sodium hydroxide: purchased by Aladdin reagent company, with purity more than 99%;
a monomer represented by the formula (V): use of "Mibu, nobuko; synthesized and anti viral activities of body 4,4'-and 2,2' -dihydroxytriphenylmethane [ J ]. Chemical & Pharmaceutical Bulletin (2005), 53 (9), 1171-1174",
phloroglucinol: shanghai Maxin Biochemical science and technology, inc., with purity > 98%;
bisphenol Z (CAS #: 843-55-0): beijing Bailingwei science and technology Limited, the purity is more than 98 percent.
Example 1
Preparing copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance:
1% by mol of the amount of the polyphenol compound of the formula (II) to the total of the compounds of the formula (IV) and the formula (III) from the dihydroxy compound of the formula (IV) and the formula (III) at a molar ratio of 1.
5.26g (0.01 mol) of the dihydroxy compound of the formula (IV), 225.72g (0.99 mol) of the dihydroxy compound of the formula (III), 2.61g (0.01 mol) of the polyphenol compound of the formula (II), 227.07 (1.06 mol) of diphenyl carbonate and 0.02g (5X 10 mol) -4 mol) sodium hydroxide was added to a reactor equipped with a stirring and distilling device and heated to 160 ℃ under normal pressure over 1 hour to melt it. Thereafter, the temperature was raised to 180 ℃ over 1 hour, and stirring was performed. Then, the pressure was adjusted to 1KPa for 30 minutes, and the ester exchange reaction was carried out by maintaining the pressure at 180 ℃ and 1KPa for 30 minutes. Then, the temperature was raised to 200 ℃ at a rate of 50 ℃ per hour, and the temperature was maintained at 200 ℃ and 1KPa for 30 minutes. Then, the temperature was adjusted to 0.5KPa for 10 minutes, and the mixture was maintained at 200 ℃ and 0.5KPa for 1 hour. Then, the pressure was adjusted to 300Pa for 10 minutes and maintained at 300Pa for 30 minutes at 200 ℃. The pressure was reduced to 133Pa or less for 30 minutes, and the mixture was stirred at 200 ℃ for 15 minutes at 133Pa or less to conduct polymerization. After the reaction, 2 times the molar amount of butyl benzoate was added to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under pressure of nitrogen, and cut into pellets by a pelletizer while cooling in a water tank to obtain a copolycarbonate resin, no. A1, weight average molecular weight 32152.
Example 2
Preparing the copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance:
the process of example 1 is referred to with the following exceptions: the molar ratio of dihydroxy compounds of formulae (IV), (III) is 5, the amount of polyphenol compound of formula (II) to the total of compounds of formulae (IV) and (III) is 2% mol; a copolycarbonate resin, no. A2, weight average molecular weight 33214 was prepared using 26.3g (0.05 mol) of the dihydroxy compound having the structure of formula (IV), 216.6g (0.95 mol) of the dihydroxy compound having the structure of formula (III), 5.22g (0.02 mol) of the polyphenol compound having the structure of formula (II), and 218.50g (1.02 mol) of diphenyl carbonate, without changing the other operations and parameters.
Example 3
Preparing the copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance:
the process of example 1 is referred to with the following differences: copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (III) in a molar ratio of 10, the amount of polyphenol compound of formula (II) to the total of compounds of formula (IV) and formula (III) being 3% mol; a copolycarbonate resin, no. A3 and weight average molecular weight 33874 was prepared using 52.6g (0.1 mol) of the dihydroxy compound of formula (IV), 205.2g (0.9 mol) of the dihydroxy compound of formula (III), and 7.83g (0.03 mol) of the polyphenol compound of formula (II), with other procedures and parameters unchanged.
Example 4
Preparing the copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance:
the process of example 1 is referred to with the following differences: copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (III) in a molar ratio of 15, the amount of polyphenol compound of formula (II) to total of compounds of formula (IV) and formula (III) calculated as 4% mol; a copolycarbonate resin, no. A4, having a weight-average molecular weight of 34128 was prepared using 78.9g (0.15 mol) of the dihydroxy compound having the structure of formula (IV), 193.8g (0.85 mol) of the dihydroxy compound having the structure of formula (III), and 10.44g (0.04 mol) of the polyphenol compound having the structure of formula (II), without changing other operations and parameters.
Example 5
Preparing copolycarbonate with low water absorption, low-temperature impact resistance and high heat resistance:
the process of example 1 is referred to with the following exceptions: synthesizing a copolycarbonate prepared from dihydroxy compounds of formula (IV), formula (III) in a molar ratio of 20% to 80, the amount of polyphenol compound of formula (II) to total of compounds of formula (IV) and formula (III) being 5% mol; a copolycarbonate resin, no. A5, having a weight-average molecular weight of 34658 was prepared by using 105.2g (0.2 mol) of the dihydroxy compound having the structure of formula (IV), 182.4g (0.8 mol) of the dihydroxy compound having the structure of formula (III), and 13.05g (0.05 mol) of the polyphenol compound having the structure of formula (II) without changing other operations and parameters.
Comparative example 1
Preparing a polycarbonate from a dihydroxy compound of formula (III):
228g (1 mol) of the dihydroxy compound of the formula (III), 227.07 (1.06 mol) of diphenyl carbonate and 0.02g (5X 10) -4 mol) sodium hydroxide is added into a reactor with stirring and distilling devicesHeated to 160 ℃ under reduced pressure over 1 hour to melt. Thereafter, other operations and parameters were not changed, and the obtained copolycarbonate resin was numbered 1, and had a weight-average molecular weight of 30215.
