CN115322356A - Copolycarbonate with high heat resistance and high chemical stability resistance, and preparation method and application thereof - Google Patents
Copolycarbonate with high heat resistance and high chemical stability resistance, and preparation method and application thereof Download PDFInfo
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- CN115322356A CN115322356A CN202210949367.2A CN202210949367A CN115322356A CN 115322356 A CN115322356 A CN 115322356A CN 202210949367 A CN202210949367 A CN 202210949367A CN 115322356 A CN115322356 A CN 115322356A
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- copolycarbonate
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- carbonate
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- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000000126 substance Substances 0.000 title abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 21
- 229920000515 polycarbonate Polymers 0.000 claims description 20
- 239000004417 polycarbonate Substances 0.000 claims description 20
- 238000005809 transesterification reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 150000007514 bases Chemical class 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 238000000071 blow moulding Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 claims description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 125000003375 sulfoxide group Chemical group 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-O triphenylazanium Chemical compound C1=CC=CC=C1[NH+](C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-O 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 229920006389 polyphenyl polymer Polymers 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 8
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 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 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000009456 molecular mechanism Effects 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a copolycarbonate with high heat resistance and high chemical resistance, which comprises the following structure: from compounds containing a structure as shown in formula (1)
The structural unit of (1); from compounds containing multiple benzene ring structures
Description
Technical Field
The present invention relates to a copolycarbonate, and more particularly, to a copolycarbonate having high heat resistance and chemical resistance.
Background introduction
Polycarbonate (PC) is a thermoplastic engineering plastic with excellent comprehensive properties, has a wide application range, can be used for manufacturing automobile parts, electric appliances, medical appliances and other products or components, and is frequently exposed to various chemical substances, so that the PC products are expected to have excellent chemical resistance. In addition, in applications in the field of medical instruments and the like, high temperature steam resistance is required during sterilization. Therefore, according to the requirements of related applications, copolycarbonates having both heat resistance and chemical resistance can be developed.
Chinese patent CN201880089604.4 describes polycarbonate with high chemical resistance containing carbonate-siloxane, which has a certain improvement on chemical resistance, but the synthesis method using phosgene is dangerous and not suitable for large-scale production.
Chinese patent CN201611021209.1 describes the preparation of a polycarbonate with high chemical resistance comprising an N-containing dihydroxy compound with a structure responsible for the monomer structure which is difficult to synthesize and does not mention the heat resistant properties of the product.
Chinese patent CN201711272381.9 describes a high-flow, chemical-resistant polycarbonate and a preparation method thereof, in which a thermoplastic polyester elastomer and ABS are added to the polycarbonate to improve the chemical resistance of the polycarbonate, which is limited to the polycarbonate and has problems of poor compatibility, etc.
The introduction of the structure containing F can be beneficial to keeping higher chemical resistance of the polymer, so that the method can be used for synthesizing and developing polymers with high heat resistance and high chemical resistance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a polycarbonate with high heat resistance and high chemical resistance, a preparation method and application thereof.
In one aspect, the present invention provides a copolycarbonate comprising the structure:
1) Derived from structural units of diphenol monomers with lateral groups containing trifluoromethyl and represented by formula (I),
2) Derived from a structural unit represented by formula (II):
in the formula, R 1 And R 2 Each independently represents hydrogen, halogen, C1-C20 alkyl, C4-C20 cycloalkyl or C6-C20 aryl; m and n independently represent an integer of 0 to 4; x represents a single bond, an ether bond, a carbonyl group, a thioether bond, a sulfone group, a sulfoxide group, a C1-C20 alkylene group, a C6-C20 arylene group, a C6-C20 alicyclic group, or a group represented by the formula:
wherein R is 3 And R 4 Each independently represents a C1-C20 alkyl group, a C4-C20 cycloalkyl group or a C4-C20 aryl group; or R 3 And R 4 Together form a C4-C20 alicyclic ring, which C4-C20 alicyclic ring may be optionally substituted with one or more C1-C20 alkyl, C6-C20 aryl, C7-C21 aralkyl, C5-C20 cycloalkyl groups, or combinations thereof.
Preferably, the structural unit represented by formula (II) having a structure represented by bisphenol C, bisphenol F or formula (III) is as follows:
in the sources of 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 (II) is from 1:99. 5:95. 10:90. 15: 85. 20:80. 30:70. 35 and 65.
