CN107022071A - A kind of specificity end-blocking Copolycarbonate of polysiloxane block and preparation method thereof - Google Patents
A kind of specificity end-blocking Copolycarbonate of polysiloxane block and preparation method thereof Download PDFInfo
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- CN107022071A CN107022071A CN201710159034.9A CN201710159034A CN107022071A CN 107022071 A CN107022071 A CN 107022071A CN 201710159034 A CN201710159034 A CN 201710159034A CN 107022071 A CN107022071 A CN 107022071A
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- copolycarbonate
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- -1 polysiloxane Polymers 0.000 title claims abstract description 45
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 8
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 39
- 239000004425 Makrolon Substances 0.000 claims abstract description 26
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005770 Eugenol Substances 0.000 claims abstract description 22
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960002217 eugenol Drugs 0.000 claims abstract description 22
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 20
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 14
- 239000004417 polycarbonate Substances 0.000 claims abstract description 14
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960003500 triclosan Drugs 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 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 claims description 36
- 238000003756 stirring Methods 0.000 claims description 30
- 239000008346 aqueous phase Substances 0.000 claims description 25
- 239000012071 phase Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 229940106691 bisphenol a Drugs 0.000 claims description 18
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 239000004033 plastic Substances 0.000 claims description 12
- 229920003023 plastic Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000000844 anti-bacterial effect Effects 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000007655 standard test method Methods 0.000 claims description 3
- 241000588724 Escherichia coli Species 0.000 claims description 2
- 241000191967 Staphylococcus aureus Species 0.000 claims description 2
- 210000000481 breast Anatomy 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000003921 oil Substances 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 17
- 235000011121 sodium hydroxide Nutrition 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 9
- 230000004044 response Effects 0.000 description 8
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 8
- 230000002421 anti-septic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229920002413 Polyhexanide Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000295644 Staphylococcaceae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000010627 cedar oil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- HKIOYBQGHSTUDB-UHFFFAOYSA-N folpet Chemical class C1=CC=C2C(=O)N(SC(Cl)(Cl)Cl)C(=O)C2=C1 HKIOYBQGHSTUDB-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000010792 warming Methods 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
- C08G64/18—Block or graft polymers
- C08G64/186—Block or graft polymers containing polysiloxane sequences
-
- 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
-
- 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
- C08G64/40—Post-polymerisation treatment
- C08G64/406—Purifying; Drying
-
- 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
- C08G64/42—Chemical after-treatment
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
- C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses specificity end-blocking Copolycarbonate of a kind of polysiloxane block and preparation method thereof, the random copolymerization makrolon is made up of polycarbonate block, polysiloxane block and specific closed-end structure.Specificity end-blocking Copolycarbonate of the invention in main chain due to introducing the polysiloxanes of proper amount of eugenol end-blocking with excellent mechanical performance, blocked again with triclosan simultaneously, so as to make it have excellent anti-microbial property, with actual application value, demand of the modern development in science and technology to material property disclosure satisfy that.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of specificity end-blocking copolymerization of polysiloxane block
Carbonic ester, and further relate to prepare the method that the specificity blocks Copolycarbonate.
Background technology
Makrolon (Polycarbonate, PC) be in strand the high molecular polymer containing carbonate group and with
The general name of the various materials of prepared by it is matrix.According to the difference of ester group structure, it can be divided into aliphatic, alicyclic, fragrance
The polytypes such as race, aliphatic-aromatic, wherein fatty poly-ester carbonate have that fusing point is low, solubility is big, heat endurance is poor,
The shortcomings of mechanical strength is not high, so as to can not be used as engineering plastics；Alicyclic and aliphatic-aromatic makrolon due to
The trend of crystallization is excessive, property is crisp and mechanical strength is not high so that it can not be used widely；From the cost of raw material, product
The many-sides such as energy, processing and forming condition consider, and only aromatic copolycarbonate just has industrial application value, especially with
Bisphenol A polycarbonate is mostly important.Typically in the case where not being illustrated especially, usually said makrolon is
Refer to bisphenol A polycarbonate and its transformed lines show.
