CN118255976A - Special isosorbide-based polycarbonate and preparation method thereof - Google Patents
Special isosorbide-based polycarbonate and preparation method thereof Download PDFInfo
- Publication number
- CN118255976A CN118255976A CN202211681955.9A CN202211681955A CN118255976A CN 118255976 A CN118255976 A CN 118255976A CN 202211681955 A CN202211681955 A CN 202211681955A CN 118255976 A CN118255976 A CN 118255976A
- Authority
- CN
- China
- Prior art keywords
- isosorbide
- based polycarbonate
- monomer
- special
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 title claims abstract description 134
- 229960002479 isosorbide Drugs 0.000 title claims abstract description 133
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 132
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003063 flame retardant Substances 0.000 claims abstract description 31
- 239000000155 melt Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 230000009477 glass transition Effects 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 238000006068 polycondensation reaction Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- FPIGBKDVHZUQJO-UHFFFAOYSA-N 2-hydroxyethyl(phenyl)phosphinic acid Chemical compound OCCP(O)(=O)C1=CC=CC=C1 FPIGBKDVHZUQJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 4
- 230000004224 protection Effects 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 2
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 claims description 2
- HSNQKJVQUFYBBY-UHFFFAOYSA-N dipentyl carbonate Chemical compound CCCCCOC(=O)OCCCCC HSNQKJVQUFYBBY-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 51
- 238000012360 testing method Methods 0.000 description 37
- 230000006750 UV protection Effects 0.000 description 25
- 239000002808 molecular sieve Substances 0.000 description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- -1 aliphatic diols Chemical class 0.000 description 5
- 229920005668 polycarbonate resin Polymers 0.000 description 5
- 239000004431 polycarbonate resin Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KLDXJTOLSGUMSJ-UHFFFAOYSA-N 2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound OC1COC2C(O)COC21 KLDXJTOLSGUMSJ-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 230000036760 body temperature Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010067572 Oestrogenic effect Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides special isosorbide-based polycarbonate and a preparation method thereof. The preparation method comprises the following steps: and (3) taking carbonic acid dibasic ester as a first monomer, isosorbide as a second monomer and a phosphorus-containing flame retardant as a third monomer, and reacting in the presence of a catalyst to obtain the special isosorbide-based polycarbonate. The special isosorbide-based polycarbonate provided by the invention is prepared by the preparation method. The preparation method of the invention is to prepare the isosorbide-based polycarbonate by a melt transesterification method under the action of a catalyst by taking carbonic acid dibasic ester as a first monomer, isosorbide as a second monomer and a phosphorus-containing flame retardant as a third monomer. The preparation method disclosed by the invention is used for carrying out copolymerization modification on the isosorbide-based polycarbonate, so that the flexibility of the isosorbide-based polycarbonate is improved and the weather resistance and the flame retardance of the isosorbide-based polycarbonate are enhanced under the condition that the thermal property and the mechanical property of the polycarbonate are not influenced.
Description
Technical Field
The invention relates to special isosorbide-based polycarbonate and a preparation method thereof, belonging to the technical field of synthesis of high molecular polymers.
Background
Polycarbonate (polycarbonate, PC), a generic term for high molecular polymers containing carbonate groups (-OROCO-) in the molecular chain, is one of five general engineering plastics. Because polycarbonate has the advantages of good impact resistance, heat stability, cold resistance, higher glass transition temperature and the like, the polycarbonate is widely applied to various fields of automobile manufacture, food packaging, electronic appliances, medical appliances and the like, and plays a great role in daily life of people.
Most of the production raw materials of polycarbonate are derived from petroleum derivatives, but with the increasing decrease of petroleum resources, BPA, one of the production raw materials of polycarbonate, will become a scarce resource in the future. More importantly, BPA is recognized as having estrogenic effects and chronic toxicity, which may be detrimental to the physical health of humans (especially infants), which greatly limits the use of BPA-PC in the fields of food packaging, medical devices, and the like. Therefore, it is urgent to find a green sustainable raw material to replace BPA to produce PC.
Among them, isosorbide derived from glucose has a chiral and rigid structure, is the only currently industrialized dicyclic monomer product, has been widely used for synthesizing polyesters, polyamides, polycarbonates and the like, and is considered to be the most promising polymerized monomer for producing PC instead of BPA. However, isosorbide-based polycarbonates are inferior in mechanical properties and processability due to the special structure (rigid and saturated heterocyclic structure) of isosorbide, and cannot meet industrial uses.
