CN117964890A - Preparation method and application of isosorbide type copolycarbonate - Google Patents
Preparation method and application of isosorbide type copolycarbonate Download PDFInfo
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- CN117964890A CN117964890A CN202311674938.7A CN202311674938A CN117964890A CN 117964890 A CN117964890 A CN 117964890A CN 202311674938 A CN202311674938 A CN 202311674938A CN 117964890 A CN117964890 A CN 117964890A
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- transesterification
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- isosorbide
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- carbonate
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- 229960002479 isosorbide Drugs 0.000 title claims abstract description 49
- 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 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 102
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 17
- 150000004650 carbonic acid diesters Chemical class 0.000 claims abstract description 13
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims abstract description 9
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims abstract description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 6
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- -1 alkali metal salt Chemical class 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- LVLZXBIWQHFREA-UHFFFAOYSA-N phenol;phosphane Chemical group [PH4+].[O-]C1=CC=CC=C1 LVLZXBIWQHFREA-UHFFFAOYSA-N 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- APIBROGXENTUGB-ZUQRMPMESA-M triphenyl-[(e)-3-phenylprop-2-enyl]phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C\C=C\C1=CC=CC=C1 APIBROGXENTUGB-ZUQRMPMESA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LZOHWIXYBMRNAP-UHFFFAOYSA-M triphenyl(trityl)phosphanium;chloride Chemical compound [Cl-].C1=CC=CC=C1C([P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LZOHWIXYBMRNAP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 24
- 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 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 10
- 229920001577 copolymer Polymers 0.000 abstract description 8
- 230000009257 reactivity Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 6
- 238000004383 yellowing Methods 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 57
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000004821 distillation Methods 0.000 description 14
- 238000009826 distribution Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WYGVRVDZSPABJU-UHFFFAOYSA-N Cl[P](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound Cl[P](c1ccccc1)(c1ccccc1)c1ccccc1 WYGVRVDZSPABJU-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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method and application of isosorbide type copolycarbonate. The invention provides a preparation method of isosorbide type copolycarbonate, which comprises the following steps: first transesterification, second transesterification, polycondensation, and post-treatment; in the first transesterification and/or the second transesterification step, the carbonic acid diester is selected from: any one or more of dimethyl carbonate, diphenyl carbonate, diethyl carbonate and dibutyl carbonate. The invention also provides application of the preparation method in preparation of bisphenol A type polycarbonate resin. The series transesterification technology is adopted, the composition of the transesterification product is regulated and controlled to control the reactivity ratio in the polycondensation process, so that the uniformity of the product is improved, and the light transmittance is further improved; meanwhile, the specific selection of the carbonic acid diester can reduce the temperature of the polycondensation reaction and prevent the yellowing of the product after the high temperature; solves the technical defect of poor light transmittance of the isosorbide copolymer in the prior art.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method and application of isosorbide type copolycarbonate.
Background
Bisphenol a polycarbonate resins (BPA-PC) are excellent in transparency, mechanical properties, thermal properties, electrical properties, weather resistance, and the like, and are used for optical members such as light guide plates. However, since BPA in BPA-PC migrates during use, which may have a bad influence on the human body, BPA has been prohibited from being used for the production of articles for daily use in europe and america. Based on the environmental protection of biological materials, bio-based polycarbonates have become a hotspot in the current research of polyester materials, wherein isosorbide, which is produced by dehydration of glucose, is an ideal substitute for bisphenol a.
However, in the prior art, since the bisfuran ring structure of isosorbide has a strong rigidity, it is necessary to carry out copolymerization modification to improve the processability thereof. In the synthesis process of the copolymerized isosorbide type carbonic ester, there may be a difference in reactivity ratios of different monomers, so that the composition of a copolymerization product is uneven, and compatibility of each phase is insufficient, so that the obtained copolymer is easy to generate a white turbidity phenomenon, has poor light transmittance and the like.