Bisphenol A polycarbonate is a kind of still engineering thermoplastic's modeling of the amorphous transparent in the life development phase now
Material, high comprehensive performance, with higher glass transition temperature, heat distortion temperature, wider temperature in use scope water absorption rate is low, make
Product size, preferably higher impact strength, mechanical strength and the advantages of electrical insulating property, are that other general engineering plastics can not
Reach.However, due to the high rigidity and big steric hindrance of strand, bisphenol A polycarbonate is viscous with higher melt
Degree, processing difficulties, it is difficult to make massive article, easily occur stress cracking, and solvent resistance, wear resistance are poor, high temperature foaming.
Therefore, in recent years, makrolon researcher and manufacturer are directed to being modified makrolon always.
Polysiloxanes is directly connected to the polymerization of organic group on being a class using the Si-O keys that repeat as main chain and silicon atom
Thing.Because the bond energy of the Si-O keys in the main chain of polysiloxanes is far above the bond energy of C-C keys, therefore it has well thermally-stabilised
Property.In addition, the electronegativity difference of Si atoms and O atom is big, so Si-O bond polarities are big, shielding is played to the alkyl connected
Effect, improves oxidation stability.Meanwhile, polysiloxanes high temperature resistant, it is low temperature resistant, have excellent weather resistance；The high and low surface of Chain Flexibility
Tension force and low-surface-energy, can be effectively improved polymer segment locomitivity；And easy processing.So, these of polysiloxanes are excellent
Point compensate for the shortcoming of makrolon just.
In addition, with the improvement of people ' s living standards and to the attention rate more and more higher of health, people are to plastic products
Environment protection health and security are also increasingly paid attention to, thus, and the production of anti-biotic material turns into an emerging industry, particularly resists
Bacterium polycarbonate plastic there has also been unprecedented development.The B of CN 103059541 disclose a kind of antibacterial polycarbonate plastic,
Including following components in parts by weight：100 parts of makrolon, 0.3-0.5 parts of complex antimicrobials, the complex antimicrobials, by following
Component is constituted by weight：2-6 parts of cedar wood oil, 4-8 parts of chitosan, 10-20 parts of nano titanium oxide, nano phase ag_2 o 15-25
Part, 30-50 parts of polyhexamethylene guanide phosphate, 2-4 parts of N- (trichloro-methylthio) phthalimides.The antibacterial makrolon
The antiseptic consumption of plastics is excessively complicated, and cost is too high, and the mechanical performance of the antibacterial polycarbonate plastic is not high.It is at present
Only, prepare antibacterial polycarbonate plastic and be usually chosen in makrolon and add antiseptic, the antiseptic often having now can be divided into
Inorganic powder antiseptic and organic liquid antiseptic, wherein organic liquid are met high temperature and easily decomposed, but the processing temperature of makrolon
It is higher, therefore add organic fluid antimicrobial agent and do not have and really given play to antibacterial action；And inorganic powder antiseptic is due to poly- carbon
Acid ester resin viscosity is difficult to be evenly dispersed in resin greatly and in process and needs to add carrier material, and these are carried
Body material can have a huge impact to the mechanical performance of makrolon, while can also make makrolon change colour.
In summary, it is necessary to which developing a kind of had not only had stronger anti-microbial property and but also new with excellent mechanical performance
Type makrolon.
The content of the invention
Present invention seek to address that there is provided a kind of specificity end-blocking of polysiloxane block is common for above mentioned problem of the prior art
Makrolon, it has excellent mechanical performance and anti-microbial property.One kind is also provided simultaneously and prepares above-mentioned specificity end-blocking copolymerization
The method of carbonic ester, process is simple and easy to control, being capable of large-scale production and products collection efficiency height.
To achieve these goals, the invention provides a kind of specificity end-blocking Copolycarbonate of polysiloxane block,
Characterized in that, the specificity end-blocking Copolycarbonate includes following three kinds of structures：
(1) polycarbonate block of following formula (I), and
(2) polysiloxane block of following formula (II),
(3) closed-end structure of following formula (III),
Wherein, m is the integer between the integer between 90 to 200, preferably 150 to 200；N is the integer between 10 to 70,
It is preferred that the integer between 50 to 60；P is the integer between 40 to 50, the integer between preferably 45 to 50, and the specificity envelope
The percentage by weight for holding the polycarbonate block of formula (I) in Copolycarbonate is 80-90%, the polysiloxane block of formula (II)
Percentage by weight is 10-20%.
