CN101654516B - Polycarbonate-polyphenylene oxide block copolymer, preparation method and application thereof - Google Patents
Polycarbonate-polyphenylene oxide block copolymer, preparation method and application thereof Download PDFInfo
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- CN101654516B CN101654516B CN2009103042768A CN200910304276A CN101654516B CN 101654516 B CN101654516 B CN 101654516B CN 2009103042768 A CN2009103042768 A CN 2009103042768A CN 200910304276 A CN200910304276 A CN 200910304276A CN 101654516 B CN101654516 B CN 101654516B
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- polyphenylene oxide
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- phenol
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 72
- 229920006380 polyphenylene oxide Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 229920001400 block copolymer Polymers 0.000 title abstract 4
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 9
- 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 abstract description 9
- 239000008346 aqueous phase Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 229960001701 chloroform Drugs 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 6
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 3
- QVYKWYMCZYPMAF-UHFFFAOYSA-N C(C)N(CC)CC[N+](CCCC)(CCCC)CCCC Chemical compound C(C)N(CC)CC[N+](CCCC)(CCCC)CCCC QVYKWYMCZYPMAF-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 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
- LNGNZSMIUVQZOX-UHFFFAOYSA-L disodium;dioxido(sulfanylidene)-$l^{4}-sulfane Chemical compound [Na+].[Na+].[O-]S([O-])=S LNGNZSMIUVQZOX-UHFFFAOYSA-L 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000004417 polycarbonate Substances 0.000 description 25
- 229920000515 polycarbonate Polymers 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polyoxymethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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Abstract
The invention discloses a polycarbonate-polyphenylene oxide block copolymer, a preparation method and application thereof. The preparation method comprises the following steps: (1) weighing raw materials; (2) adding bisphenol, part of alkali, an antioxidant and a catalyzer into water to prepare an aqueous phase; (3) separately dissolving polyphenylene oxide and triphosgene in an organic solvent to obtain a polyphenylene oxide solution and a triphosgene solution; adding part of the polyphenylene oxide solution in the aqueous phase prepared in the step (2), evenly stirring, adding part of the triphosgene solution, stirring and reacting for 30-60 min under the condition that the reaction temperature is 20-40 DEG C and pH is between 9 and 11; and then adding the rest of the polyphenylene oxide solution and the triphosgene solution; and (4) adding a monophenol molecular weight regulator and the rest of alkali, keeping reaction for 0.5-2h, separating and purifying to obtain the polycarbonate-polyphenylene oxide block copolymer. The polycarbonate-polyphenylene oxide block copolymer has the advantages of excellent stability, processibility and solvent resistance and belongs to the modification filed of copolymer.
Description
Technical field
The present invention relates to a kind of carbonic ether-polyphenylether segmented multipolymer, be specifically related to the good polycarbonate of a kind of thermostability, processibility and solvent resistance-polyphenylether segmented multipolymer, the present invention also relates to the preparation method and its usage of this polycarbonate-polyphenylether segmented multipolymer.
Background technology
Polycarbonate and polyphenylene oxide all have the excellent comprehensive performances engineering plastics that are widely used, such as electronic apparatus, automobile, household electrical appliance, office equipment and machinery etc.The mechanical property of polyphenylene oxide is better than polycarbonate, nylon and polyoxymethylene, its electrical property, water-fast steam, excellent in dimensional stability, and have chemical resistant properties, scoring resistance, high temperature resistant plating, thermal shock resistance, be difficult to burning, thereby the use temperature scope is wide, and water-absorbent is little.Shortcoming is that melt viscosity is big, and mobile poor, softening temperature is more than 300 ℃, and thermal-oxidative degradation easily takes place high temperature process (330 ℃), and machine-shaping difficulty and energy consumption are excessive, have limited its application to a great extent.The polycarbonate water white transparency, the specific refractory power height, have heat-resisting, shock resistance, fire-retardant and resisting heat distortion performance, and good weatherability, the hardness height, good processability all has the favorable mechanical performance in common use temperature; Though PC has good comprehensive performances, exist defectives such as processing fluidity is poor, easily stress cracking, wearing and tearing, aging and chemical resistant properties be relatively poor.In order to improve the use properties of polycarbonate and polyphenylene oxide product, extensively carried out their study on the modification work both at home and abroad.Except that adopting inorganic materials to fill to strengthen or improving with method such as other resinous blending and the performance of improving them is widened its range of application, the main path of another modification is to adopt modification by copolymerization.