In view of the foregoing, patent (CN 105175706A) describes a process for producing a polycarbonate by transesterification and precondensation of dinaphthyl carbonate and 2, 2-bis (2-methyl-7-hydroxy-benzoxazole) propane in the presence of a catalyst, followed by polycondensation by addition of isosorbide. The isosorbide type copolycarbonate produced by the technical scheme has the light transmittance reaching more than 92 percent. However, the pre-polycondensation is required after the transesterification of the third monomer, the vacuum degree is 5-10 kPa, and the polycondensation temperature is high and the production cost is high because the boiling point of naphthol is as high as 285℃. Meanwhile, the isosorbide is easy to absorb water, oxidize and the like, and the excessive reaction temperature can aggravate side reactions to cause yellowing of the hue of the product, so that good light transmittance can not be realized.
Therefore, a preparation method and application of isosorbide type copolycarbonate are developed to solve the technical defect of poor light transmittance of the isosorbide copolymer in the prior art, and the problem to be solved by the person skilled in the art is urgent.
Disclosure of Invention
Based on the above, it is necessary to provide a method for preparing isosorbide type copolycarbonate and application thereof, aiming at the technical defect of poor light transmittance of the isosorbide copolymer in the prior art.
The invention provides a preparation method of isosorbide type copolycarbonate, which comprises the following steps:
Step one, first transesterification: mixing polyol, carbonic diester and a catalyst, and performing first transesterification to obtain a first product;
Step two, second transesterification: mixing the first product, the isosorbide and the catalyst, and performing a second transesterification to obtain a second product;
step three, polycondensation reaction: performing polycondensation reaction on the second product to obtain a third product;
Step four, post-treatment: extruding, cooling and granulating the third product to obtain an isosorbide type copolycarbonate product;
In step one and/or step two, the carbonic acid diester is selected from: any one or more of dimethyl carbonate, diphenyl carbonate, diethyl carbonate and dibutyl carbonate.
In one embodiment, in step one, the polyol is selected from: any one or more of tricyclodecanedimethanol, 1, 4-butanediol, diethylene glycol, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 1, 4-terephthalenedimethanol and 1, 4-cyclohexanedimethanol.
In one embodiment, in step one, the catalyst is an alkali metal salt solution having a concentration of 50 to 1000 μg/g.
In one embodiment, the alkali metal salt solution is an alkali metal salt selected from the group consisting of: any one or more of calcium acetate, calcium carbonate, potassium carbonate, magnesium acetate, zinc acetate, sodium methoxide and zinc nitrate;
In the alkali metal salt solution, the solvent is selected from the group consisting of: any one or more of water, dimethyl carbonate, methanol, ethanol, butanol and ethylene glycol.
In one embodiment, in the second step, the mass ratio of the catalyst to the carbonic acid diester is 400-1000 mug/g;
And/or the number of the groups of groups,
The feeding mole ratio of the isosorbide in the second step to the polyol in the first step is 1 (0.5-5);
And/or the number of the groups of groups,
In the second step, the feeding mole ratio of the isosorbide to the carbonic acid diester is 1 (0.5-5).
In one embodiment, in step two, the catalyst is selected from: one or more of tetrapropylammonium hydroxide, di-n-propylamine, cinnamyl triphenyl phosphonium bromide, (trityl) triphenyl phosphonium chloride, cetyl trimethyl ammonium bromide, and trihexyltetradecyl quaternary phosphonium phenolate.
In one embodiment, in the first step, the temperature of the first transesterification is 160-210 ℃, the time of the first transesterification is 0.5-5 h, the pressure of the first transesterification is 0.09-0.1 MPa, and the stirring speed of the first transesterification is 50-200 r/min;
And/or the number of the groups of groups,
In the second step, the temperature of the second transesterification is 160-210 ℃, the time of the second transesterification is 0.5-5 h, the pressure of the second transesterification is 0.09-0.1 MPa, and the stirring rotating speed of the second transesterification is 50-200 r/min.