The molecular weight of the copolycarbonate according to the present invention is not particularly limited, and Mw (weight average molecular weight, measured by GPC after calibration with polystyrene or polycarbonate calibration substances in advance) is preferably 10000 to 100000, preferably 20000 to 60000, and more preferably 30000 to 40000.
The copolycarbonates described herein may additionally comprise various conventional additives commonly added to thermoplastic resins. The proportion of additives is from 0 to 3% by weight, relative to the total weight of copolycarbonate, and optional conventional additives include: one or more of a heat stabilizer, an antioxidant, a flame retardant, a mold release agent, a flow aid, and the like. The copolycarbonates described in the present invention can be prepared by melt transesterification methods known to those skilled in the art.
The melt transesterification method of the present invention is a method for producing a polycarbonate by melt-reacting a compound represented by the formula (I) with a compound represented by the formula (II) in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst composed of both of them.
The basic compound catalyst is selected from one or more of magnesium hydroxide, sodium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, cesium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, triphenylammonium, diethylamine, and the transesterification catalyst is selected from one or more of magnesium carbonate, cesium carbonate, sodium hydroxide, sodium bicarbonate, tetramethylammonium hydroxide; the catalyst is used in a molar ratio of 5X 10 relative to the sum of the dihydroxy compounds -10 ～5×10 -2 Preferably 5×10 -8 ～5×10 -4 。
Melt transesterification is described in Encyclopedia of polymer science, volume 10 (1969), chemistry and physics of polycarbonates, polymer reviews, H.Schne11, volume 9, john Wiley and Sons, inc. (1964) and is therefore well known to those skilled in the art.
In a specific embodiment, the melt transesterification method is specifically to add the dihydroxy compounds represented by the general formula (I) and the general formula (II), the carbonic acid diester, the catalyst and the optional auxiliary agent into a reactor, fully replace the air in the reactor with nitrogen for 3 to 4 times, and then raise the temperature to melt the materials in the reactor, wherein the melting temperature is 140 to 240 ℃, preferably 160 to 220 ℃, and the time for the stage is 10 to 60min, preferably 20 to 40min. After the materials are completely melted, starting stirring, simultaneously keeping the system pressure at 10-30 Kpa, and simultaneously heating the reactor to the transesterification reaction temperature, wherein the transesterification reaction temperature is 180-280 ℃, and preferably 200-260 ℃. The reaction residence time in this stage is 40 to 120min, preferably 60 to 90min. The polycondensation is then started by continuing to reduce the pressure while increasing the temperature, the reaction pressure being in the range from 50 to 1000Pa, preferably from 100 to 300Pa, at this stage. The reaction temperature in this stage is 220 to 300 ℃ and preferably 240 to 280 ℃. The residence time in this stage is 20 to 100min, preferably 30 to 80min. The micromolecule compounds and the like generated in the reaction process can be removed by adopting a vacuum-pumping mode and a distillation method, and finally the copolycarbonate resin with high molecular weight is obtained in the reactor.
The prepared copolycarbonate can change the glass transition temperature of the prepared copolycarbonate within the range of 190-220 ℃ by adjusting the proportion of the monomers in the formula (I) and the formula (II), so that the prepared copolycarbonate has good chemical resistance, and the retention rate of the tensile modulus and the elongation at break of the prepared copolycarbonate is more than 90% after the prepared copolycarbonate is soaked in ethyl acetate for 24 hours at normal temperature.
The invention likewise relates to shaped parts produced from the copolycarbonates according to the invention or the compositions thereof, and to the use of the shaped parts. Solutions of the copolycarbonates according to the invention are also included for applications requiring high heat resistance and high chemical resistance.
The copolycarbonates according to the invention or the compositions thereof can be used for producing shaped parts of any type, which can be produced by injection molding, extrusion and blow molding processes.
The invention has the beneficial effects that:
researches show that the comprehensive performance of the polymer can be remarkably improved by introducing a multi-benzene-ring structure and a heterocyclic molecular mechanism into the molecular chain segment structure of the polymer material. The heat resistance of the polymer can be obviously improved by introducing a polyphenyl ring structure and heteroatoms at the polymerization end, and the introduction of the F-containing structure can be beneficial to maintaining higher chemical resistance of the polymer, so that the polymer can be used for synthesis and development of high-heat-resistance and high-chemical-resistance polymers.
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 also includes any other changes within the scope of the claims of the present invention.
