CN107082877B - A method of preparing nontransparent type polysiloxane-polycarbonate random copolymer - Google Patents
A method of preparing nontransparent type polysiloxane-polycarbonate random copolymer Download PDFInfo
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- CN107082877B CN107082877B CN201710159016.0A CN201710159016A CN107082877B CN 107082877 B CN107082877 B CN 107082877B CN 201710159016 A CN201710159016 A CN 201710159016A CN 107082877 B CN107082877 B CN 107082877B
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- polycarbonate
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- hydroxyphenyl
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 58
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 57
- 229920005604 random copolymer Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 25
- -1 polysiloxanes Polymers 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 23
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003426 co-catalyst Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 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 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000003512 tertiary amines Chemical group 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 2
- KCCUBRRTVWFOGF-UHFFFAOYSA-N 2-tritylphenol Chemical compound OC1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 KCCUBRRTVWFOGF-UHFFFAOYSA-N 0.000 claims description 2
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 claims description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- DZUVRHUBQHAJFT-UHFFFAOYSA-N C(CCC)C1=C(C([N+](C)(C)CCCCCCCCCCCCCCCC)(CCCC)CCCC)C=CC=C1 Chemical compound C(CCC)C1=C(C([N+](C)(C)CCCCCCCCCCCCCCCC)(CCCC)CCCC)C=CC=C1 DZUVRHUBQHAJFT-UHFFFAOYSA-N 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 claims description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical group C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
- 239000005770 Eugenol Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 238000012360 testing method Methods 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
- 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
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000005401 siloxanyl group Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- 238000005406 washing 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
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 present invention provides a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer, the following steps are included: (1) polycarbonate synthesis: reactant includes dihydric phenol, alkali metal hydroxide, phosgene, end-capping reagent, inert organic solvents and catalyst, generates polycarbonate prepolymer；(2) it synthesizes nontransparent type polysiloxane-polycarbonate random copolymer: step (1) being obtained into polycarbonate prepolymer and polysiloxanes, co-catalyst, end-capping reagent and phosgene carry out random copolymerization；Remember by mass percentage, in the step (1), dihydric phenol: phosgene: end-capping reagent=(9-10): (4-5): (0.02-0.04)；In the step (2), polysiloxanes: end-capping reagent: phosgene=(5-6): (1-2): (20-30).Realize that obtained polysiloxane-polycarbonate random copolymer has preferable low-temperature impact resistance and chemical-resistance.
Description
Technical field
The present invention relates to the synthetic methods of polycarbonate, and in particular to a kind of to prepare nontransparent type polysiloxanes-poly- carbonic acid
The method of ester random copolymer.
Background technique
Polycarbonate is the synthetic material that the fifties end starts development, and visible light transmittance has 90% or more
Impact resistance, creep resistance, good stability of the dimension and chemical corrosion resistance outstanding, heat-resisting, water absorption rate is low, nontoxic, dielectricity
Can be excellent, there are also excellent performances such as self-extinguishment, Yi Zengqiang anti-flammabilitys, be widely used in electric, electric tool, communications and transportation,
Automobile, machinery, instrument, building, information storage, optical material, medical instrument, sports goods, civilian product, security personnel, aviation boat
The fields such as it and defence and military are that uniquely have the product of good transparency in five large-engineering plastics, and increase speed in recent years
Spend most fast general engineering plastic.Because technology is limited, at present except some external monopoly enterprises, the country is still without commercial scale
Manufacturing enterprise.Polycarbonate production is mainly divided vapor interface condensation methods and two kinds of melt transesterification process at present, wherein phosgene interface
Condensation methods are the preparation methods being most widely used at present.
Carbonate polymer is useful in the manufacture of the product and component of the application for wide scope.But perhaps
Poly carbonate polymer be especially at low temperature it is brittle, although polycarbonate has good impact resistance at room temperature,
But its impact resistance quickly becomes grain at low temperature.Therefore, the polycarbonate with preferable impact resistance has at low temperature for preparation
It is significant.Polycarbonate-organo-siloxanes polymer has high-impact, chemical-resistant and anti-flammability etc. excellent
Heterogeneity and attracted attention.
Application No. is 96112350.8 to disclose the preparation method of polycarbonate-polysiloxane block copolymers, with fourth
Polycarbonate block copolymer derived from dimethyl silicone polymer-bisphenol-A of fragrant phenol sealing end, the poly- diformazan of eugenol sealing end
When radical siloxane block copolymer is used to prepare polycarbonate blend as blending components, it is shown that polycarbonate can be improved
The advantages of energy is to be copolymerized with the polysiloxanes and polycarbonate block of eugenol sealing end, and cooperate using method
Specific phase transfer catalyst can realize that being achieved with complete weight average molecular weight under less phosgene effect increases.But it is prepared
The low temperature impact performance of copolymer do not protrude.