The incorporation of aliphatic diols is an effective method of modifying their mechanical properties and has been reported in the prior art. 1, 4-butanediol was introduced in literature (Polymer Chemistry:2015,6 (4), 633-642) and a polycarbonate copolymer was obtained with a weight average molecular weight of 36500g/mol, a glass transition temperature of 129℃and a tensile strength significantly higher than that of the homopolycarbonate. The incorporation of aliphatic diols into isosorbide-based polycarbonates can maintain their dimensional stability and help to improve their flexibility and processability. However, the copolymer polycarbonate has insufficient performances such as weather resistance, ultraviolet resistance, linearity and the like, and cannot meet more market requirements. CN108727578a discloses an isosorbide-based polycarbonate and a preparation method thereof, wherein the isosorbide-based polycarbonate is prepared by melt transesterification polycondensation reaction with an alkaline molecular sieve as a catalyst and diphenyl carbonate, isosorbide and aliphatic diol as raw materials, but the method has the defect of low product yield. CN110003458a discloses a method for preparing isosorbide-based polycarbonate and its derivatives, which takes diphenyl carbonate and dihydroxyl compound as raw materials, and synthesizes the isosorbide-based polycarbonate and its derivatives through transesterification and polycondensation. CN102746504a discloses a high heat-resistant aliphatic polycarbonate based on 1,4:3, 6-diglycidyl hexaol and a preparation method thereof, the method comprises the steps of under inert gas atmosphere, respectively or mixing 1,4:3, 6-diglycidyl hexaol and aliphatic diol with carbonic ester to complete ester exchange reaction under the action of a catalyst, obtaining prepolymer, and then polycondensing in a polycondensation catalyst to obtain the product. However, the copolycarbonate prepared by the method has insufficient performances such as weather resistance, ultraviolet resistance, linearity and the like, and cannot meet more market requirements.
Therefore, the development of a novel isosorbide-based polycarbonate and a method for preparing the same, which are capable of improving the above-mentioned disadvantages of the prior isosorbide-based polycarbonate, is one of the problems to be solved in the art.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide special isosorbide-based polycarbonate and a preparation method thereof. The special isosorbide-based polycarbonate provided by the invention has good flexibility, weather resistance and flame retardance.
In order to achieve the above object, the first aspect of the present invention provides a method for preparing a special isosorbide-based polycarbonate, comprising the steps of: and (3) reacting in the presence of a catalyst by taking carbonic acid dibasic ester as a first monomer, isosorbide as a second monomer and a phosphorus-containing flame retardant as a third monomer to obtain the special isosorbide-based polycarbonate.
In the above preparation method, preferably, the carbonic acid dibasic ester includes one or a combination of several of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dioctyl carbonate, and the like. More preferably, the carbonic acid dibasic ester comprises diphenyl carbonate and/or dimethyl carbonate.
In the above preparation process, the isosorbide is more specifically referred to as 2, 6-dioxabicyclo [3.3.0] octane-4, 8-diol, 1,4:3, 6-dianhydro-D-glucitol, and 2, 3a,5,6 a-hexahydrofuro (hexahydrofuro) [3,2-b ] furan-3, 6-diol, and isomers thereof.
In the above preparation method, preferably, the phosphorus-containing flame retardant includes 2' -hydroxybiphenyl-2-phosphinic acid and/or 2-hydroxyethyl phenyl phosphinic acid. Wherein, the structure of the 2' -hydroxy biphenyl-2-phosphinic acid is shown in the following structural formula (I):
The structure of the 2-hydroxyethyl phenyl hypophosphorous acid is shown in the following structural formula (II):
both the above-mentioned 2' -hydroxybiphenyl-2-phosphinic acid and 2-hydroxyethyl phenyl phosphinic acid are commercially available. Such as, but not limited to, 2-hydroxyethyl phenyl hypophosphorous acid, commercially available from Shanghai sea, inc.
In the above preparation method, preferably, the molar ratio of the first monomer, the second monomer and the third monomer is 1 (0.5 to 0.95): 0.05 to 0.5. More preferably, the ratio of the molar amount of the first monomer to the sum of the molar amounts of the second monomer and the third monomer is 1:1.
In the above preparation method, preferably, the catalyst is a basic catalyst; more preferably, the catalyst is a basic titanium silicalite catalyst. The basic titanium silicalite molecular sieve catalyst can be a basic titanium silicalite molecular sieve conventional in the art, and can be obtained commercially or by self-preparation through a conventional method.
In the above preparation method, preferably, the catalyst is used in an amount of 0.001% to 1% by weight of the carbonic acid diester; more preferably, the catalyst is used in an amount of 0.01% to 0.5% by weight of the carbonic acid diester.
In the above-mentioned production method, preferably, the reaction includes a transesterification reaction and a polycondensation reaction; the reaction temperature of the transesterification reaction is 100 ℃ -200 ℃ (more preferably 130 ℃ -150 ℃), the reaction pressure is 10 kPa-50 kPa (more preferably 15 kPa-30 kPa), and the reaction time is 0.5 h-3 h (more preferably 1.5 h-3 h); the reaction temperature of the polycondensation reaction is 200 to 300 ℃ (more preferably 200 to 260 ℃), the reaction pressure is 0 to 1kPa (more preferably 100 to 1000 Pa), and the reaction time is 0.5 to 3 hours (more preferably 0.5 to 2.5 hours).