In one embodiment, the temperature of the polycondensation reaction is 190-260 ℃, the vacuum degree of the polycondensation reaction is 0.03-1 kPa, and the time of the polycondensation reaction is 0.5-5 hours.
In one embodiment, the first product has a weight average molecular weight Mw of 500 to 2000 and a PDI of 1.5 to 3;
And/or the number of the groups of groups,
The weight average molecular weight Mw of the second product is 500-2000, and the PDI of the second product is 1.5-3;
And/or the number of the groups of groups,
The isosorbide type copolycarbonate product has a weight average molecular weight Mw of 30000-60000 and a PDI of 1.5-3.
The invention also provides an application of the preparation method in preparation of bisphenol A type polycarbonate resin.
In summary, the invention provides a method for preparing isosorbide type copolycarbonate, which comprises the following steps: first transesterification, second transesterification, polycondensation, and post-treatment; in the first transesterification and/or the second transesterification step, the carbonic acid diester is selected from: any one or more of dimethyl carbonate, diphenyl carbonate, diethyl carbonate and dibutyl carbonate. The invention also provides application of the preparation method in preparation of bisphenol A type polycarbonate resin. In the invention, a serial transesterification process is adopted to regulate and control the composition of a transesterification product to control the reactivity ratio in the polycondensation process, thereby improving the uniformity of the product and further improving the light transmittance; meanwhile, the specific selection of the carbonic acid diester can reduce the temperature of the polycondensation reaction and prevent the yellowing of the product after the high temperature. The preparation method and the application of the isosorbide type copolycarbonate provided by the invention solve the technical defect of poor light transmittance of the isosorbide type copolycarbonate in the prior art.
Detailed Description
The embodiment of the invention provides a preparation method and application of isosorbide type copolycarbonate, which are used for solving the technical defect of poor light transmittance of the isosorbide type copolycarbonate in the prior art.
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "upper," "lower," "left," "right," and the like are used herein for illustrative purposes only and are not meant to be the only embodiment.
In the examples and comparative examples of the present invention, the isosorbide material used was pharmaceutical grade and recrystallized 3 times from acetone.
Example 1
107G (0.5 mol) of diphenyl carbonate, 72g (0.5 mol) of 1,4 cyclohexanedimethanol and 0.015g of aqueous solution of potassium carbonate (potassium carbonate concentration: 50. Mu.g/g) were added into a transesterification reaction vessel, and the transesterification reaction was carried out under N 2 protection, and the temperature was raised to 160℃under a pressure of 0.09MPa and a stirring rate of 80r/min, and phenol produced by the reaction was discharged through a distillation apparatus, and after the transesterification reaction was carried out for 1 hour, a first product was obtained.
Mixing 40g (0.25 mol) of isosorbide, 69g (0.32 mol) of diphenyl carbonate and 0.03g of cinnamyl triphenyl phosphonium bromide uniformly by a mixer, adding the mixture into a first product, carrying out transesterification under the protection of N 2, wherein the temperature is still 160 ℃, the pressure is normal pressure, the stirring speed is 80r/min, discharging phenol generated by the reaction by a distillation device, and carrying out transesterification for 1h to obtain a second product.
In this example, the means for removing monohydroxy byproducts as much as possible is: by gradually decreasing the polycondensation pressure at a certain temperature, when the polycondensation pressure is kept substantially stable and the stirring torque is kept substantially stable, it can be considered that the polycondensation end point is substantially reached and the removal of the monohydroxy by-product is substantially achieved. The removal mode of the monohydroxy byproducts in the other embodiments is basically the same as that in the present embodiment, and will not be described in detail later.
After the transesterification reaction is finished, vacuumizing and decompressing until the system pressure is lower than 100Pa, gradually heating to 200 ℃, reacting for 120min, extruding a product from the bottom of a polymerization kettle after the reaction is finished, cooling and granulating, wherein the weight average molecular weight Mw of the obtained polymer is 58245, the molecular weight distribution index PDI is=2.04, and the light transmittance is 92%.
Example 2
270G (3 mol) of dimethyl carbonate, 53g (0.5 mol) of diethylene glycol and 0.03g of dimethyl carbonate solution of calcium acetate (potassium carbonate concentration is 500 mu g/g) are added into a transesterification reaction kettle, transesterification reaction is carried out under the protection of N 2, the temperature is raised to 200 ℃, the pressure is normal pressure, the stirring speed is 150r/min, methanol generated by the reaction is discharged through a distillation device, and the first product is obtained after 3 hours of transesterification reaction.
292G (2 mol) of isosorbide, 45g (0.5 mol) of dimethyl carbonate and 0.06g of tetrapropylammonium hydroxide are added into the first product after being uniformly mixed by a mixer, the transesterification reaction is carried out under the protection of N 2, the temperature is raised to 210 ℃, the pressure is normal pressure, the stirring speed is 200r/min, the ethanol generated by the reaction is discharged through a distillation device, and the second product is obtained after 3 hours of transesterification reaction.
After the transesterification reaction is finished, vacuumizing and decompressing until the system pressure is lower than 100Pa, gradually heating to 240 ℃, reacting for 60min, extruding a product from the bottom of a polymerization kettle after the reaction is finished, cooling and granulating to obtain a polymer with the weight average molecular weight Mw of 36887, the molecular weight distribution index PDI=3.22 and the light transmittance of 95%.
Example 3
336G (2 mol) of diethyl carbonate, 69g (0.5 mol) of 1, 4-terephthalyl alcohol and 0.6g of ethylene glycol solution of zinc nitrate (the concentration of zinc nitrate is 100 mu g/g) are added into a transesterification reaction kettle, transesterification reaction is carried out under the protection of N 2, the temperature is raised to 180 ℃, the pressure is normal pressure, the stirring speed is 100r/min, ethanol generated by the reaction is discharged through a distillation device, and the first product is obtained after the transesterification reaction is carried out for 2 hours.
146G (1 mol) of isosorbide, 118g (1 mol) of diethyl carbonate and 0.036g of trihexyl tetradecyl quaternary phosphonium phenolate are uniformly mixed by a mixer and added into a first product, the transesterification reaction is carried out under the protection of N 2, the temperature is increased to 210 ℃, the pressure is normal pressure, the stirring speed is 200r/min, the ethanol generated by the reaction is discharged through a distillation device, and the transesterification reaction is carried out for 5 hours, so that a second product is obtained.
After the transesterification reaction is finished, vacuumizing and decompressing until the system pressure is lower than 300Pa, gradually heating to 230 ℃ and reacting for 200min, extruding a product from the bottom of a polymerization kettle after the reaction is finished, cooling and granulating to obtain a polymer with the weight average molecular weight Mw of 43193, the molecular weight distribution index PDI=2.87 and the light transmittance of 88%.
Example 4
135G (1.5 mol) of dimethyl carbonate, 69g (0.5 mol) of 1, 4-terephthalyl methane and 0.03g of methanol solution of calcium carbonate (the concentration of the calcium carbonate is 300 mu g/g) are added into a transesterification reaction kettle, transesterification reaction is carried out under the protection of N 2, the temperature is raised to 190 ℃, the pressure is normal pressure, the stirring speed is 100r/min, methanol generated by the reaction is discharged through a distillation device, and the first product is obtained after 3 hours of transesterification reaction.
292G (2 mol) of isosorbide, 360g (4 mol) of dimethyl carbonate and 0.21g (trityl) of triphenylphosphine chloride are mixed uniformly by a mixer and added into the first product, the transesterification reaction is carried out under the protection of N 2, the temperature is increased to 200 ℃, the pressure is normal pressure, the stirring speed is 200r/min, the methanol generated by the reaction is discharged by a distillation device, and the second product is obtained after 3 hours of transesterification reaction.
After the transesterification reaction is finished, vacuumizing and decompressing until the system pressure is lower than 200Pa, gradually heating to 230 ℃ and reacting for 60min, extruding a product from the bottom of a polymerization kettle after the reaction is finished, cooling and granulating to obtain a polymer with the weight average molecular weight Mw of 38095, the molecular weight distribution index PDI=3.37 and the light transmittance of 87%.