Application No. is 200710138368.4 to disclose transparent and high-heat polycarbonate-polysiloxane copolymers and containing poly-
The transparent blends and its manufacturing process of carbonic ester.Select lower pH value prepare bischloroformates can generate it is shorter oligomeric
Body simultaneously generates the bigger bischloroformates of relative concentration, and the polycarbonate polycarbonate-polysiloxane for thus preparing high transparency is total
Polymers.Although the transparency reach requirement, can not simultaneously low-temperature impact resistance with higher.
Application No. is 201280053477.5 to provide a kind of polysiloxane-polycarbonate copolymer and its manufacturing method.
The molecular weight for wherein constituting the siloxanyl monomers of the copolymer maintains extra high horizontal and therefore contains in even low siloxanes
, it can be achieved that excellent low-temperature impact resistance in the case where amount.This method preparation condition is more harsh.
The present invention takes different thinkings, adds phosgene by substep, adds the end-capping reagent of reasonable amount, and cooperation respectively
The proportion of other reactants, realize has good impact resistance and chemical resistance at low temperature.
Summary of the invention
The present invention provides a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer, including following
Step:
(1) polycarbonate synthesis: reactant includes that dihydric phenol, alkali metal hydroxide, phosgene, end-capping reagent, inertia are organic
Solvent and catalyst generate polycarbonate prepolymer；
(2) it synthesizes nontransparent type polysiloxane-polycarbonate random copolymer: step (1) is obtained into polycarbonate prepolymer
Object and polysiloxanes, co-catalyst, end-capping reagent and phosgene carry out random copolymerization；
(3) step (2) is post-processed to obtain after reaction nontransparent type polysiloxane-polycarbonate random copolymerization
Object；
Remember by mass percentage,
In the step (1), dihydric phenol: phosgene: end-capping reagent=(9-10): (4-5): (0.02-0.04)；
In the step (2), polysiloxanes: end-capping reagent: phosgene=(5-6): (1-2): (20-30).
Preferably, remember by mass percentage, the dihydric phenol: polysiloxanes=(92-96): (4-8).
Preferably, the invention also includes iron removing reagent is added in step (2) for removing usual impurities iron ion, shadow is avoided
Ring product quality；It is furthermore preferred that the iron removing reagent is sodium gluconate.
Preferably, the end-capping reagent is selected from phenol, p -cumylphenol, p-tert-butylphenol, octyl phenol or trityl
Phenol.
Preferably, the catalyst amount is the 1-5% of dihydric phenol molal quantity, and preferred catalyst amount is dihydric phenol
The 0.001-10% of molal quantity.
Preferably, the alkali metal hydroxide is selected from lithium hydroxide, sodium hydroxide or potassium hydroxide.
Preferably, the inert organic solvents be selected from can about 20 DEG C at a temperature of polycarbonate is dissolved at least
Or mixtures thereof the solvent of 5wt% degree,.Preferably, the one or more selected from aromatics, aromatic hydrocarbons and aliphatic chlorinated hydrocarbons；It is more excellent
Choosing, it states inert organic solvents and is selected from methylene chloride, trichloro ethylene, 1,1,1- trichloroethanes, 1,1,2- trichloroethanes, benzene, first
Benzene, m-/o-/p-xylene and chlorobenzene and its mixture.
Preferably, the catalyst can be selected from quaternary ammonium salt, and the quaternary ammonium salt is tetrabutylammonium, tributyl hexadecyldimethyl benzyl ammonium, tetraethyl
Hydroxide, chloride or the bromide of ammonium.
Preferably, the co-catalyst is tertiary amine, and the tertiary amine is triethylamine, tri-n-butylamine, trioctylamine；In N- Alkylpiperidine
One or more.
Preferably, the dihydric phenol is selected from: 4,4 '-dihydroxybiphenyls；2,2- bis- (4- hydroxyphenyl) -1- phenyl third
Alkane；1,1- bis- (4- hydroxyphenyl) diphenylphosphino ethanes；2,2- bis- (4- hydroxyphenyl) propane；2,4- bis- (4- hydroxyphenyl) -2- methybutanes；
1,3- bis- [2- (4- hydroxyphenyl) -2- propyl] benzene；2,2- bis- (3- methyl -4- hydroxyphenyl) propane；Bis- (3,5- dimethyl -4- hydroxyls
Phenyl) methane；2,2- bis- (3,5- dimethyl -4- hydroxyphenyl) propane；Bis- (3,5- dimethyl -4- hydroxyphenyl) sulfones；2,4- bis- (3,
5- dimethyl -4- hydroxyphenyl) -2- methybutane；1,3- bis- [2- (3,5- dimethyl -4- hydroxyphenyl) -2- propyl] benzene；1,1- is bis-
(4- hydroxyphenyl) hexamethylene；With bis- (the 4- hydroxyphenyls) -3 of 1,1-, one or more of 3,5- trimethyl-cyclohexanes.