According to a specific embodiment of the present invention, preferably, the above-mentioned method for preparing a specific isosorbide-based polycarbonate comprises the steps of:
(1) Under the protection of inert gas, adding a first monomer carbonic acid dibasic ester, a second monomer isosorbide and a third monomer phosphorus-containing flame retardant into a reaction kettle, setting the temperature of the reaction kettle to be 100-200 ℃, melting raw materials under the stirring condition, and fully mixing the raw materials;
(2) Adding a catalyst into a reaction kettle, setting the temperature of the reaction kettle to be 100 ℃ -200 ℃ (more preferably 130 ℃ -150 ℃), setting the pressure to be 10 kPa-50 kPa (more preferably 15 kPa-30 kPa), carrying out transesterification under stirring for 0.5 h-3 h (more preferably 1.5 h-3 h), then gradually raising the temperature of the reaction kettle to be 200 ℃ -300 ℃ (more preferably 200 ℃ -260 ℃), adjusting the pressure to be 0 kPa-1 kPa (more preferably 100 Pa-1000 Pa), and carrying out polycondensation under stirring for 0.5 h-3 h (more preferably 0.5 h-2.5 h) to obtain a melt polycarbonate copolymer;
(3) Extruding and granulating the melt polycarbonate copolymer to obtain the special isosorbide-based polycarbonate.
In the above preparation method, preferably, the stirring rotation speed is 100-130 r/min.
In the above preparation method, the extrusion and pelletization in the step (3) may be performed using a device conventional in the art, such as a single screw or twin screw extrusion pelletizer or the like.
In a second aspect, the present invention provides a specialty isosorbide-based polycarbonate prepared by the method of preparing a specialty isosorbide-based polycarbonate described above.
According to a specific embodiment of the present invention, it is preferable that the number average molecular weight of the specific isosorbide-based polycarbonate is 47000 to 55000g/mol.
According to a specific embodiment of the present invention, it is preferable that the melt index of the special isosorbide-based polycarbonate is 10 to 12g/10min.
According to a specific embodiment of the present invention, preferably, the glass transition temperature of the special isosorbide-based polycarbonate is 165 to 170 ℃.
According to a specific embodiment of the present invention, it is preferable that the specific isosorbide-based polycarbonate has an elongation at break of 103 to 121% and a tensile modulus of 2200 to 2350MPa.
According to a specific embodiment of the present invention, it is preferred that the Limiting Oxygen Index (LOI) of the specialty isosorbide-based polycarbonate is 28 to 30% and that the specialty isosorbide-based polycarbonate achieve a UL 94V-0 flame retardant rating.
The invention provides a special isosorbide type polycarbonate copolymer and a preparation method thereof. The preparation method of the invention is to prepare the isosorbide-based polycarbonate by a melt transesterification method under the action of an alkaline catalyst by taking carbonic acid dibasic ester as a first monomer, isosorbide as a second monomer and a phosphorus-containing flame retardant as a third monomer. The preparation method of the invention carries out copolymerization modification on the isosorbide-based polycarbonate, creatively adopts the phosphorus-containing flame retardant as a third monomer, solves the problems of poor flexibility, weather resistance and insufficient flame retardance of the existing isosorbide-based polycarbonate, improves the flexibility of the isosorbide-based polycarbonate to meet the processing requirement under the condition of not influencing the thermal property and mechanical property of the polycarbonate, enhances the weather resistance and the ultraviolet resistance of the isosorbide-based polycarbonate, and enhances the flame retardance of the isosorbide-based polycarbonate, thereby widening the application range of the isosorbide-based polycarbonate.
The special isosorbide-based polycarbonate and the preparation method thereof provided by the invention have at least the following excellent effects:
1. The alkaline titanium silicalite molecular sieve catalyst has excellent catalytic performance and extremely low dosage, can be used as an inorganic filler to be directly remained in a polycarbonate product, and does not influence the quality of the polycarbonate product, so that separation and subsequent treatment are not required.
2. The high-performance isosorbide-based polycarbonate prepared by the method disclosed by the invention has the advantages that the flexibility of the product is improved under the condition that the thermal property and mechanical property of the polycarbonate product are not affected, the processing requirement is met, and meanwhile, the weather resistance, the ultraviolet resistance and the flame retardance of the product are improved, so that more market demands are met.
3. The preparation method provided by the invention has simple and efficient technical process and is easy to realize large-scale production.
4. The preparation method provided by the invention can be widely applied to the preparation of isosorbide-based polycarbonate, and has good universality.
In summary, the invention provides a high-efficiency, safe and economical preparation method of high-performance isosorbide-based polycarbonate, and the special isosorbide-based polycarbonate product is prepared, so that the flexibility of the polycarbonate product is improved, the processing requirement is met, and meanwhile, the weather resistance, the ultraviolet resistance and the flame retardance of the product are improved, and more market demands are met.