Raw materials and sources:
bisphenol A: aladdin reagent Gc
Bisphenol C: GC from Aladdin reagent Ltd
Bisphenol F: GC from Aladdin reagent Ltd
Sodium hydroxide: aladdin reagent Limited AR
Diphenyl carbonate 99% by Aladdin reagent Co., ltd
Other raw materials are all commercially available raw materials unless otherwise specified
Method for testing weight average molecular weight:
weight average molecular weight, synthesis of a monomer of a diphenol containing trifluoromethyl in its side groups, determined by GPC after preliminary calibration with polystyrene or polycarbonate calibration substances
Specifically, the compound can be prepared by referring to example 1 in the Chinese patent CN 114181053A-a method for preparing diphenol monomer with lateral group containing trifluoromethyl and polyarylether polymer thereof.
Example 1
Copolycarbonates prepared from formula (I), formula (III) were synthesized in a molar ratio of 1.
4g (0.01 mol) of the compound of the formula (I), 225.72g (0.99 mol) of the compound of the formula (III), 218.28g (1.02 mol) of diphenyl carbonate and 0.02g (5X 10 mol) -4 mol) NaOH is added into a reactor with a stirring and flowing device, air in the reactor is fully replaced by nitrogen for 3 times, then the temperature is increased to melt the materials in the reactor, the melting temperature is 180 ℃, and the NaOH stays for 30min in the stage. After the materials are completely melted, stirring is started, the system pressure is kept at 20Kpa, the reactor temperature is heated to the transesterification reaction temperature, the transesterification reaction temperature is 240 ℃, and the reaction residence time in the stage is 60min. Then, the pressure was further lowered while the temperature was raised to start the polycondensation reaction, the stage reaction pressure was 120Pa, the stage reaction temperature was 260 ℃ and the stage residence time was 80min. After the reaction was completed, ethyl benzoate was added in an amount of 1.5 times by mole based on the amount of the catalyst to deactivate the catalyst. The reaction mixture was discharged from the bottom of the autoclave under a pressure of nitrogen, passed through a cooling water tank, and cut and granulated by a cutter to obtain a copolycarbonate having the number P1 and the weight-average molecular weight of 30254.
Example 2
Copolycarbonates prepared according to formula (I) and formula (III) were synthesized in a molar ratio of 5.
A copolycarbonate was synthesized in accordance with example 1, with the exception that 20g (0.05 mol) of the compound having the structure of the formula (I) and 216.6g (0.95 mol) of the compound having the structure of the formula (III) were used, and the number P2 and the weight average molecular weight were 31257.
Example 3
Copolycarbonates prepared according to formula (I) and formula (III) were synthesized in a molar ratio of 10.
A copolycarbonate was synthesized in accordance with example 1, except that 40g (0.10 mol) of the compound having the structure of the formula (I) and 205.2g (0.9 mol) of the compound having the structure of the formula (III) were used, and the number P3 and the weight average molecular weight were 32542.
Example 4
Copolycarbonates prepared according to formula (I) and formula (III) were synthesized in a molar ratio of 20.
A copolycarbonate, no. P4, having a weight average molecular weight of 33101 was synthesized in accordance with example 1 except that 80g (0.20 mol) of the compound having the structure of the formula (I) and 182.4g (0.80 mol) of the compound having the structure of the formula (III) were used.
Example 5
Copolycarbonates prepared according to formula (I) and formula (III) were synthesized in a molar ratio of 30.
A copolycarbonate was synthesized in accordance with example 1, except that 120g (0.30 mol) of the compound having the structure of the formula (I) and 159.6g (0.70 mol) of the compound having the structure of the formula (III) were used, the number P5 and the weight average molecular weight were 33548.
Example 6
Copolycarbonates prepared according to formula (I) and formula (III) were synthesized in a molar ratio of 35.
A copolycarbonate was synthesized in accordance with example 1, except that 140g (0.35 mol) of the compound having the structure of the formula (I) and 148.2g (0.65 mol) of the compound having the structure of the formula (III) were used, the number P6 was changed, and the weight average molecular weight was 33910.
Example 7
A copolycarbonate prepared from formula (I), bisphenol C was synthesized in a 1 molar ratio.
A copolycarbonate was synthesized in accordance with example 1, except that 4g (0.01 mol) of the compound having the structure of formula (I) and 253.44g of bisphenol C were used, and the number P7 and the weight average molecular weight 30835 were determined.
Example 8
A copolycarbonate prepared from formula (I), bisphenol F was synthesized in a 1 molar ratio.
A copolycarbonate was synthesized in accordance with example 1, except that 4g (0.01 mol) of the compound having the structure of formula (I) and 198g of bisphenol F were used, and the polycarbonate was numbered P8 and had a weight average molecular weight of 29642.