The specificity end-blocking Copolycarbonate of the present invention has an especially excellent mechanical performance, particularly with higher low
Warm impact strength and relatively low ductility/brittle transition temperature, and there is preferable anti-microbial property simultaneously, it disclosure satisfy that satisfaction
The need for modern society.
Preferably, in above-mentioned specificity end-blocking Copolycarbonate, the specificity end-blocking Copolycarbonate Chinese style (II)
Polysiloxane block percentage by weight be 15-20%.
Preferably, in above-mentioned specificity end-blocking Copolycarbonate, formula (I) in the specificity end-blocking Copolycarbonate
The weight ratio of polycarbonate block and the polysiloxane block of formula (II) is (80-85)：(15-20).If in Copolycarbonate
Polysiloxane block relative quantity very little, low temperature impact strength can be damaged；And if the relative quantity of polysiloxane block too
It is many, then it can damage other performances such as heat endurance of Copolycarbonate and can also increase cost.
Preferably, in above-mentioned specificity end-blocking Copolycarbonate, the specificity blocks dividing equally again for Copolycarbonate
Son amount is 30000-60000, and polydispersity index is 1.1-2.4.If the weight of the specificity end-blocking Copolycarbonate is equal
Molecular weight is too small, then its mechanical performance can be significantly reduced；If if the Weight-average molecular of the specificity end-blocking Copolycarbonate
Amount is excessive, then it will be difficult to, i.e., can not be applied.The polydispersity of the specificity end-blocking Copolycarbonate refers to simultaneously
If number is excessive, due to being unfavorable for its performance.
It is highly preferred that in above-mentioned specificity end-blocking Copolycarbonate, the weight of the specificity end-blocking Copolycarbonate is equal
Molecular weight is 30000-50000, most preferably 35000-45000, and polydispersity index is 1.2-1.6.
Preferably, in above-mentioned specificity end-blocking Copolycarbonate, the specificity end-blocking Copolycarbonate is at -50 DEG C
Izod notched impact strength be >=550J/m2, it is the Chalpy impact of the plastics according to as defined in ASTM D256-1997
The standard test method of performance detection is measured the value of gained.
Preferably, it is above-mentioned specificity end-blocking Copolycarbonate in, it is described specificity end-blocking Copolycarbonate ductility/
Brittle transition temperature is -25 to -60 DEG C.In the present invention, the ductility/brittle transition temperature refers to that sample lacks in cantilever beam
In the experiment of mouthful impact property from 100% ductility be converted to 100% fragility in the case of temperature.
Preferably, in above-mentioned specificity end-blocking Copolycarbonate, the specificity end-blocking copolymerization polycarbonate is small 24
When it is interior be more than 99% to the bacteriostasis rate of Escherichia coli and staphylococcus aureus under conditions of 37 DEG C, it is according to JIS Z
The method of antimicrobial product antibacterial activity and effect test as defined in 2801 is measured the value of gained.
Specificity end-blocking Copolycarbonate prepared by the present invention is due to the polysiloxanes containing eugenol end-blocking in main chain
Structure and with excellent mechanical performance, simultaneously because special closed-end structure and with preferable anti-microbial property, expand it
Application.
In addition, present invention also offers a kind of method for preparing above-mentioned specificity end-blocking Copolycarbonate, it includes following
Step：
(1) aqueous phase is prepared：Bisphenol-A, alkali metal hydroxide, water are pressed 1:(2.5-4.0):The mol ratio of (80-140) is mixed
Close, after bisphenol-A is completely dissolved, add catalyst and triclosan end-capping reagent, constitute aqueous phase；
(2) oil phase is prepared：Phosgene and inert organic solvents are pressed 1:The weight of (45-65) constitutes oil phase than mixing；
(3) polymerisation is carried out：By oil phase and the polysiloxanes of eugenol end-blocking under 700-900rpm stir speed (S.S.)
It is added dropwise into aqueous phase to carry out polymerisation, while being maintained at the pH of reaction system with alkali metal hydroxide aqueous solution
10.5-11.5, and the temperature of reaction system is maintained at 45-50 DEG C, after reacting 2-4 hours, obtain specificity end-blocking copolymerization carbon
Acid esters emulsion；
(4) post-process：Specificity end-blocking Copolycarbonate emulsion prepared by step (3) is purified and removed organic molten
Agent, you can obtain product,
Wherein, in step (3), the phosgene added is (1.3-1.4) with bisphenol-A mol ratio:1, the eugenol envelope
The polysiloxanes at end and the weight ratio of bisphenol-A are 1：(4-9), and the weight average molecular weight of the polysiloxanes of the eugenol end-blocking is
3500-4200, polydispersity index is less than 3.5.