Drawings
FIG. 1 is a flow chart of a method for preparing a special isosorbide-based polycarbonate according to an embodiment of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
According to one embodiment of the present invention, preferably, as shown in fig. 1, the method for preparing a specific isosorbide-based polycarbonate of the present invention may comprise the steps of:
Step one, air tightness checking: carrying out three times of gas replacement on the reaction kettle by using inert gas, observing a pressure gauge, and checking the air tightness of the reaction kettle;
Step two, charging: under the protection of inert gas, adding a first monomer carbonic acid dibasic ester, a second monomer isosorbide and a third monomer phosphorus-containing flame retardant into a reaction kettle;
step three, pulping: setting the temperature of the reaction kettle to be 100-200 ℃, and after raw materials are melted, starting a stirring device in the reaction kettle to fully mix the raw materials;
Step four, transesterification reaction stage: adding a catalyst into a reaction kettle, setting the temperature of the reaction kettle to be 100 ℃ -200 ℃ (more preferably 130 ℃ -150 ℃), setting the pressure to be 10 kPa-50 kPa (more preferably 15 kPa-30 kPa), and carrying out transesterification under stirring for 0.5 h-3 h (more preferably 1.5 h-3 h), wherein byproducts can be removed by adopting a conventional method;
Step five, polycondensation reaction stage: then gradually raising the temperature of the reaction kettle to 200 ℃ -300 ℃ (more preferably 200 ℃ -260 ℃), adjusting the pressure to 0 kPa-1 kPa (more preferably 100 Pa-1000 Pa), carrying out polycondensation reaction under stirring condition, and removing byproducts by adopting a conventional method to obtain a melt polycarbonate copolymer, wherein the reaction time is 0.5 h-3 h (more preferably 0.5 h-2.5 h);
step six, extruding and granulating: extruding and granulating the melt polycarbonate copolymer to obtain the special isosorbide-based polycarbonate.
The molecular weight, melt index, glass transition temperature, mechanical properties, weather resistance, uv linearity resistance, flame retardancy of the products of the following examples and comparative examples were measured using the following instruments or according to the following methods:
molecular weight: gel Permeation Chromatography (GPC) was performed using chloroform as a solvent and polystyrene as a standard.
Melt index: melt index tester, temperature 240 ℃,2.16kg.
Glass transition temperature: the method for measuring the glass transition temperature of the plastic comprises the following steps: thermo-mechanical analysis (GB/T11998-1989).
Mechanical properties: universal Testing Machine (UTM).
Weather resistance: testing the color difference of the sample after aging by using a xenon lamp aging tester; xenon lamp aging tester (ISO 4892.2-2013), irradiance 0.51W/m 2, wave band 340nm, box body temperature 60 ℃, humidity 50 (+ -10)%, irradiation time 1500h.
Uv resistance: testing the yellowness of the sample before and after aging by using a UV aging test box; UV aging test box (GB/T16422.3), irradiance 0.76W/m 2, wave band 313nm, box body temperature 60 ℃, humidity 50 (+ -10)%, irradiation time 120h. The samples were tested before and after aging according to ASTM D1925-1988, and yellowness was calculated according to the yellowness calculation formula YI (yellowness) =100 (1.28X-1.06Z)/Y in the CIE1931-1976 standard colorimetry system, wherein X, Y, Z is the tristimulus value representing the color of the sample measured with a colorimeter under standard C light source.
Color difference: colorimeter (ASTM D2244-2016).
Flame retardancy: oxygen index method (GB/T2406.2-2009) and American flame retardant Material Standard ANSI/UL-94-1985 are utilized.
Example 1
The embodiment provides a special isosorbide-based polycarbonate which is prepared by the following steps:
Checking the air tightness of a reaction kettle, adding diphenyl carbonate, isosorbide and 2' -hydroxybiphenyl-2-phosphinic acid with the molar ratio of 1:0.5:0.5 into a 1L reaction kettle at room temperature, protecting in nitrogen atmosphere, heating to 100 ℃, melting raw materials, starting a stirring device in the reaction kettle, fully mixing the raw materials, adding an alkaline titanium-silicon molecular sieve catalyst, performing transesterification reaction for 3 hours under the conditions of 130 ℃ and 30kPa and stirring, gradually heating to 240 ℃ and gradually reducing the pressure to 100Pa, performing polycondensation reaction for 0.5 hour under the conditions of stirring, finishing the reaction, extruding and granulating to obtain the special isosorbide-based polycarbonate. The yield of the product was calculated to be 98%. The product was characterized as a special isosorbide-based polycarbonate with a number average molecular weight of 55000 g/mol.
Wherein, the alkaline titanium silicalite molecular sieve catalyst is prepared by a conventional method: 1) Uniformly mixing tetrabutyl titanate Ti (OC 4H9)4, tetraethyl orthosilicate TEOS, tetrapropylammonium hydroxide TPAOH and deionized water according to a proper proportion, heating to 60 ℃, and reacting for 2 hours to obtain a clear guiding agent solution; 2) The preparation method comprises the steps of uniformly mixing cetyl trimethyl ammonium bromide CTAB, 25% ammonia water, deionized water and the guiding agent solution according to a proper proportion, reacting for 5 hours at 40 ℃, transferring into a reaction kettle with a polytetrafluoroethylene lining, aging for 12 hours at 60 ℃, and sequentially carrying out suction filtration, washing, room temperature drying and vacuum drying at 150 ℃ for 6-8 hours on the obtained product to obtain the alkaline titanium silicalite molecular sieve catalyst.