The patent No. that open day is on November 21st, 1972 is US 3,703,564 United States Patent (USP) and open day are that on 04 01st, 1975 the patent No. is US3, the preparation method of low-molecular-weight polycarbonate-polyphenylether segmented multipolymer in the presence of alkali, basic metal or tertiary amine has been described in 875,256 the United States Patent (USP).The patent No. of open day 03 month 22 days nineteen eighty-three is US 4,377, has described the preparation of the polyphenylene oxide/aromatic copolycarbonate multipolymer that contains random or alternating structure in 662 the United States Patent (USP).And the implementation method of describing in the above-mentioned patent is all carried out in homogeneous phase, and needs harsh reaction conditions such as gas shield.
Summary of the invention
The object of the present invention is to provide the good polycarbonate of a kind of stability, processibility and solvent resistance-polyphenylether segmented multipolymer.
Another object of the present invention is to provide the preparation method of a kind of above-mentioned polycarbonate-polyphenylether segmented multipolymer.
A further object of the present invention is to provide the application of described polycarbonate-polyphenylether segmented multipolymer aspect the preparation engineering plastics.
For achieving the above object, the present invention proposes a kind of polycarbonate-polyphenylether segmented multipolymer, the structural formula of described polycarbonate-polyphenylene ether copolymer is:
Wherein, 1≤m≤1000,10≤n≤1000 and m, n is integer, and R is the alkyl of C1-C4 in the formula, and R ' is a hydrogen or halogen.
A kind of method for preparing described polycarbonate-polyphenylether segmented multipolymer comprises the steps:
1. take by weighing raw material by following mol ratio:
Bis-phenol: polyphenylene oxide: alkali: oxidation inhibitor: catalyzer: triphosgene: the monohydric phenol molecular weight regulator is 1: 0.0013-0.0075: 2.05-2.5: 0.0008-0.0034: 0.0014-0.54: 0.26-0.37: 0.0027-0.0034;
2. bis-phenol, part alkali, oxidation inhibitor and catalyzer are added in the entry, be made into water;
3. polyphenylene oxide and triphosgene are dissolved in respectively in the organic solvent, get polyphenylene oxide solution and triphosgene solution; Part polyphenylene oxide solution is joined step aqueous phase 2., stir, add part triphosgene solution again, stirring reaction 30-60min, temperature of reaction is at 20-40 ℃, and pH adds the polyphenylene oxide solution and the triphosgene solution of surplus again at 9-11;
4. add monohydric phenol molecular weight regulator and surplus alkali, continue reaction 0.5-2h, separate and purify, promptly.
Its chemical equation is:
Described bis-phenol is tetrabromo-bisphenol or dihydroxyphenyl propane.
Described alkali is sodium hydroxide, potassium hydroxide or calcium hydroxide.
Described oxidation inhibitor is V-Brite B, sodium thiosulfite or S-WAT.
Described catalyzer is triethylamine, tetrabutylammonium, tetrabutylammonium chloride or Diethylaminoethyl tributyl ammonium.
Described polyphenylene oxide is the terminal polyphenylene oxide that contains hydroxyl, is preferably two hydroxyl polyphenylene oxide, and weight-average molecular weight is 2000-40000.
The 3. middle organic solvent of described step is tetrahydrofuran (THF) or trichloromethane, the concentration of described polyphenylene oxide solution is 0.05-0.3g/ml, the concentration of triphosgene solution is 0.05-0.5g/ml, preferably, the concentration of polyphenylene oxide solution is 0.07-0.24g/ml, and the concentration of triphosgene solution is 0.1-0.36g/ml.
Described monohydric phenol molecular weight regulator is a kind of or wherein several mixture in cumylphenol, tert.-butyl phenol, phenol or the cumyl phenol.
The application of described polycarbonate-polyphenylether segmented multipolymer aspect the preparation engineering plastics.
The separation of described step in 4. purified and comprised the steps:
(1) standing demix is collected organic phase, uses alkali, acid, water washing respectively 3 times;
(2) solution is dripped in the methyl alcohol of 40 times of volumes, polycarbonate-polyphenylether segmented multipolymer white precipitate is separated out filtration washing;
(3) will dissolve in the trichloromethane that polycarbonate-polyphenylether segmented multipolymer is deposited in that obtain, washing of precipitate in methyl alcohol three times at least repeatedly, obtains polycarbonate-polyphenylether segmented multipolymer and precipitates thick product;
(4) will obtain polycarbonate-polyphenylether segmented multipolymer precipitation with methylene dichloride and toluene subsequently and carry out extracting.Residuum 120 ℃ of oven dry at least 5 hours, is promptly made polycarbonate-polyphenylether segmented multipolymer.
Among the present invention, described polyphenylene oxide is the terminal polyphenylene oxide that contains hydroxyl, preferably contains two hydroxyls, and weight-average molecular weight is at two hydroxyl polyphenylene oxide of 2000-40000.
The present invention adopts interfacial polymerization method to prepare polycarbonate various excellent propertys, different molecular weight-polyphenylether segmented multipolymer, undesirable gas protection, reaction conditions gentleness.Polycarbonate-polyphenylether segmented the multipolymer of preparation has been gathered the good mechanical property of polycarbonate and polyphenylene oxide, dimensional stability, shock resistance, characteristics such as fire-retardant on the one hand, the introducing of the polyphenylene oxide of different molecular weight, different polymerization degree on the other hand, improve defectives such as the easy stress cracking, wearing and tearing of polycarbonate itself, aging and chemical resistant properties be relatively poor, can effectively improve polymkeric substance chemical resistant properties, scoring resistance, the transparency and processing characteristics etc. to a certain extent.Technology of the present invention is simple, feasible, is easy to suitability for industrialized production.Can be widely used in field, especially high transparent and high impact fields such as electric, building, packing, medicine equipment, opticinstrument, communications and transportation according to the difference of multipolymer component.The invention provides a kind of new polycarbonate-block-polyphenylene ether copolymer and preparation method thereof, for people understand and use polycarbonate-polyphenylether segmented multipolymer to open up a kind of new thinking and approach.
The present inventor also utilizes GPC and IR that the polymkeric substance that obtains has been carried out characterizing as depicted in figs. 1 and 2.After we carried out interfacial polymerization as can be seen from Fig. 1, the polymkeric substance that obtains what deserves to be mentioned is that to the skew of high molecular direction this segmented copolymer does not carry out the GPC test of carrying out before the extracting.The characteristic absorbance that we can see the existing polycarbonate of polymkeric substance that obtains after the extracting from Fig. 2 has the characteristic absorbance of polyphenylene oxide again, and changes with the composition of segmented copolymer.Confirm that thus the contriver successfully synthesizes the polycarbonate of design-polyphenylether segmented multipolymer.
The present inventor also tests the thermal characteristics of segmented copolymer by TGA and DSC, as shown in Figure 3 and Figure 4.We can see different along with polyphenylene oxide content thermogravimetric curve by polyphenylene oxide and polycarbonate-polyphenylether segmented multipolymer, and the thermal characteristics of polycarbonate has obtained improvement in various degree.And we can see two approaching mutually and second-order transition temperatures between polycarbonate and polyphenylene oxide in dsc analysis.
Description of drawings
Fig. 1 is the GPC graphic representation of the polycarbonate-polyphenylether segmented multipolymer of polyphenylene oxide and embodiment 3 preparations;
Fig. 2 is the infrared spectrum of the polycarbonate-polyphenylether segmented multipolymer of polycarbonate, polyphenylene oxide and embodiment 1-2 preparation;
Fig. 3 is the thermogravimetric curve figure of the polycarbonate-polyphenylether segmented multipolymer of polyphenylene oxide and embodiment 1-3 preparation;
Fig. 4 is the DSC graphic representation of the polycarbonate-polyphenylether segmented multipolymer of polycarbonate, polyphenylene oxide and embodiment 3 preparations.
Fig. 1 wherein: according to away from X-coordinate order from bottom to top: article one curve is the GPC curve of polyphenylene oxide, and the second curve is the GPC curve of embodiment 3 gained polycarbonate-polyphenylether segmented multipolymers;
Fig. 2: according to away from X-coordinate from bottom to top the order, article one, curve is the infrared spectrum of polycarbonate, the second curve is the infrared spectrum of polyphenylene oxide, article three, curve is the infrared spectrum of the polycarbonate-polyphenylether segmented multipolymer of embodiment 1 preparation, and the 4th curve is the infrared spectrum of the polycarbonate-polyphenylether segmented multipolymer of embodiment 2 preparations.
Fig. 3: according to away from the X-coordinate of 550-700 ℃ of section order from bottom to top, article one, curve is the thermogravimetric curve of the polycarbonate-polyphenylether segmented multipolymer of embodiment 2 preparations, the second curve is the thermogravimetric curve of the polycarbonate-polyphenylether segmented multipolymer of embodiment 1 preparation, article three, curve is the thermogravimetric curve of the polycarbonate-polyphenylether segmented multipolymer of embodiment 3 preparations, and the 4th curve is the thermogravimetric curve of polyphenylene oxide.
Fig. 4: according to away from X-coordinate order from bottom to top, article one curve is the DSC graphic representation of polycarbonate, the DSC graphic representation of the polycarbonate-polyphenylether segmented multipolymer of second curve embodiment 3 preparation, and the 3rd curve is for being the DSC graphic representation of polyphenylene oxide.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
Separation among the embodiment is purified and is comprised the steps:
(1) standing demix is collected organic phase, is respectively sodium hydroxide solution, the hydrochloric acid soln of 5wt%, the water washing 3 times of 5wt% with concentration;
(2) solution after above-mentioned steps (1) washing is dripped in the methyl alcohol of 40 times of volumes, polycarbonate-polyphenylether segmented multipolymer white precipitate is separated out filtration washing;
(3) polycarbonate-polyphenylether segmented multipolymer that obtains is deposited in the trichloromethane and dissolves, washing of precipitate in methyl alcohol three times at least repeatedly, obtains polycarbonate-polyphenylether segmented multipolymer and precipitates thick product;
(4) with methylene dichloride and toluene the polycarbonate-polyphenylether segmented multipolymer precipitation that obtains is carried out extracting subsequently.Residuum 120 ℃ of oven dry at least 5 hours, is promptly made polycarbonate-polyphenylether segmented thing.
Embodiment 1
1. 2.283g dihydroxyphenyl propane, 1g sodium hydroxide, 60mg oxidation inhibitor V-Brite B and 0.003ml catalyst of triethylamine are added in the 20ml water, be made into water;
2. be that two hydroxyl polyphenylene oxide of 40000 are dissolved in the 10ml trichloromethane with the 2.4277g weight-average molecular weight, polyphenylene oxide solution; The 1.263g triphosgene is dissolved in the 12ml trichloromethane, gets triphosgene solution; 9.5ml polyphenylene oxide solution is joined step aqueous phase 1., stir, add 11.5ml triphosgene solution again, stirring reaction 30min, temperature of reaction is at 30 ℃, and pH adds the polyphenylene oxide solution and the triphosgene solution of surplus again 10; The concentration of described polyphenylene oxide solution is 0.24g/ml, and the concentration of triphosgene solution is 0.1g/ml.
3. the sodium hydroxide solution 7mL that adds 4mg monohydric phenol molecular weight regulator tert.-butyl phenol and 5wt% continues reaction 1h, separates and purifies, promptly.
Dihydroxyphenyl propane wherein: polyphenylene oxide: alkali: oxidation inhibitor: catalyzer: triphosgene: monohydric phenol molecular weight regulator mol ratio is 1: 0.0061: 2.5: 0.0034: 0.002: 0.42: 0.0027.
The IR figure of the polycarbonate that present embodiment obtains-polyphenylether segmented thing sees Fig. 2; Its thermogravimetric curve is seen PC-b-PPEI curve among Fig. 3.
Embodiment 2
1. 2.283g dihydroxyphenyl propane, 0.822g sodium hydroxide, 14mg oxidation inhibitor V-Brite B and 0.002mL catalyst of triethylamine are added in the 15ml water, be made into water;
2. be that two hydroxyl polyphenylene oxide of 40000 are dissolved in the 7ml trichloromethane with the 0.5g weight-average molecular weight, polyphenylene oxide solution; The 1.1g triphosgene is dissolved in the 15ml trichloromethane, gets triphosgene solution; 6.5ml polyphenylene oxide solution is joined step aqueous phase 1., stir, add 14ml triphosgene solution again, stirring reaction 30min, temperature of reaction is at 30 ℃, and pH adds the polyphenylene oxide solution and the triphosgene solution of surplus again 10; The concentration of described polyphenylene oxide solution is 0.07g/ml, and the concentration of triphosgene solution is 0.13g/ml;
3. add 4mg monohydric phenol molecular weight regulator cumylphenol and sodium hydroxide 0.35g, and 3% triethylamine solution of 0.2mL, continue reaction 1h, separate and purify, promptly.
Bis-phenol: polyphenylene oxide: alkali: oxidation inhibitor: catalyzer: triphosgene: monohydric phenol molecular weight regulator mol ratio is 1: 0.0013: 2.055: 0.0008: 0.0014: 0.37: 0.0027.
The IR figure of the polycarbonate that present embodiment obtains-polyphenylether segmented thing sees Fig. 2; Its thermogravimetric curve is seen PC-b-PPEII curve among Fig. 3.
Embodiment 3
1. 1.1415g dihydroxyphenyl propane, 0.425g sodium hydroxide, 25mg oxidation inhibitor V-Brite B and 0.015ml catalyst of triethylamine are added in the 10ml water, be made into water;
2. be that two hydroxyl polyphenylene oxide of 40000 are dissolved in the 7mL trichloromethane with 1.5g weight-average molecular weight molecular weight, polyphenylene oxide solution; The 0.8g triphosgene is dissolved in the 5ml trichloromethane, gets triphosgene solution; 6.5ml polyphenylene oxide solution is joined step aqueous phase 1., stir, add 14ml triphosgene solution again, stirring reaction 30min, temperature of reaction is at 30 ℃, and pH adds the polyphenylene oxide solution and the triphosgene solution of surplus again 10; The concentration of described polyphenylene oxide solution is 0.2g/ml, and the concentration of triphosgene solution is 0.36g/ml.
3. add 2.5mg monohydric phenol molecular weight regulator cumylphenol and sodium hydroxide 0.1g, continue reaction 1h, separate and purify, promptly.
Bis-phenol: polyphenylene oxide: alkali: oxidation inhibitor: catalyzer: triphosgene: monohydric phenol molecular weight regulator mol ratio is 1: 0.0075: 2.125: 0.0014: 0.54: 0.26: 0.0034.
The GPC curve of the polycarbonate that present embodiment obtains-polyphenylether segmented thing is seen Fig. 1, and its thermogravimetric curve is seen PC-b-PPE III curve among Fig. 3, and the DSC curve is seen Fig. 4.
After we carried out interfacial polymerization as can be seen from Fig. 1, the polymkeric substance that obtains what deserves to be mentioned is that to the skew of high molecular direction this segmented copolymer does not carry out the GPC test of carrying out before the extracting.The characteristic absorbance that we can see the existing polycarbonate of polymkeric substance that obtains after the extracting from Fig. 2 has the characteristic absorbance of polyphenylene oxide again, and changes with the composition of segmented copolymer.Confirm that thus the contriver successfully synthesizes the polycarbonate of design-polyphenylether segmented multipolymer.
Can see different along with polyphenylene oxide content by the thermogravimetric curve of polyphenylene oxide shown in Figure 3 and polycarbonate-polyphenylether segmented multipolymer, the thermal characteristics of polycarbonate has obtained improvement in various degree.And in DSC curve shown in Figure 4, can see two mutually near and the second-order transition temperatures between polycarbonate and polyphenylene oxide.
The above; only be a part of embodiment of the present invention, protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.
Claims (9)
1. method for preparing polycarbonate-polyphenylether segmented multipolymer, the structural formula of described polycarbonate-polyphenylether segmented multipolymer is:
Wherein, 1≤m≤1000,10≤n≤1000 and m, n is integer, and R is the alkyl of C1-C4 in the formula, and R ' is a hydrogen or halogen, it is characterized in that comprising the steps:
1. take by weighing raw material by following mol ratio:
Bis-phenol: polyphenylene oxide: alkali: oxidation inhibitor: catalyzer: triphosgene: the monohydric phenol molecular weight regulator is 1: 0.0013-0.0075: 2.05-2.5: 0.0008-0.0034: 0.0014-0.54: 0.26-0.37: 0.0027-0.0034;
2. bis-phenol, part alkali, oxidation inhibitor and catalyzer are added in the entry, be made into water;
3. polyphenylene oxide and triphosgene are dissolved in respectively in the organic solvent, get polyphenylene oxide solution and triphosgene solution; Part polyphenylene oxide solution is joined step aqueous phase 2., stir, add part triphosgene solution again, stirring reaction 30-60min, temperature of reaction is at 20-40 ℃, and pH adds surplus polyphenylene oxide solution and triphosgene solution again at 9-11;
4. add monohydric phenol molecular weight regulator and surplus alkali, continue reaction 0.5-2h, separate and purify, promptly.
2. method according to claim 1 is characterized in that described bis-phenol is a dihydroxyphenyl propane.
3. method according to claim 1 is characterized in that described alkali is sodium hydroxide, potassium hydroxide or calcium hydroxide.
4. method according to claim 1 is characterized in that described oxidation inhibitor is V-Brite B, sodium thiosulfite or S-WAT.
5. method according to claim 1 is characterized in that described catalyzer is triethylamine, tetrabutylammonium, tetrabutylammonium chloride or Diethylaminoethyl tributyl ammonium.
6. method according to claim 1 is characterized in that described polyphenylene oxide is the terminal polyphenylene oxide that contains hydroxyl.
7. method according to claim 6 is characterized in that described polyphenylene oxide is two hydroxyl polyphenylene oxide, and weight-average molecular weight is 2000-40000.
8. method according to claim 2 is characterized in that the 3. middle organic solvent of described step is tetrahydrofuran (THF) or trichloromethane, and the concentration of described polyphenylene oxide solution is 0.05-0.3g/ml, and the concentration of triphosgene solution is 0.05-0.5g/ml.
9. method according to claim 1 is characterized in that described monohydric phenol molecular weight regulator is a kind of or wherein several mixture in cumylphenol, tert.-butyl phenol, phenol or the cumyl phenol.
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| CN114163602A (en) * | 2021-12-26 | 2022-03-11 | 大连中沐化工有限公司 | Polyphenyl ether-polyether block copolymer |
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| WO2015174533A1 (en) * | 2014-05-16 | 2015-11-19 | 出光興産株式会社 | Polycarbonate copolymer, coating solution, electrophotographic photoreceptor, and electric device |
| KR102308714B1 (en) | 2018-09-14 | 2021-10-01 | 주식회사 엘지화학 | Diol compound, polycarbonate and method for preparing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446278A (en) * | 1981-05-18 | 1984-05-01 | General Electric Company | Polyphenylene oxide blends |
| US4740554A (en) * | 1985-11-23 | 1988-04-26 | Bayer Aktiengesellschaft | Thermoplastic moulding compositions based on polyphenylene oxide/polycarbonate block condensates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446278A (en) * | 1981-05-18 | 1984-05-01 | General Electric Company | Polyphenylene oxide blends |
| US4740554A (en) * | 1985-11-23 | 1988-04-26 | Bayer Aktiengesellschaft | Thermoplastic moulding compositions based on polyphenylene oxide/polycarbonate block condensates |
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| Title |
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| JP平3-287658A 1991.12.18 |
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| CN114163602A (en) * | 2021-12-26 | 2022-03-11 | 大连中沐化工有限公司 | Polyphenyl ether-polyether block copolymer |
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