The present invention also provides a kind of nontransparent type polysiloxane-polycarbonate random copolymerizations prepared by the above method
Object.
Beneficial effects of the present invention:
1. the present invention uses the rational proportion of reactant, and adds phosgene using two steps, two steps add end-capping reagent, pass through elder generation
Polycarbonate synthesis prepolymer, then reacted with polysiloxanes and add phosgene and end-capping reagent simultaneously, the polysiloxanes-realized is poly-
Carbonic ester random copolymer has preferable low-temperature impact resistance and chemical-resistance.
2. the present invention is copolymerized using polysiloxanes and polycarbonate random, and the usage ratio of polysiloxanes is reasonable, system
Standby product has preferable flame retardant property.
3. the present invention selects tertiary amine that can help to remove chloro-formate as co-catalyst, keep reaction more complete.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further described, but the scope of protection of present invention is not limited to the range of embodiment expression.
Embodiment 1 (5% copolymeric siloxane PC):
907g bisphenol-A is dissolved in (alkali metal hydroxide) 10% aqueous solution of the sodium hydroxide containing 160g, bisphenol-A is obtained
Saline solution；Above-mentioned bisphenol-A saline solution, 600ml deionized water, 2500ml methylene chloride (inertia are added in the reactor
Organic solvent), 3g phenol (end-capping reagent), 75% aqueous solution of 5.9ml methyltributylammonichloride chloride (catalyst), 1.5g sodium gluconate
It stirs evenly, 450g phosgene is passed through with the speed of 25 gram/minutes and is reacted, control reaction temperature at 32-40 DEG C, hydrogen-oxygen is added
Changing sodium solution control pH value of reaction system is 5.3；Continue stirring 10 minutes, adding sodium hydroxide solution increases the pH value of above-mentioned system
To 11.5.59g polysiloxanes is at the uniform velocity added dropwise in 15-20 minutes, carries out random copolymerization, reaction temperature is 30-40 DEG C, reactant
Be pH value it is 11.5, continues stirring 10 minutes, be added 4.1 milliliters of triethylamines (co-catalyst) and 10g phenol (end-capping reagent), then with
The speed of 25 gram/minutes is passed through 200g phosgene, keeps solution ph=10.Organic be added to is taken dilute hydrochloric acid and to go after reaction
Ionized water carries out washing and processing after correlation.
The raw material of polysiloxane-polycarbonate random copolymer is prepared according to the formula adjustment in embodiment 1, wherein according to
The requirement adjustment related substances of following table and its dosage of substance, other techniques are constant, and the specific situation that adjusts is shown in Table 1.
Table 1
Effect example:
Polysiloxane-polycarbonate random copolymer prepared by above-described embodiment 1-3 and comparative example 1-8 carries out performance survey
Examination, specific data are as shown in table 2.
Oxygen index (OI): the flame-retarding characteristic of material generally indicates that oxygen index (OI) refers to the material (test piece) of certain size with oxygen index (OI)
It is fitted into experimental rig, under prescribed conditions, is passed through the mixed gas of oxygen and nitrogen, test piece is lighted with igniter, measurement is kept
As necessary to wax-like sustained combustion minimum oxygen concentration (is indicated) with percentage.
Impact strength: by using impact tester (RESIL IMPACTOR, CEAST Co., Ltd.), in 23 DEG C, 0
DEG C, measure impact strength at -20 DEG C and -40 DEG C.
Table 2
Can be seen that polysiloxane-polycarbonate random copolymer prepared by embodiment 1-3 from the data of table 1 will compare
Ratio 1-8 standby polysiloxane-polycarbonate random copolymer anti-flammability and cold temperature impact will be got well.
The ratio for the end-capping reagent being added when can be seen that polycarbonate synthesis prepolymer from the data of comparative example 1 and comparative example 2
Example has an impact to the anti-flammability and low temperature impact strength of polysiloxane-polycarbonate random copolymer.When end-capping reagent dosage is less,
Product sealing end effect is bad, and segment more interlocks；When end-capping reagent dosage is more, polycarbonate prepolymer be blocked it is more, it is remaining with
The end group of polysiloxanes reaction is less.
Comparative example 3 and comparative example 4 are it can be seen that in polycarbonate prepolymer and polysiloxanes random copolymerization, the envelope of addition
The ratio of end agent also has an impact to the anti-flammability and low temperature impact strength of polysiloxane-polycarbonate random copolymer.In poly- carbon
When acid esters prepolymer and polysiloxanes random copolymerization, suitable end-capping reagent, which is added, can make product possess preferable anti-flammability and low temperature punching
Hit intensity.
The present invention makes to react more complete when polycarbonate prepolymer is with polysiloxanes random copolymerization, is additionally added phosgene.
It can be seen that the additional amount of phosgene at this time to polysiloxane-polycarbonate random copolymerization from the data of comparative example 5 and comparative example 6
The anti-flammability and low temperature impact strength of object have an impact.
The data of comparative example 7 and comparative example 8 can be seen that the ratio of polysiloxanes and dihydric phenol to the poly- carbonic acid of polysiloxanes-
The anti-flammability and low temperature impact strength of ester random copolymer have an impact.Polysiloxane level is higher and lower is all unfavorable for finally producing
The anti-flammability and low temperature impact strength of product.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-described embodiment
It changes and modifies.Therefore, the invention is not limited to specific embodiments disclosed and described above, repair to some of invention
Change and change should also be as falling into the scope of the claims of the present invention.In addition, although having been used in this specification some
Specific term, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer, which is characterized in that including following step
It is rapid:
(1) polycarbonate synthesis: reactant includes dihydric phenol, alkali metal hydroxide, phosgene, end-capping reagent, inert organic solvents
And catalyst, generate polycarbonate prepolymer；
(2) nontransparent type polysiloxane-polycarbonate random copolymer: the polycarbonate prepolymer that step (1) is obtained is synthesized
Random copolymerization is carried out with polysiloxanes, co-catalyst, end-capping reagent and phosgene；
(3) step (2) is post-processed to obtain after reaction nontransparent type polysiloxane-polycarbonate random copolymer；
It counts in mass ratio,
In the step (1), dihydric phenol: phosgene: end-capping reagent=(9-10): (4-5): (0.02-0.04)；
In the step (2), polysiloxanes: end-capping reagent: phosgene=(5-6): (1-2): (20-30).
2. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer according to claim 1,
It is characterized in that, counts in mass ratio, the dihydric phenol: polysiloxanes=(92-96): (4-8).
3. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer according to claim 1,
It is characterized in that, the end-capping reagent is selected from phenol, p -cumylphenol, p-tert-butylphenol, octyl phenol or trityl phenol.
4. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer according to claim 1,
It is characterized in that, the catalyst amount is the 1-5% of dihydric phenol molal quantity.
5. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer according to claim 1,
It is characterized in that, the alkali metal hydroxide is selected from lithium hydroxide, sodium hydroxide or potassium hydroxide.
6. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer according to claim 1,
Be characterized in that, the inert organic solvents be selected from can 20 DEG C at a temperature of polycarbonate is dissolved at least 5wt% degree
Solvent, or mixtures thereof.
7. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer according to claim 1,
It is characterized in that, the catalyst is selected from quaternary ammonium salt, and the quaternary ammonium salt is the hydrogen-oxygen of tetrabutylammonium, tributyl hexadecyldimethyl benzyl ammonium, tetraethyl ammonium
Compound, chloride or bromide.
8. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer according to claim 1,
It is characterized in that, the co-catalyst is tertiary amine, and the tertiary amine is one of triethylamine, tri-n-butylamine, trioctylamine, N- Alkylpiperidine
Or it is several.
9. a kind of method for preparing nontransparent type polysiloxane-polycarbonate random copolymer according to claim 1,
It is characterized in that, the dihydric phenol is selected from: 4,4 '-dihydroxybiphenyls；2,2- bis- (4- hydroxyphenyl) -1- phenyl-propanes；1,1- bis- (4-
Hydroxyphenyl) diphenylphosphino ethane；2,2- bis- (4- hydroxyphenyl) propane；2,4- bis- (4- hydroxyphenyl) -2- methybutanes；1,3- bis- [2- (4-
Hydroxyphenyl) -2- propyl] benzene；2,2- bis- (3- methyl -4- hydroxyphenyl) propane；Bis- (3,5- dimethyl -4- hydroxyphenyl) methane；2,
Bis- (3, the 5- dimethyl -4- hydroxyphenyl) propane of 2-；Bis- (3,5- dimethyl -4- hydroxyphenyl) sulfones；2,4- bis- (3,5- dimethyl -4-
Hydroxyphenyl) -2- methybutane；1,3- bis- [2- (3,5- dimethyl -4- hydroxyphenyl) -2- propyl] benzene；1,1- bis- (4- hydroxyphenyls)
Hexamethylene；With bis- (the 4- hydroxyphenyls) -3 of 1,1-, one or more of 3,5- trimethyl-cyclohexanes.
10. a kind of nontransparent type polysiloxane-polycarbonate being prepared by any one of claim 1-9 the method is random
Copolymer.
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