Preparation method step of the present invention is simple to operation, and mild condition reduces production cost, can mass produce,
And products collection efficiency is high.
Preferably, in the above-mentioned method for preparing the specificity end-blocking Copolycarbonate, prepared in the step (1)
The mol ratio of catalyst and bisphenol-A is 0.001-0.0015 in aqueous phase:1, so that reaction speed is suitable, molecular weight of product will not mistake
It is small or excessive, prepared specificity end-blocking Copolycarbonate mist degree ＜ 4, smooth in appearance, system when the amount of catalyst is in the range of
It is more attractive in appearance into plastic products.
Preferably, in the above-mentioned method for preparing the specificity end-blocking Copolycarbonate, prepared in the step (1)
The percentage of quality of the quality of triclosan in aqueous phase based on the aqueous phase is 0.1-0.3%
Preferably, in the above-mentioned method for preparing the specificity end-blocking Copolycarbonate, the catalyst is selected from four fourths
Base ammonium bromide, triethylamine and/or tetrabutylammonium chloride.
Preferably, in the above-mentioned method for preparing the specificity end-blocking Copolycarbonate, the inert organic solvents choosing
From makrolon can be dissolved to the solvent of at least 5wt% degree, or its mixture at a temperature of about 20 DEG C.More preferably
Ground, the inert organic solvents are selected from the one or more of aromatics, aromatic hydrocarbons and aliphatic chlorinated hydrocarbons；Most preferably, the inertia has
Machine solvent be selected from dichloromethane, dichloroethanes, trichloro ethylene, 1,1,1- trichloroethanes, 1,1,2- trichloroethanes, carbon tetrachloride,
Benzene, toluene, m-/o-/p-xylene and chlorobenzene and its mixture.
Preferably, in the above-mentioned method for preparing the specificity end-blocking Copolycarbonate, in the step (3), phosgene
Addition speed be 100-200g/min.
Preferably, it is described in the step (3) in the above-mentioned method for preparing the specificity end-blocking Copolycarbonate
The addition speed of the polysiloxanes of eugenol end-blocking is 150-200g/min.
Preparation method of the present invention is passed through speed and other specification by point regulation pH value of reaction system, phosgene, constantly
Optimizing reaction system, makes parameters cooperate, and prepares the specificity envelope with excellent anti-microbial property and mechanical performance
Copolycarbonate is held, its application is expanded.
Compared with prior art, the present invention has advantages below and effect：
(1) poly- silicon of the present invention specificity end-blocking Copolycarbonate due to introducing proper amount of eugenol end-blocking in main chain
Oxygen alkane and with excellent mechanical performance, while blocked with triclosan again, so as to make it have excellent anti-microbial property, tool
There is actual application value, disclosure satisfy that demand of the modern development in science and technology to material property；
(2) preparation method of the present invention is simple and easy to apply, and controllability is high, can realize the production of industrially scalable, be conducive to
Product specificities of the present invention are promoted to block the large-scale application of Copolycarbonate.
Embodiment
In order that objects and advantages of the present invention are more concise, the present invention will be explained with specific examples below
It is bright, but the present invention is only limitted to absolutely not these embodiments.Following examples are only more preferably embodiment, and be only used for explaining of the invention
State the present invention, it is impossible to be interpreted as limiting the scope of the present invention.It should be pointed out that it is all the present invention essence and principle it
Interior done any modifications, equivalent substitutions and improvements etc., should be included in the scope of the protection.Therefore, it is of the invention
The protection domain of patent should be determined by the appended claims.
Viscosity is measured according to GB/T 7193-2008 unsaturated polyester resin test methods in the present invention.
Preparative Example<The preparation of the polysiloxanes of eugenol end-blocking>
Octamethylcy-clotetrasiloxane (142kg, 480mol), tetramethyl disiloxane (4.02kg, 30mol) and carclazyte are urged
Agent Filtrol 20 (2.34kg, 1.6 weight %), which is added to, is equipped with the reactor of agitator and thermometer and stirs 30
Minute is so that reaction system uniformly, is then warming up to 50 DEG C with 2 DEG C/min speed and stirred at this temperature by mixtures of materials
Mix 2.5 hours, the temperature of reaction system is then continuously heating to 110 DEG C and violent at such a temperature with 5 DEG C/min speed
Stirring reaction 6 hours, is filtered to remove clay catalyst afterwards.Then the material after removal clay catalyst is put into equipment
Have in the reactor of agitator and thermometer and in the case of stirring with the speed of 25g/ minutes be added dropwise eugenol (16.72kg,
102mol) and karstedt platinum catalysts (67g) mixed solution, stirring reaction 13 hours at a temperature of 80 DEG C afterwards.With
0.2kPa is decompressed at 200 DEG C afterwards unreacted raw material is distilled off, obtain the polysiloxanes of eugenol end-blocking, yield is
99%, its viscosity at 25 DEG C be in 70 this, using gpc analysis product, its weight average molecular weight is 3854, polydispersity index
For 2.7.
Prepare embodiment<The synthesis of specificity end-blocking Copolycarbonate>
Prepare embodiment 1
228.3kg bisphenol-As, 100kg sodium hydroxides, the mixing of 1600kg water are added in a mixer, are completely dissolved in bisphenol-A
Afterwards, then add 324g catalyst TBAB and stir until all dissolvings, add 2.4kg triclosans simultaneously afterwards
Stir, form aqueous phase；128.9kg liquid phosgene and 4851L dichloromethane are added in another blender, shape is well mixed
Into oil phase；Then sodium phenolate aqueous phase is put into polymer reactor, afterwards under 700rpm stir speed (S.S.) by oil phase and
The polysiloxanes of eugenol end-blocking prepared by 26.4kg Preparative Examples is added with 100g/min and 150g/min speed respectively
Into polymer reactor, while concentration is added dropwise into reaction system keeps reaction system for 10 weight % sodium hydrate aqueous solution
PH value maintain 45 DEG C 10.5, and by the temperature of reaction system；After question response 2 hours, isolate and purify reaction system and remove
Organic solvent, obtains random copolymerization makrolon of the present invention.After measured, yield is 99%, and is divided equally again using gpc analysis product
Son amount is 34983, and polydispersity index is 2.27.
Prepare embodiment 2
228.3kg bisphenol-As, 129kg sodium hydroxides, the mixing of 1900kg water are added in a mixer, are completely dissolved in bisphenol-A
Afterwards, then add 365g catalyst TBAB and stir until all dissolvings, add 3.9kg triclosans simultaneously afterwards
Stir, form aqueous phase；130.5kg liquid phosgene and 5417L dichloromethane are added in another blender, shape is well mixed
Into oil phase；Then sodium phenolate aqueous phase is put into polymer reactor, afterwards under 800rpm stir speed (S.S.) by oil phase and
The polysiloxanes of eugenol end-blocking prepared by 39.5kg Preparative Examples is added with 120g/min and 170g/min speed respectively
Into polymer reactor, while concentration is added dropwise into reaction system keeps reaction system for 10 weight % sodium hydrate aqueous solution
PH value maintain 47 DEG C 10.9, and by the temperature of reaction system；After question response 2.5 hours, isolate and purify reaction system and take off
Except organic solvent, random copolymerization makrolon of the present invention is obtained.After measured, yield is 99%, and equal using gpc analysis product weight
Molecular weight is 37592, and polydispersity index is 1.97.
Prepare embodiment 3
228.3kg bisphenol-As, 145kg sodium hydroxides, the mixing of 2100kg water are added in a mixer, are completely dissolved in bisphenol-A
Afterwards, then add 400g catalyst TBAB and stir until all dissolvings, add 3.9kg triclosans simultaneously afterwards
Stir, form aqueous phase；135.1kg liquid phosgene and 6118L dichloromethane are added in another blender, shape is well mixed
Into oil phase；Then sodium phenolate aqueous phase is put into polymer reactor, afterwards under 900rpm stir speed (S.S.) by oil phase and
The polysiloxanes of eugenol end-blocking prepared by 51.2kg Preparative Examples is added with 150g/min and 180g/min speed respectively
Into polymer reactor, while concentration is added dropwise into reaction system keeps reaction system for 10 weight % sodium hydrate aqueous solution
PH value maintain 50 DEG C 11.2, and by the temperature of reaction system；After question response 2.5 hours, isolate and purify reaction system and take off
Except organic solvent, random copolymerization makrolon of the present invention is obtained.After measured, yield is 99%, and equal using gpc analysis product weight
Molecular weight is 38531, and polydispersity index is 1.32.
Prepare embodiment 4
228.3kg bisphenol-As, 160kg sodium hydroxides, the mixing of 2500kg water are added in a mixer, are completely dissolved in bisphenol-A
Afterwards, then add 473g catalyst TBAB and stir until all dissolvings, add 7.6kg triclosans simultaneously afterwards
Stir, form aqueous phase；138.5kg liquid phosgene and 6272L dichloromethane are added in another blender, shape is well mixed
Into oil phase；Then sodium phenolate aqueous phase is put into polymer reactor, afterwards under 1000rpm stir speed (S.S.) by oil phase and
The polysiloxanes of eugenol end-blocking prepared by 56.2kg Preparative Examples is added with 180g/min and 200g/min speed respectively
Into polymer reactor, while concentration is added dropwise into reaction system keeps reaction system for 10 weight % sodium hydrate aqueous solution
PH value maintain 50 DEG C 11.5, and by the temperature of reaction system；After question response 3 hours, isolate and purify reaction system and remove
Organic solvent, obtains random copolymerization makrolon of the present invention.After measured, yield is 99%, and is divided equally again using gpc analysis product
Son amount is 46130, and polydispersity index is 1.71.
Comparative example
Comparative example 1
228.3kg bisphenol-As, 100kg sodium hydroxides, the mixing of 1600kg water are added in a mixer, are completely dissolved in bisphenol-A
Afterwards, then add 324g catalyst TBAB and stir until all dissolvings, add 2.4kg phenol and stir afterwards
Mix uniform, form aqueous phase；128.9kg liquid phosgene and 4851L dichloromethane are added in another blender, is well mixed and is formed
Oil phase；Then sodium phenolate aqueous phase is put into polymer reactor, afterwards by oil phase and 26.4kg under 700rpm stir speed (S.S.)
The polysiloxanes of eugenol end-blocking prepared by Preparative Example is added to polymerization with 100g/min and 150g/min speed respectively
In reactor, while the pH value that concentration keeps reaction system for 10 weight % sodium hydrate aqueous solution is added dropwise into reaction system
45 DEG C are maintained 10.5, and by the temperature of reaction system；After question response 2 hours, isolate and purify reaction system and remove organic molten
Agent, obtains random copolymerization makrolon of the present invention.After measured, yield is 99%, and use gpc analysis product weight average molecular weight for
36124, polydispersity index is 1.93.
Comparative example 2
228.3kg bisphenol-As, 100kg sodium hydroxides, the mixing of 1600kg water are added in a mixer, are completely dissolved in bisphenol-A
Afterwards, then add 324g catalyst TBAB and stir until all dissolvings, add 2.4kg triclosans simultaneously afterwards
Stir, form aqueous phase；128.9kg liquid phosgene and 4851L dichloromethane are added in another blender, shape is well mixed
Into oil phase；Then sodium phenolate aqueous phase is put into polymer reactor, afterwards under 500rpm stir speed (S.S.) by oil phase and
20.1kg Preparative Examples prepare eugenol end-blocking polysiloxanes respectively with 90g/min and 120g/min speed add to
In polymer reactor, while concentration is added dropwise into reaction system keeps reaction system for 10 weight % sodium hydrate aqueous solution
PH value maintains 35 DEG C 10.1, and by the temperature of reaction system；After question response 2 hours, isolating and purifying reaction system and removing has
Machine solvent, obtains random copolymerization makrolon of the present invention.After measured, yield is 99%, and uses gpc analysis product Weight-average molecular
Measure as 48641, polydispersity index is 2.89.
Comparative example 3
228.3kg bisphenol-As, 100kg sodium hydroxides, the mixing of 1600kg water are added in a mixer, are completely dissolved in bisphenol-A
Afterwards, then add 324g catalyst TBAB and stir until all dissolvings, add 2.4kg triclosans simultaneously afterwards
Stir, form aqueous phase；128.9kg liquid phosgene and 4851L dichloromethane are added in another blender, shape is well mixed
Into oil phase；Then sodium phenolate aqueous phase is put into polymer reactor, afterwards under 1100rpm stir speed (S.S.) by oil phase and
The polysiloxanes of eugenol end-blocking prepared by 20.1kg Preparative Examples is added with 220g/min and 220g/min speed respectively
Into polymer reactor, while concentration is added dropwise into reaction system keeps reaction system for 10 weight % sodium hydrate aqueous solution
PH value maintain 55 DEG C 11.6, and by the temperature of reaction system；After question response 2 hours, isolate and purify reaction system and remove
Organic solvent, obtains random copolymerization makrolon of the present invention.After measured, yield is 99%, and is divided equally again using gpc analysis product
Son amount is 22345, and polydispersity index is 3.45.
Comparative example 4
228.3kg bisphenol-As, 80kg sodium hydroxides, the mixing of 1300kg water are added in a mixer, are completely dissolved in bisphenol-A
Afterwards, then add 324g catalyst TBAB and stir until all dissolvings, add 2.4kg triclosans simultaneously afterwards
Stir, form aqueous phase；128.9kg liquid phosgene and 4851L dichloromethane are added in another blender, shape is well mixed
Into oil phase；Then sodium phenolate aqueous phase is put into polymer reactor, afterwards under 700rpm stir speed (S.S.) by oil phase and
The polysiloxanes of eugenol end-blocking prepared by 20.1kg Preparative Examples is added with 100g/min and 160g/min speed respectively
Into polymer reactor, while concentration is added dropwise into reaction system keeps reaction system for 10 weight % sodium hydrate aqueous solution
PH value maintain 45 DEG C 10.5, and by the temperature of reaction system；After question response 2 hours, isolate and purify reaction system and remove
Organic solvent, obtains random copolymerization makrolon of the present invention.After measured, yield is 99%, and is divided equally again using gpc analysis product
Son amount is 29635, and polydispersity index is 1.67.
PERFORMANCE EXAMPLES
Product and commercially available carbonic ester-Organosiliconcopolymere prepared by embodiment 1-4 and comparative example 1-4 will be prepared
With antioxidant IRGAFOS 168 with 1000:1 weight is supplied to ventilated type single shaft extrusion shaper, in resin temperature than mixing
280 DEG C of progress melting mixings of degree, obtain evaluation particulate samples.By the evaluation particulate samples after 120 DEG C are dried 8 hours,
Using injection machine, in 280 DEG C of shaping resin temperature, 80 DEG C of progress injection mouldings of mold temperature, make for carrying out each examination
The standard testing batten tested, is as a result shown in table 1 below, wherein the testing standard of each performance test is as follows：
Izod notched impact strength：According to the Chalpy impact performance detection of plastics as defined in ASTM D256-1997
Standard test method is measured；
Ductility/brittle transition temperature refers to that sample turns in Izod notched impact performance test from 100% ductility
The temperature faded in the case of 100% fragility；
Tensile strength：It is measured according to plastic tensile method for testing performance as defined in GB/T 1040-1992；
Bending strength：It is measured according to Plastics-Oetermination of flexural properties method as defined in GB/T 9341-2000；
Elongation at break：It is measured according to plastic tensile method for testing performance as defined in ASTM D638-2003；
Anti-microbial property：According to the method for antimicrobial product antibacterial activity and effect test as defined in JIS Z 2801 at 24 hours
It is interior to be measured under conditions of 37 DEG C.
The performance test results of table 1
Show from the result observed, under the phosgene of the bisphenol-A of proper ratio, sodium hydroxide and water and appropriate consumption,
By the addition speed of the polysiloxanes of the amount, phosgene and the eugenol end-blocking that adjust end-capping reagent, the mixing speed of reaction system and
PH value, present invention obtains a kind of good mechanical performance, and the Copolycarbonate with preferable anti-microbial property.Institute of the present invention
The specificity end-blocking Copolycarbonate of preparation has higher relative to makrolon and commercially available carbonic ester-Organosiliconcopolymere
Izod notched impact strength, and ductility/brittle transition temperature is than relatively low, while tensile strength, bending strength and fracture are stretched
It is more excellent that long rate has also obtained obvious improvement, particularly anti-microbial property, anti-Escherichia coli rate and anti-gold-coloured staphylococci rate
Up to more than 99, it is seen that present invention specificity end-blocking Copolycarbonate mechanical performance and anti-microbial property are excellent, expand it and apply model
Enclose.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-described embodiment
Changed and changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, invention some are repaiied
Change and change and should also be as falling into the scope of the claims of the present invention.Although in addition, having used some in this specification
Specific term, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (8)
1. a kind of specificity end-blocking Copolycarbonate of polysiloxane block, it is characterised in that the specificity end-blocking copolymerization carbon
Acid esters includes following three kinds of structures：
(1) polycarbonate block of following formula (I), and
(2) polysiloxane block of following formula (II),
(3) closed-end structure of following formula (III),
Wherein, m is the integer between the integer between 90 to 200, preferably 150 to 200；N is the integer between 10 to 70, preferably
Integer between 50 to 60；P is the integer between the integer between 40 to 50, preferably 45 to 50, and the specificity end-blocking is altogether
The percentage by weight of the polycarbonate block of formula (I) is 80-90%, the weight of the polysiloxane block of formula (II) in makrolon
Percentage is 10-20%.
2. specificity end-blocking Copolycarbonate according to claim 1, it is characterised in that the specificity end-blocking copolymerization carbon
The percentage by weight in acid esters being the polysiloxane block of formula (II) is 15-20%.
3. specificity end-blocking Copolycarbonate according to claim 1, it is characterised in that the specificity end-blocking copolymerization carbon
The weight ratio of the polycarbonate block of formula (I) and the polysiloxane block of formula (II) is (80-85) in acid esters：(15-20).
4. specificity end-blocking Copolycarbonate according to claim 1, it is characterised in that the specificity end-blocking copolymerization carbon
The weight average molecular weight of acid esters is 30000-70000, and polydispersity index is 1.1-1.9.
5. specificity end-blocking Copolycarbonate according to claim 1, it is characterised in that the specificity end-blocking copolymerization carbon
Ductility/brittle transition temperature of acid esters is for -25 to -60 DEG C.
6. specificity end-blocking Copolycarbonate according to claim 1, it is characterised in that the specificity end-blocking copolymerization carbon
Izod notched impact strength of the acid esters at -50 DEG C is >=550J/m2, it is the plastics according to as defined in ASTM D256-1997
Chalpy impact performance detection standard test method be measured gained value.
7. specificity end-blocking Copolycarbonate according to claim 1, it is characterised in that the specificity end-blocking copolymerization gathers
Bacteriostasis rate of the carbonic ester to Escherichia coli and staphylococcus aureus under conditions of 37 DEG C in 24 hours is more than 99%, its
It is that the method for antimicrobial product antibacterial activity and effect test according to as defined in JIS Z 2801 is measured the value of gained.
8. a kind of method of the specificity end-blocking Copolycarbonate prepared any one of claim 1-6, it is characterised in that
It comprises the following steps：
(1) aqueous phase is prepared：Bisphenol-A, alkali metal hydroxide, water are pressed 1:(2.5-4.0):The mixed in molar ratio of (80-140),
After bisphenol-A is completely dissolved, catalyst and triclosan end-capping reagent are added, aqueous phase is constituted；
(2) oil phase is prepared：Phosgene and inert organic solvents are pressed 1:The weight of (45-65) constitutes oil phase than mixing；
(3) polymerisation is carried out：Oil phase and the polysiloxanes of eugenol end-blocking are added dropwise under 700-900rpm stir speed (S.S.)
Enter into aqueous phase to carry out polymerisation, while the pH of reaction system is maintained at into 10.5- with alkali metal hydroxide aqueous solution
11.5, and the temperature of reaction system is maintained at 45-50 DEG C, after reacting 2-4 hours, obtain specificity end-blocking Copolycarbonate breast
Liquid；
(4) post-process：Specificity end-blocking Copolycarbonate emulsion prepared by step (3) is purified and removes organic solvent,
Product is can obtain,
Wherein, in step (3), the phosgene added is (1.3-1.4) with bisphenol-A mol ratio:1, the eugenol end-blocking
The weight ratio of polysiloxanes and bisphenol-A is 1：(4-9), and the weight average molecular weight of the polysiloxanes of the eugenol end-blocking is
3500-4200, polydispersity index is less than 3.5.
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