The melt index of the special isosorbide-based polycarbonate of this example was 10g/10min; the glass transition temperature is 170 ℃; elongation at break of 115% and tensile modulus of 2325MPa; limiting Oxygen Index (LOI) of 30% and flame retardant rating of UL94V-0; after weather resistance test, the color difference is 1.21, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 13.67 and 14.41, respectively, and the ultraviolet resistance was excellent.
Example 2
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the 2' -hydroxybiphenyl-2-phosphinic acid of example 1 was replaced by 2-hydroxyethylphenyl phosphinic acid in unchanged amounts and under unchanged other preparation conditions.
The yield of the product was calculated to be 96%. The product was characterized as a special isosorbide-based polycarbonate with a number average molecular weight of 51200 g/mol. The melt index of the special isosorbide-based polycarbonate is 10g/10min; the glass transition temperature is 169 ℃; elongation at break of 109% and tensile modulus of 2300MPa; the limiting oxygen index is 29%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.47, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 14.03 and 15.11, respectively.
Example 3
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the 2 '-hydroxybiphenyl-2-phosphinic acid of example 1 was replaced by a mixture of 2' -hydroxybiphenyl-2-phosphinic acid and 2-hydroxyethylphenyl phosphinic acid in a molar ratio of 1:1, the total amount of the third monomer being unchanged and the other preparation conditions being unchanged.
The yield of the product was calculated to be 96%. The product was characterized as a specialty isosorbide-based polycarbonate with a number average molecular weight of 50700 g/mol. The melt index of the special isosorbide-based polycarbonate is 10g/10min; the glass transition temperature is 168 ℃; elongation at break 103% and tensile modulus 2288MPa; the limiting oxygen index is 29%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.51, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 14.22 and 15.34, respectively.
Example 4
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the catalyst amount is 0.005wt% of diphenyl carbonate amount, and other preparation conditions are unchanged.
The yield of the product was calculated to be 95%. The product was characterized as a specialty isosorbide-based polycarbonate with a number average molecular weight of 47900 g/mol. The melt index of the special isosorbide-based polycarbonate is 11g/10min; the glass transition temperature is 167 ℃; elongation at break 107% and tensile modulus 2265MPa; the limiting oxygen index is 29%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.56, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 15.11 and 16.55, respectively.
Example 5
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the catalyst amount is 0.05wt% of diphenyl carbonate amount, and other preparation conditions are unchanged.
The yield of the product was calculated to be 96%. The product was characterized as a specialty isosorbide-based polycarbonate with a number average molecular weight of 47900 g/mol. The melt index of the special isosorbide-based polycarbonate is 11g/10min; the glass transition temperature is 167 ℃; elongation at break 108% and tensile modulus 2257MPa; the limiting oxygen index is 28%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.68, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 15.22 and 16.68, respectively.
Example 6
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the catalyst amount is 0.075wt% of diphenyl carbonate amount, and other preparation conditions are unchanged.
The yield of the product was calculated to be 96%. The product was characterized as a specialty isosorbide-based polycarbonate with a number average molecular weight of 49200 g/mol. The melt index of the special isosorbide-based polycarbonate is 11g/10min; the glass transition temperature is 167 ℃; elongation at break 110% and tensile modulus 2260MPa; the limiting oxygen index is 28%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.65, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 15.26 and 16.77, respectively.
Example 7
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the catalyst amount is 0.1wt% of diphenyl carbonate amount, and other preparation conditions are unchanged.
The yield of the product was calculated to be 97%. The product was characterized as a specialty isosorbide-based polycarbonate with a number average molecular weight of 47400 g/mol. The melt index of the special isosorbide-based polycarbonate is 12g/10min; the glass transition temperature is 165 ℃; elongation at break 106% and tensile modulus 2225MPa; the limiting oxygen index is 28%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.66, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 15.39 and 16.86, respectively.
Example 8
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the molar ratio of diphenyl carbonate, isosorbide and 2' -hydroxybiphenyl-2-phosphinic acid is 1:0.6:0.4, and other preparation conditions are unchanged.
The yield of the product was calculated to be 96%. The product was characterized as a special isosorbide-based polycarbonate with a number average molecular weight of 53600 g/mol. The melt index of the special isosorbide-based polycarbonate is 10g/10min; the glass transition temperature is 169 ℃; elongation at break 114% and tensile modulus 2295MPa; the limiting oxygen index is 30%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.32, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 14.33 and 15.21, respectively.
Example 9
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the molar ratio of diphenyl carbonate, isosorbide and 2' -hydroxybiphenyl-2-phosphinic acid is 1:0.7:0.3, the other preparation conditions are unchanged.