Example 9
Copolycarbonates prepared according to formula (I) and formula (III) were synthesized in a molar ratio of 1.
4g (0.01 mol) of the compound of the formula (I), 225.72g (0.99 mol) of the compound of the formula (III), 218.28g (1.02 mol) of diphenyl carbonate and 0.02g (5X 10 mol) -4 mol) NaOH is added into a reactor with a stirring and flowing device, air in the reactor is fully replaced by nitrogen for 3 times, then the temperature is increased to melt the materials in the reactor, the melting temperature is 160 ℃, and the NaOH stays for 20min in the stage. When the materials are completely mixedAfter melting, stirring was started while maintaining the system pressure at 10Kpa, and the reactor temperature was heated to the transesterification reaction temperature, which was 200 ℃, and the reaction residence time at this stage was 60min. Then, the pressure was further decreased while the temperature was increased to start the polycondensation reaction, the reaction pressure in this stage was 100Pa, the reaction temperature in this stage was 240 ℃ and the residence time in this stage was 30min. After the reaction was completed, ethyl benzoate was added in an amount of 1.5 times by mole based on the amount of the catalyst to deactivate the catalyst. The reaction mixture was discharged from the bottom of the autoclave under a pressure of nitrogen, passed through a cooling water tank, and cut and granulated by a pelletizer to obtain a copolycarbonate having a weight average molecular weight of 30248 and No. P9.
Example 10
Copolycarbonates prepared according to formula (I) and formula (III) were synthesized in a molar ratio of 1.
4g (0.01 mol) of the compound of the formula (I), 225.72g (0.99 mol) of the compound of the formula (III), 218.28g (1.02 mol) of diphenyl carbonate and 0.02g (5X 10 mol) -4 mol) NaOH is added into a reactor with a stirring and flowing-out device, air in the reactor is fully replaced by nitrogen for 3 times, then the temperature is increased to melt the materials in the reactor, the melting temperature is 220 ℃, and the NaOH stays in the stage for 40min. After the materials are completely melted, stirring is started, the system pressure is kept at 30Kpa, the temperature of the reactor is heated to the ester exchange reaction temperature, the ester exchange reaction temperature is 260 ℃, and the reaction residence time in the stage is 90min. The polycondensation was then started by continuing to decrease the pressure while increasing the temperature, the reaction pressure in this stage being 300Pa, the reaction temperature in this stage being 280 ℃ and the residence time in this stage being 80min. After the reaction was completed, ethyl benzoate was added in an amount of 1.5 times by mole based on the amount of the catalyst to deactivate the catalyst. The reaction mixture was discharged from the bottom of the reactor under a nitrogen pressure, passed through a cooling water tank, and cut and granulated by a cutter to obtain a copolycarbonate having a weight average molecular weight of 30357, no. P10.
Comparative example 1
Synthesis of a polycarbonate prepared by formula (III).
228g (1 mol) of the compound of the formula (II), 218.28g (1.02 mol) of diphenyl carbonate and 0.01g (5X 10) -4 mol) NaOH is added into a reactor with a stirring and flowing device, air in the reactor is fully replaced by nitrogen for 3 times, then the temperature is increased to melt the materials in the reactor, the melting temperature is 180 ℃, and the NaOH stays for 30min in the stage. After the materials are completely melted, stirring is started, the system pressure is kept at 20Kpa, the temperature of the reactor is heated to the ester exchange reaction temperature, the ester exchange reaction temperature is 240 ℃, and the reaction residence time in the stage is 60min. Then, the pressure was further decreased while the temperature was increased to start the polycondensation reaction, the reaction pressure in this stage was 120Pa, the reaction temperature in this stage was 260 ℃ and the residence time in this stage was 80min. And carrying out polycondensation reaction. After the reaction was completed, ethyl benzoate was added in an amount of 1.5 times by mole based on the amount of the catalyst to deactivate the catalyst. The reaction product was discharged from the bottom of the autoclave under a nitrogen pressure, passed through a cooling water tank, and cut and granulated by a cutter to obtain a polycarbonate having a number D1 and a weight-average molecular weight of 25419.
Comparative example 2
Copolycarbonates prepared according to formula (I) and formula (III) were synthesized in a molar ratio of 50.
A copolycarbonate was synthesized in accordance with example 1 except that 200g (0.50 mol) of the compound having the structure of the formula (I) and 114g (0.50 mol) of the compound having the structure of the formula (III) were used, and the number D2 and the weight average molecular weight were 35785.