Example 5
135G (1.5 mol) of dimethyl carbonate, 142g (0.5 mol) of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane and 0.05g of sodium methoxide in methanol (calcium carbonate concentration: 80. Mu.g/g) were added to a transesterification reactor, the transesterification reaction was carried out under the protection of N 2, the temperature was raised to 200℃and the pressure was normal pressure, the stirring rate was 100r/min, and the methanol produced by the reaction was discharged through a distillation apparatus, and after 3 hours of the transesterification reaction, a first product was obtained.
292G (2 mol) of isosorbide, 360g (4 mol) of dimethyl carbonate and 0.21g (trityl) of triphenylphosphine chloride are mixed uniformly by a mixer and added into the first product, and the mixture is subjected to transesterification under the protection of N 2 at the temperature of 200 ℃ and the pressure of normal pressure, the stirring speed of 200r/min, methanol generated by the reaction is discharged by a distillation device, and the transesterification is carried out for 3 hours, so that a second product is obtained.
After the transesterification reaction is finished, vacuumizing and decompressing until the system pressure is lower than 500Pa, gradually heating to 240 ℃, reacting for 120min, extruding a product from the bottom of a polymerization kettle after the reaction is finished, cooling and granulating, wherein the weight average molecular weight Mw of the obtained polymer is 45187, the molecular weight distribution index PDI is=2.56, and the light transmittance is 95%.
Example 6
174G (1 mol) of dibutyl carbonate, 142g (0.5 mol) of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane and 0.2g of zinc acetate in butanol (zinc acetate concentration: 80. Mu.g/g) were added into a transesterification reactor, and the transesterification reaction was carried out under the protection of N 2, the temperature was raised to 180℃and the pressure was normal, the stirring rate was 150r/min, butanol produced by the reaction was discharged through a distillation apparatus, and after 1 hour of the transesterification reaction, a first product was obtained.
146G (1 mol) of isosorbide, 261g (1.5 mol) of dibutyl carbonate and 0.05g (trityl) of triphenyl phosphorus chloride are added into the first product after being uniformly mixed by a mixer, the transesterification reaction is carried out under the protection of N 2, the temperature is increased to 200 ℃, the pressure is 0.9MPa, the stirring speed is 150r/min, butanol generated by the reaction is discharged through a distillation device, and the second product is obtained after the transesterification reaction for 1 h.
After the transesterification reaction is finished, vacuumizing and decompressing until the system pressure is lower than 500Pa, gradually heating to 240 ℃, reacting for 250min, extruding a product from the bottom of a polymerization kettle after the reaction is finished, cooling and granulating, wherein the weight average molecular weight Mw of the obtained polymer is 48204, the molecular weight distribution index PDI is=2.89, and the light transmittance is 92%.
Comparative example 1
135G (1.5 mol) of dimethyl carbonate, 142g (0.5 mol) of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 292g (2 mol) of isosorbide, 360g (4 mol) of dimethyl carbonate, 0.05g of methanol solution of sodium methoxide (calcium carbonate concentration is 80 mu g/g) and 0.21g (trityl) of triphenylphosphine chloride are mixed uniformly by a mixer and then added into a transesterification reactor, and the transesterification reaction is carried out under the protection of N 2, wherein the temperature is 200 ℃ and the pressure is normal pressure, the stirring rate is 200r/min, and the methanol generated by the reaction is discharged through a distillation device, so that the transesterification product is obtained after the transesterification reaction is carried out for 6 hours.
After the transesterification reaction is finished, vacuumizing and decompressing until the system pressure is lower than 500Pa, gradually heating to 240 ℃, reacting for 120min, extruding a product from the bottom of a polymerization kettle after the reaction is finished, cooling and granulating, wherein the weight average molecular weight Mw of the obtained polymer is 68187, the molecular weight distribution index PDI is=4.15, and the light transmittance is 82%.