The yield of the product was calculated to be 95%. The product was characterized as a specialty isosorbide-based polycarbonate with a number average molecular weight of 52300 g/mol. The melt index of the special isosorbide-based polycarbonate is 10g/10min; the glass transition temperature is 169 ℃; elongation at break 113% and tensile modulus 2280MPa; the limiting oxygen index is 30%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.37, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 14.41 and 15.56, respectively.
Example 10
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the molar ratio of diphenyl carbonate, isosorbide and 2' -hydroxybiphenyl-2-phosphinic acid is 1:0.8:0.2, and other preparation conditions are unchanged.
The yield of the product was calculated to be 96%. The product was characterized as a special isosorbide-based polycarbonate with a number average molecular weight of 51900 g/mol. The melt index of the special isosorbide-based polycarbonate is 10g/10min; the glass transition temperature is 168 ℃; elongation at break 113% and tensile modulus 2266MPa; the limiting oxygen index is 29%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.47, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 14.52 and 15.93, respectively.
Example 11
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the molar ratio of diphenyl carbonate, isosorbide and 2' -hydroxybiphenyl-2-phosphinic acid is 1:0.9:0.1, and other preparation conditions are unchanged.
The yield of the product was calculated to be 97%. The product was characterized as a specialty isosorbide-based polycarbonate having a number average molecular weight of 49900 g/mol. The melt index of the special isosorbide-based polycarbonate is 11g/10min; the glass transition temperature is 167 ℃; elongation at break 121% and tensile modulus 2212MPa; the limiting oxygen index is 28%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.58, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 15.01 and 16.89, respectively.
Example 12
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the molar ratio of the dimethyl carbonate, the isosorbide and the 2' -hydroxy biphenyl-2-phosphinic acid is 1:0.9:0.1, and other preparation conditions are unchanged.
The yield of the product was calculated to be 96%. The product was characterized as a specialty isosorbide-based polycarbonate with a number average molecular weight of 48300 g/mol. The melt index of the special isosorbide-based polycarbonate is 12g/10min; the glass transition temperature is 166 ℃; elongation at break 118% and tensile modulus 2200MPa; the limiting oxygen index is 28%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.61, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 15.11 and 16.98, respectively.
Example 13
This example provides a specialty isosorbide-based polycarbonate prepared in substantially the same manner as in example 1, except that: the molar ratio of the dimethyl carbonate, the isosorbide and the 2' -hydroxy biphenyl-2-phosphinic acid is 1:0.95:0.05, and other preparation conditions are unchanged.
The yield of the product was calculated to be 98%. The product was characterized as a specialty isosorbide-based polycarbonate with a number average molecular weight of 50500 g/mol. The melt index of the special isosorbide-based polycarbonate is 12g/10min; the glass transition temperature is 165 ℃; elongation at break 118% and tensile modulus 2200MPa; the limiting oxygen index is 28%, and the flame retardant grade is UL94V-0; after weather resistance test, the color difference is 1.55, so that the general outdoor use requirement is met, and the weather resistance is enhanced; YI values before and after the ultraviolet resistance test were 15.71 and 17.05, respectively.
Comparative example 1
The present comparative example provides an isosorbide-based polycarbonate resin composition prepared by the steps of:
Checking the air tightness of a reaction kettle, adding diphenyl carbonate and isosorbide with the molar ratio of 1:1 into a 1L reaction kettle at room temperature, protecting the nitrogen atmosphere, heating to 100 ℃, starting a stirring device in the reaction kettle after raw materials are melted, fully mixing the raw materials, then adding an alkaline titanium silicalite molecular sieve catalyst (the preparation method is the same as that of example 1), carrying out transesterification reaction for 3 hours at 130 ℃ and 30kPa under stirring, then gradually heating to 240 ℃ and gradually reducing the pressure to 100Pa, carrying out polycondensation reaction for 0.5 hour under stirring, finishing the reaction, extruding and granulating, and carrying out blending modification on the obtained isosorbide-based polycarbonate product and 2 '-hydroxy biphenyl-2-phosphinic acid, wherein the dosage of the 2' -hydroxy biphenyl-2-phosphinic acid is as follows: the molar ratio of the isosorbide-based polycarbonate resin composition to diphenyl carbonate in the raw material is 0.3:1, and the isosorbide-based polycarbonate resin composition is obtained by extrusion and granulation.
The isosorbide-based polycarbonate product was characterized as having a number average molecular weight of 42800g/mol. The melt index of the isosorbide-based polycarbonate resin composition obtained after blending modification is 15g/10min; the glass transition temperature is 159 ℃; elongation at break 118% and tensile modulus 2180MPa; the limiting oxygen index is 26%, and the flame retardant grade is UL94V-1; after weather resistance test, the color difference is 5.6; YI values before and after the ultraviolet resistance test were 16.08 and 21.22, respectively. It can be seen that the isosorbide-based polycarbonate resin composition of this comparative example is weaker in weather resistance, ultraviolet ray resistance and flame retardancy than the product of example 1.