Comparative example 3
The polycarbonate prepared by the bisphenol structural monomer in the example 3 in the Chinese patent CN104628543 is selected.
A polycarbonate was synthesized in accordance with example 1, except that 339.6g (1 mol) of the bisphenol structural monomer in example 3 and 218.28g (1.02 mol) of diphenyl carbonate in China patent CN104628543 were used, and the polycarbonate was numbered D3 and had a weight average molecular weight of 34525.
Performance testing
The copolycarbonates were characterized by means of glass transition temperature, tg, tensile modulus, elongation at break tests, tg measured by dynamic differential thermal analysis (DSC) according to ASTM E1356.
Tensile modulus
The tensile modulus and the elongation at break are characterized by a universal tester according to ISO527, and the values before and after soaking in ethyl acetate (23 ℃) are respectively tested after soaking in ethyl acetate for 24 hours at normal temperature (23 ℃), and the retention rate is calculated according to the results.
The test results are shown in table 1 below.
TABLE 1
As shown in Table 1, the heat resistance of the copolycarbonate can be remarkably improved by adding the monomer with the polyphenyl ring structure in the polymerization process, and the chemical corrosion resistance of the copolymer is remarkably improved by introducing the F element. Therefore, it is considered that the performance of the polymer can be improved by introducing a polyphenyl ring, a heteroatom and a halogen element in the polymerization process of the copolycarbonate.
Claims (9)
1. A copolycarbonate comprising the structure:
1) Derived from structural units of diphenol monomers with lateral groups containing trifluoromethyl and represented by formula (I),
2) Derived from a structural unit represented by formula (II):
in the formula, R 1 And R 2 Each independently represents hydrogen, halogen, C1-C20 alkyl, C4-C20 cycloalkyl or C6-C20 aryl; m and n independently represent an integer of 0 to 4; x represents a single bond, an ether bond, a carbonyl group, a thioether bond, a sulfone group, a sulfoxide group, a C1-C20 alkylene group, a C6-C20 arylene group, a C6-C20 alicyclic group, or a group represented by the formula:
wherein R is 3 And R 4 Each independently represents a C1-C20 alkyl group, a C4-C20 cycloalkyl group or a C4-C20 aryl group; or R 3 And R 4 Together form a C4-C20 alicyclic ring, which C4-C20 alicyclic ring may be optionally substituted with one or more C1-C20 alkyl, C6-C20 aryl, C7-C21 aralkyl, C5-C20 cycloalkyl groups, or combinations thereof.
2. The copolycarbonate of claim 1, wherein the structural unit represented by formula (II) is represented by bisphenol C, bisphenol F, or formula (III) as follows:
3. the copolycarbonate of claim 1 or 2, wherein the molar ratio of the dihydroxy compound represented by formula (I) to the dihydroxy compound represented by formula (II) is 1:99. 5:95. 10:90. 15: 85. 20:80. 30:70. 35 and (b) a power supply unit.
4. The copolycarbonate of any of claims 1-3, further comprising additives in a proportion of 0 to 3wt% relative to the total weight of the copolycarbonate, the additives comprising one or more selected from the group consisting of heat stabilizers, antioxidants, flame retardants, mold release agents, flow aids, and the like.
5. A process for the preparation of a copolycarbonate according to any of claims 1 to 4, wherein the process comprises the steps of: the polycarbonate is produced by melt-reacting the formula (I) and the formula (II) by a melt transesterification method in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst composed of both.
6. The method of claim 5, wherein the basic compound catalyst is selected from one or more of magnesium hydroxide, sodium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, cesium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, triphenylammonium, diethylamine; and/or the transesterification catalyst is selected from one or more of magnesium carbonate, cesium carbonate, sodium hydroxide, sodium bicarbonate and tetramethylammonium hydroxide.
7. The method of claim 5 or 6, wherein the catalyst is used in an amount of 5 x 10 relative to the molar ratio of the sum of the dihydroxy compounds -10 ～5×10 -2 Preferably 5X 10 -8 ～5×10 -4 。
8. Use of a copolycarbonate according to any one of claims 1 to 4 or produced by the production method according to any one of claims 5 to 7 for producing molded parts by injection molding, extrusion or blow molding.
9. A shaped part which is obtained from the copolycarbonate according to any one of claims 1 to 5 or the copolycarbonate produced by the production method according to any one of claims 6 to 7 by injection molding, extrusion, or blow molding.
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