Comparative example 2
174G (1 mol) of dibutyl carbonate, 142g (0.5 mol) of 2, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 146g (1 mol) of isosorbide, 261g (1.5 mol) of dibutyl carbonate, 0.2g of zinc acetate in butanol (zinc acetate concentration of 80 mu g/g) and 0.05g (trityl) of triphenylphosphine chloride are mixed uniformly by a mixer and then added into a transesterification reactor, the transesterification reaction is carried out under the protection of N 2, the temperature is raised to 200 ℃, the pressure is 0.9MPa, the stirring rate is 150r/min, butanol generated by the reaction is discharged by a distillation device, and the transesterification product is obtained after the transesterification reaction is carried out for 2 hours.
After the transesterification reaction is finished, vacuumizing and decompressing until the system pressure is lower than 300Pa, gradually heating to 240 ℃, reacting for 250min, extruding a product from the bottom of a polymerization kettle after the reaction is finished, cooling and granulating, wherein the weight average molecular weight Mw of the obtained polymer is 60983, the molecular weight distribution index PDI is=3.78, and the light transmittance is 85%.
Compared with example 5, the isosorbide type copolycarbonate product obtained in comparative example 1 has higher molecular weight, but obviously reduced light transmittance and obvious white turbidity phenomenon, and the adoption of the one-pot transesterification process leads to the existence of a large amount of embedded and homogenized copolymers in copolymerization products due to the problem of large difference of monomer boiling point and monomer reactivity ratio, so that two or more different homopolymers of the block copolymer are formed, and obvious phase separation phenomenon occurs in the copolymers, so that the light transmittance is obviously reduced. By the serial transesterification method, the uniformity of the transesterification product can be improved, the reactivity ratio difference can be reduced, and the monomer chain unit composition ratio in the copolymer can be regulated and controlled, so that the light transmittance of the copolymer can be improved, and the white turbidity phenomenon can be inhibited.
From the above technical solution, the technical solution provided by the present invention has the following advantages:
Firstly, the isosorbide type copolycarbonate is prepared by adopting a serial transesterification process, and in the first step of transesterification, a dihydroxyl compound serving as a third monomer and carbonic diester are subjected to transesterification reaction, and the effective regulation and control on the transesterification reaction degree and the composition of a transesterification product are realized by regulating and controlling a catalyst and process conditions. And adding isosorbide and carbonic diester into the transesterification product to perform a second transesterification reaction. The reactivity ratio in the polycondensation process is controlled by regulating and controlling the composition of the transesterification product, so that the uniformity of the copolymerization product is improved, and the problems of white turbidity and light transmittance reduction caused by the composition difference of the copolymerization product are effectively inhibited. The process is simple, the transesterification process can be normal pressure or micro negative pressure, the production cost is low, and the large-scale production is easy to realize.
Secondly, the invention adopts the carbonic acid diester monomers such as dimethyl carbonate, diphenyl carbonate and the like as raw materials, can reduce the reaction temperature, improve the hue of the isosorbide type carbonic acid ester product, does not need to carry out a pre-polycondensation process, and effectively solves the problem of yellowing of the hue of the product caused by high temperature and long time during polycondensation.