Comparative example 2
This comparative example provides an isosorbide-based polycarbonate prepared by the steps of:
Checking the air tightness of a reaction kettle, adding diphenyl carbonate, isosorbide and an organic silsesquioxane flame retardant (Si 9800) in a molar ratio of 1:0.7:0.3 into a 1L reaction kettle at room temperature, protecting the nitrogen atmosphere, heating to 100 ℃, melting raw materials, starting a stirring device in the reaction kettle, fully mixing the raw materials, adding an alkaline titanium-silicon molecular sieve catalyst (the preparation method is the same as that of the example 1), performing transesterification reaction for 3 hours at 130 ℃ and 30kPa under stirring, gradually heating to 240 ℃ and gradually reducing the pressure to 100Pa, performing polycondensation reaction for 0.5 hour under stirring, and extruding and granulating to obtain the product of the isosorbide-based polycarbonate.
The yield of the product was calculated to be 95%. Characterizing the product, wherein the number average molecular weight of the product is 41000g/mol; the melt index is 15g/10min; the glass transition temperature is 160 ℃; elongation at break 93%; after weather resistance test, the color difference is 5.9, and the weather resistance is weaker; YI values before and after ultraviolet resistance test are 16.44 and 21.57 respectively, and ultraviolet resistance linearity is weak; the limiting oxygen index was 25% and the UL 94V-1 flame retardant rating was achieved, with flame retardancy being weaker than the product of example 1.
Comparative example 3
The comparative example provides a special isosorbide-based polycarbonate prepared by the steps of:
Checking the air tightness of a reaction kettle, adding diphenyl carbonate, isosorbide and 2' -hydroxybiphenyl-2-phosphinic acid with the molar ratio of 1:0.7:0.3 into a 1L reaction kettle at room temperature, protecting the nitrogen atmosphere, heating to 100 ℃, after melting raw materials, starting a stirring device in the reaction kettle, fully mixing the raw materials, adding an alkaline molecular sieve catalyst, performing transesterification reaction for 3 hours under the conditions of 130 ℃ and 30kPa and stirring, gradually heating to 240 ℃ and gradually reducing the pressure to 100Pa, performing polycondensation reaction for 0.5 hour under the condition of stirring, finishing the reaction, extruding and granulating to obtain the special isosorbide-based polycarbonate.
Wherein, the basic molecular sieve catalyst is prepared by the following method: ca (NO 3)2·4H2 O) is dissolved in deionized water, then SBA-15 molecular sieve is added, stirring reaction is carried out for 12 hours, evaporation drying is carried out at 100 ℃ to obtain white powder, and the white powder is roasted for 6 hours at 550 ℃ to obtain the alkaline molecular sieve catalyst.
The yield of the product was calculated to be 93%. Characterizing the product, wherein the number average molecular weight of the product is 35000g/mol; the melt index is 18g/10min; the glass transition temperature is 155 ℃; elongation at break 82%; after weather resistance test, the color difference is 6.8, and the weather resistance is weaker; YI values before and after ultraviolet resistance test are 16.79 and 21.98 respectively, and ultraviolet resistance linearity is weak; the limiting oxygen index was 24% and a UL 94V-1 flame retardant rating was achieved, with flame retardancy being weaker than the product of example 1.
Claims (10)
1. A method for preparing special isosorbide-based polycarbonate, which comprises the following steps: and (3) reacting in the presence of a catalyst by taking carbonic acid dibasic ester as a first monomer, isosorbide as a second monomer and a phosphorus-containing flame retardant as a third monomer to obtain the special isosorbide-based polycarbonate.
2. The preparation method according to claim 1, wherein the carbonic acid dibasic ester comprises one or a combination of several of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate and dioctyl carbonate;
Preferably, the carbonic acid dibasic ester comprises diphenyl carbonate and/or dimethyl carbonate.
3. The method of claim 1, wherein the phosphorus-containing flame retardant comprises 2' -hydroxybiphenyl-2-phosphinic acid and/or 2-hydroxyethyl phenyl phosphinic acid.
4. The production process according to any one of claims 1 to 3, wherein a molar ratio of the first monomer, the second monomer and the third monomer is 1 (0.5 to 0.95): 0.05 to 0.5; preferably, the ratio of the molar amount of the first monomer to the sum of the molar amounts of the second monomer and the third monomer is 1:1.
5. The production method according to claim 1, wherein the catalyst is a basic catalyst; preferably, the catalyst is a basic titanium silicalite catalyst.
6. The preparation method according to claim 1,2 or 5, wherein the catalyst is used in an amount of 0.001% to 1% by weight of the carbonic acid diester; preferably, the catalyst is used in an amount of 0.01 to 0.5% by weight of the carbonic acid diester.
7. The production method according to claim 1, wherein the reaction comprises a transesterification reaction and a polycondensation reaction; the reaction temperature of the transesterification reaction is 100-200 ℃, the reaction pressure is 10-50 kPa, and the reaction time is 0.5-3 h; the reaction temperature of the polycondensation reaction is 200-300 ℃, the reaction pressure is 0-1 kPa, and the reaction time is 0.5-3 hours.