Comparative example 2
The process of reference example 3 differs only in that: the dihydroxy compound of formula (IV) was replaced with the dihydroxy compound of formula (V) and the other operations and parameters were unchanged to give a copolycarbonate resin, no. 2, weight average molecular weight 33215.
Comparative example 3
The method of example 3 is referred to, except that: the dihydroxy compound of formula (III) was replaced with bisphenol Z dihydroxy compound and other procedures and parameters were unchanged to produce a copolycarbonate resin, no. 3, weight average molecular weight 35184.
Comparative example 4
The method of example 3 is referred to, except that: the polyphenol compound of formula (II) was replaced with phloroglucinol, and other operations and parameters were unchanged to prepare a copolycarbonate resin, no. 4, weight average molecular weight 33842.
Performance test
The copolycarbonates were characterized by means of Vicat temperature (Vicat), impact strength, light transmittance, and water absorption tests.
Vicat was tested according to ISO306 (B120);
impact strength was tested according to ASTM D256;
the transmittance was obtained by measuring a copolycarbonate film and measured according to ASTM D1003; the film is prepared by dissolving copolycarbonate resin in dichloromethane to prepare 10wt% solution, and then performing spin coating to obtain the film with the thickness of 50 μm;
water absorption: measurement (saturation value) according to ISO 62.
The results of the property tests of the copolycarbonates prepared in examples and comparative examples are shown in Table 1.
TABLE 1
As can be seen from the table, the overall properties of the copolycarbonates can be improved by controlling the comonomer ratio. Especially, the monomer proportion of the formula (IV) and the formula (II) is controlled within a certain range, the thermal property and the impact resistance can be improved, and meanwhile, the water absorption of the copolycarbonate can be obviously reduced, so that the material meets special purposes.
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 copolycarbonate having low water absorption, low temperature impact resistance, and high heat resistance, characterized by the following structure:
1) A structural unit derived from a dihydroxy compound represented by formula (I):
wherein, X 1 、X 2 Independently represent C1-C10 alkylene, C6-C20 arylene, or represent a chemical bond only, preferably C1-C4 alkylene, C6-C10 arylene, or represent a chemical bond only, more preferably methylene, ethylene, phenylene, or represent a chemical bond only;
2) A structural unit derived from a polyphenol compound represented by formula (II):
3) A structural unit derived from a dihydroxy compound represented by formula (III):
3. the copolycarbonate according to claim 1 or 2, wherein the molar ratio of the dihydroxy compound represented by formula (I) to the dihydroxy compound represented by formula (III) is from 1;
preferably, the ratio of the polyphenol compound represented by the formula (II) to the total amount of the dihydroxy compounds represented by the formula (I) and the formula (III) is 1 to 5% by mol, preferably 3 to 4% by mol.
4. The copolycarbonate according to any of claims 1 to 3, wherein the weight average molecular weight is 10000 to 50000, preferably 25000 to 40000, more preferably 30000 to 35000.
5. The copolycarbonate of any of claims 1-4, wherein the transmittance is 88 to 90%, corresponding to a copolymer Vicat temperature of 150 to 210 ℃;
the copolycarbonate has the impact strength of 750-850J/m at 23 ℃ and the impact strength of 400-700J/m at-40 ℃;
the water absorption of the copolycarbonate is 0.05-0.25%.
6. Copolycarbonates according to any of claims 1 to 5, characterized in that additives are contained in a proportion of 0 to 5 wt.%, preferably 0 to 2.5 wt.%, particularly preferably 0 to 2 wt.%, relative to the total weight of the copolycarbonate;
the additive is selected from one or more of a mold release agent, a flow auxiliary agent, a heat stabilizer, a hydrolysis stabilizer, an antioxidant, a UV absorbent, a flame retardant, an antistatic agent, a pigment and a reinforcing filler.
7. A process for producing a copolycarbonate having low water absorption, low temperature impact resistance and high heat resistance according to any one of claims 1 to 6, which comprises the step of preparing the copolycarbonate by a melt transesterification method;
the melt transesterification method is to prepare polycarbonate by reacting a dihydroxy compound represented by formula (I) or formula (III), a polyphenol compound represented by formula (II) and a carbonic diester by a melt transesterification polycondensation method in the presence of a basic compound catalyst, an ester exchange catalyst or a mixed catalyst composed of the two;
preferably, the molar ratio of carbonic acid diester to dihydroxy compounds represented by formula (I), formula (III) is 0.99 to 1.20:1.
8. use of a copolycarbonate having low water absorption, low temperature impact resistance and high heat resistance according to any one of claims 1 to 6, wherein a molded article prepared from said copolycarbonate or a composition thereof further comprises a solution prepared from said copolycarbonate according to the present invention.
9. Use according to claim 8 for transparent, translucent or colored injection-molded parts, extrudates such as sheets, film laminates, profiles, semi-finished products, and cast films made of high molecular weight polycarbonate.
10. Use according to claim 8, characterized in that the copolycarbonates or the compositions thereof, are optionally blended with other thermoplastic polymers and/or usual additives for processing into arbitrary shaped parts, extrudates, all where known polycarbonates, polyester carbonates and polyesters have been used.
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CN114763407A (en) * | 2021-01-15 | 2022-07-19 | 万华化学集团股份有限公司 | Copolycarbonate with high transmittance and low-temperature impact resistance, and preparation method and application thereof |
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CN101898968A (en) * | 2009-09-16 | 2010-12-01 | 青岛生物能源与过程研究所 | Method for synthesizing trinitrophloroglucinol |
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