In summary, the invention provides a method for preparing isosorbide type copolycarbonate, which comprises the following steps: first transesterification, second transesterification, polycondensation, and post-treatment; in the first transesterification and/or the second transesterification step, the carbonic acid diester is selected from: any one or more of dimethyl carbonate, diphenyl carbonate, diethyl carbonate and dibutyl carbonate. The invention also provides application of the preparation method in preparation of bisphenol A type polycarbonate resin. In the invention, a serial transesterification process is adopted to regulate and control the composition of a transesterification product to control the reactivity ratio in the polycondensation process, thereby improving the uniformity of the product and further improving the light transmittance; meanwhile, the specific selection of the carbonic acid diester can reduce the temperature of the polycondensation reaction and prevent the yellowing of the product after the high temperature. The preparation method and the application of the isosorbide type copolycarbonate provided by the invention solve the technical defect of poor light transmittance of the isosorbide type copolycarbonate in the prior art.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description. Also, other implementations may be derived from the above-described embodiments, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method for preparing isosorbide type copolycarbonate, which is characterized by comprising the following steps:
Step one, first transesterification: mixing polyol, carbonic diester and a catalyst, and performing first transesterification to obtain a first product;
Step two, second transesterification: mixing the first product, the isosorbide and the catalyst, and performing a second transesterification to obtain a second product;
step three, polycondensation reaction: performing polycondensation reaction on the second product to obtain a third product;
Step four, post-treatment: extruding, cooling and granulating the third product to obtain an isosorbide type copolycarbonate product;
In step one and/or step two, the carbonic acid diester is selected from: any one or more of dimethyl carbonate, diphenyl carbonate, diethyl carbonate and dibutyl carbonate.
2. The method of claim 1, wherein in step one, the polyol is selected from the group consisting of: any one or more of tricyclodecanedimethanol, 1, 4-butanediol, diethylene glycol, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 1, 4-terephthalenedimethanol and 1, 4-cyclohexanedimethanol.
3. The method according to claim 1 or 2, wherein in the first step, the catalyst is an alkali metal salt solution having a concentration of 50 to 1000 μg/g.
4. A method of preparation according to claim 3, wherein in the alkali metal salt solution, the alkali metal salt is selected from the group consisting of: any one or more of calcium acetate, calcium carbonate, potassium carbonate, magnesium acetate, zinc acetate, sodium methoxide and zinc nitrate;
In the alkali metal salt solution, the solvent is selected from the group consisting of: any one or more of water, dimethyl carbonate, methanol, ethanol, butanol and ethylene glycol.
5. The preparation method according to claim 1, wherein in the second step, the mass ratio of the catalyst to the carbonic acid diester is 400-1000 μg/g;
And/or the number of the groups of groups,
The feeding mole ratio of the isosorbide in the second step to the polyol in the first step is 1 (0.5-5);
And/or the number of the groups of groups,
In the second step, the feeding mole ratio of the isosorbide to the carbonic acid diester is 1 (0.5-5).
6. The method according to claim 1 or 5, wherein in the second step, the catalyst is selected from the group consisting of: one or more of tetrapropylammonium hydroxide, di-n-propylamine, cinnamyl triphenyl phosphonium bromide, (trityl) triphenyl phosphonium chloride, cetyl trimethyl ammonium bromide, and trihexyltetradecyl quaternary phosphonium phenolate.
7. The preparation method according to claim 1, wherein in the first step, the temperature of the first transesterification is 160-210 ℃, the time of the first transesterification is 0.5-5 h, the pressure of the first transesterification is 0.09-0.1 MPa, and the stirring speed of the first transesterification is 50-200 r/min;
And/or the number of the groups of groups,
In the second step, the temperature of the second transesterification is 160-210 ℃, the time of the second transesterification is 0.5-5 h, the pressure of the second transesterification is 0.09-0.1 MPa, and the stirring rotating speed of the second transesterification is 50-200 r/min.
8. The method according to claim 1 or 7, wherein the temperature of the polycondensation reaction is 190 to 260 ℃, the vacuum degree of the polycondensation reaction is 0.03 to 1kPa, and the time of the polycondensation reaction is 0.5 to 5 hours.
9. The process according to any one of claims 1 to 8, wherein the first product has a weight average molecular weight Mw of 500 to 2000 and a PDI of 1.5 to 3;
And/or the number of the groups of groups,
The weight average molecular weight Mw of the second product is 500-2000, and the PDI of the second product is 1.5-3;
And/or the number of the groups of groups,
The isosorbide type copolycarbonate product has a weight average molecular weight Mw of 30000-60000 and a PDI of 1.5-3.
10. Use of a process comprising the process according to any one of claims 1 to 9 in the preparation of a bisphenol a type polycarbonate resin.
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