8. The preparation method according to claim 1, wherein the preparation method comprises the steps of:
(1) Under the protection of inert gas, adding a first monomer carbonic acid dibasic ester, a second monomer isosorbide and a third monomer phosphorus-containing flame retardant into a reaction kettle, setting the temperature of the reaction kettle to be 100-200 ℃, melting raw materials under the stirring condition, and fully mixing the raw materials;
(2) Adding a catalyst into a reaction kettle, setting the temperature of the reaction kettle to be 100-200 ℃, setting the pressure to be 10-50 kPa, carrying out transesterification reaction under stirring for 0.5-3 hours, then gradually raising the temperature of the reaction kettle to be 200-300 ℃, adjusting the pressure to be 0-1 kPa, and carrying out polycondensation reaction under stirring for 0.5-3 hours to obtain a melt polycarbonate copolymer;
(3) Extruding and granulating the melt polycarbonate copolymer to obtain the special isosorbide-based polycarbonate.
9. A special isosorbide-based polycarbonate prepared by the method of preparing a special isosorbide-based polycarbonate of any one of claims 1-8.
10. The specialty isosorbide-based polycarbonate of claim 9 wherein the specialty isosorbide-based polycarbonate has a number average molecular weight of 47000 to 55000g/mol;
Preferably, the melt index of the special isosorbide-based polycarbonate is 10-12 g/10min;
preferably, the glass transition temperature of the special isosorbide-based polycarbonate is 165-170 ℃;
Preferably, the elongation at break of the special isosorbide-based polycarbonate is 103-121%, and the tensile modulus is 2200-2350 MPa;
Preferably, the specialty isosorbide-based polycarbonate has a limiting oxygen index of 28 to 30% and the specialty isosorbide-based polycarbonate achieves a UL 94V-0 flame retardant rating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211681955.9A CN118255976A (en) | 2022-12-26 | 2022-12-26 | Special isosorbide-based polycarbonate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211681955.9A CN118255976A (en) | 2022-12-26 | 2022-12-26 | Special isosorbide-based polycarbonate and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118255976A true CN118255976A (en) | 2024-06-28 |
Family
ID=91609953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211681955.9A Pending CN118255976A (en) | 2022-12-26 | 2022-12-26 | Special isosorbide-based polycarbonate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118255976A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119286226A (en) * | 2024-11-14 | 2025-01-10 | 昆山地博光电材料有限公司 | Antibacterial polycarbonate film and preparation process thereof |
-
2022
- 2022-12-26 CN CN202211681955.9A patent/CN118255976A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119286226A (en) * | 2024-11-14 | 2025-01-10 | 昆山地博光电材料有限公司 | Antibacterial polycarbonate film and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4962007B2 (en) | Flame retardant polyester and method for producing the same | |
| TWI848929B (en) | Biobased polycarbonate ester and preparing method thereof | |
| KR20240146110A (en) | High-viscosity polyester with improved impact properties | |
| EP2478031A2 (en) | Polyester resin and method for preparing the same | |
| EP2586828A1 (en) | Polycarbonate resin composition and molded article | |
| CN118255976A (en) | Special isosorbide-based polycarbonate and preparation method thereof | |
| CN112898550B (en) | Biodegradable polyester and preparation method thereof | |
| CN102775590A (en) | Poly(butylene succinate) and preparation method thereof | |
| CN116023644A (en) | Carbon dioxide-based tetrablock copolymer and preparation method thereof | |
| CN115850641A (en) | Flame-retardant modified polyurethane material and synthesis method thereof | |
| CN115558084B (en) | Cardanol-terminated medium-high molecular weight brominated epoxy resin and method thereof, flame-retardant polyester filament and method thereof and flame-retardant high molecular material | |
| CN115850944A (en) | High-light-transmittance thin-wall flame-retardant polycarbonate composition and preparation method thereof | |
| CN112724385B (en) | Hydrolysis-resistant flame-retardant polyester and preparation method thereof | |
| CN111621006B (en) | Preparation method of high-toughness bio-based antibacterial polyester | |
| KR102292023B1 (en) | Polycarbonate resin and method for preparing the same | |
| WO2005103112A1 (en) | A flame retardant polyester with excellent color tone, and a process of preparing the same | |
| CN109206865B (en) | Phosphorus-containing copolymerized flame-retardant polylactic acid and preparation method thereof | |
| TW200808867A (en) | Method for making molded polycarbonate articles with improved color | |
| CN118085361B (en) | Preparation method of modified regenerated PETG polyester film | |
| CN112708123B (en) | Preparation method of flame-retardant polycarbonate | |
| CN114349949B (en) | Scratch-resistant copolycarbonate and preparation method and application thereof | |
| CN117209754B (en) | A DOPO-based halogen-free intrinsic flame-retardant nylon 66 and a preparation method thereof | |
| CN116063672B (en) | Triphenol A type polycarbonate and preparation method thereof | |
| CN116656211B (en) | Water-based epoxy insulating paint and preparation method thereof | |
| CN114958285B (en) | Low-temperature activated single-component polyurethane sealant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |