CN1786045A - Poly methyl ethylene cyclo hexamethylene carbonate material and its preparation method - Google Patents
Poly methyl ethylene cyclo hexamethylene carbonate material and its preparation method Download PDFInfo
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- CN1786045A CN1786045A CN 200510101885 CN200510101885A CN1786045A CN 1786045 A CN1786045 A CN 1786045A CN 200510101885 CN200510101885 CN 200510101885 CN 200510101885 A CN200510101885 A CN 200510101885A CN 1786045 A CN1786045 A CN 1786045A
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- cyclo
- poly methyl
- catalyzer
- methyl ethylene
- hexamethylene carbonate
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- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 title claims description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 229920006027 ternary co-polymer Polymers 0.000 abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 125000004956 cyclohexylene group Chemical group 0.000 abstract 1
- 229920006238 degradable plastic Polymers 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 229920001897 terpolymer Polymers 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229960001701 chloroform Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention belongs to the field of high-molecular material, in particular, it relates to a polymethylethylene-cyclohexylene carbonic ester material and its preparation method. Said invention adopts carbon dioxide, epoxy propane and epoxy cyclohexane, under the action of high-effective catalyst load zinc binary carboxylate to synthesize degradable plastic polymethylethylene-cyclohexylene carbonic ester. The epoxy cyclohexane has rigid lexatomic ring, can be used as third monomer and added into copolymerization reaction of epoxy propane and carbon dioxide. Said invention utilizes the regulation of epoxy cyclohexane content in the reaction so as to obtain the ternary copolymer on whose main chain the different cyclohexylene contents can be contained. Said ternary copolymer has high mechanical strength and thermal property.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of poly methyl ethylene cyclo hexamethylene carbonate material and preparation method thereof.
Background technology
Carbonic acid gas is the main gas that causes Global warming of generally acknowledging, carbonic acid gas has caused about 66% Greenhouse effect according to estimates.Since 20th century, along with the progress of science and technology, people's standard of living improves constantly, and white pollution that industrial development brings and Greenhouse effect also make mankind itself's living environment constantly worsen.Atmospheric Carbon Dioxide is become the degradable polymer plastics with synthesis of epoxy compounds, can effectively alleviate problems such as serious day by day Greenhouse effect and white pollution.Carbonic acid gas is the high-quality carbon source that a kind of cheapness should get, but because how the inertia of itself efficiently utilizes carbonic acid gas attracting various countries scientist's concern.This laboratory success utilize efficient catalyst by carbonic acid gas and propylene oxide production lined polymethyl ethylene carbonate.Lined polymethyl ethylene carbonate is a kind of degradable high polymer material with applications well prospect, and cost and common plastics are approaching.Low-molecular-weight lined polymethyl ethylene carbonate as barrier material [WO 9 925 751,1999, WO 9 925 751,1999], whipping agent [JP 08 031 700,1996], tamanori [WO 9 606 877,1996; US 5 744907,1998] research patent is appeared in the newspapers.The patent of matrix materials such as high-molecular weight lined polymethyl ethylene carbonate/natural fiber or mineral filler appear in the newspapers [CN 1422899A, 2003; CN 1422898A, 2003].But the mechanical property of copolymer lined polymethyl ethylene carbonate is relative with thermal characteristics relatively poor, and its range of application is restricted.
Summary of the invention
The objective of the invention is to overcome the relative relatively poor problem with thermal characteristics of mechanical property of existing copolymer lined polymethyl ethylene carbonate, a kind of poly methyl ethylene cyclo hexamethylene carbonate terpolymer material is provided, its mechanical property and thermal characteristics are improved greatly.
Another object of the present invention provides above-mentioned poly methyl ethylene cyclo hexamethylene carbonate terpolymer preparation methods.
To achieve these goals, the present invention adopts following technical scheme:
A kind of poly methyl ethylene cyclo hexamethylene carbonate material, its chemical structure are as (I) formula:
The preparation method of this poly methyl ethylene cyclo hexamethylene carbonate material is: putting into catalyzer, is reactant with propylene oxide and epoxy cyclohexane, and the feeding carbonic acid gas fully reacts and can synthesize poly methyl ethylene cyclo hexamethylene carbonate.
Be specially: catalyzer is added in the autoclave, whole reaction system is connected with vacuum system, the autoclave that will put into catalyzer then is 80 ℃ of following vacuum-dryings; Behind dry the end, cooling is injected a certain proportion of propylene oxide and epoxy cyclohexane in autoclave, and feeds carbonic acid gas, and heating starts and stirs, and regulates pressure carbon dioxide, and reaction system is reacted under setting pressure and design temperature; After reaction finishes, release of carbon dioxide, and with heavy-gravity mixture taking-up in the still; This mixture is dissolved in the chloroform, removes catalyzer in the system, and clean with distilled water with 5% dilute hydrochloric acid solution; With the chloroformic solution of gained co-polymer, precipitate with ethanol then, the white precipitate product of gained is a poly methyl ethylene cyclo hexamethylene carbonate.
The molar ratio of above-mentioned epoxy cyclohexane and propylene oxide is 0.01～0.10; Catalyzer is the load binary zine carboxylate; Temperature of reaction is at 60 ℃, and setting pressure is 5.2MPa, and the reaction times is 40 hours, can make the transformation efficiency of polyreaction and yield reach optimum.Can certainly add more the 3rd monomer epoxy cyclohexane, still the increase of the mechanical property of the polymkeric substance that obtains and thermal characteristics is not obvious, and the affiliation that adds of more epoxy cyclohexane increases the cost of polymkeric substance.The factor that material property is had the greatest impact is the molar ratio of propylene oxide and epoxy cyclohexane, and other factor is little to the performance impact of material.
Compared with prior art, the present invention has following beneficial effect:
Multiple aggregation is one of a polymer modification very important techniques, is one of important means that improves its performance.Through adding the 3rd monomer modified polymkeric substance its performance is significantly improved, can improve its mechanical property and thermal characteristics, thereby for the widespread use of carbon dioxide plastic provides the foundation, for the industrial applications of degradable carbon dioxide plastic has been opened up new approach.Epoxy cyclohexane has the inflexible six-ring, joins as the 3rd monomer in the copolymerization of propylene oxide and carbonic acid gas, by regulating the terpolymer that the content of epoxy cyclohexane in reaction obtains different thermal characteristicss and mechanical property.The present invention adopts propylene oxide and the epoxy cyclohexane and the carbonic acid gas of technical pure level, a kind of methyl ethylene carbonate is carried out multicomponent copolymerized and modified, and technology is simple, and raw materials cost is cheap.The gained terpolymer has physical strength and the modulus that is significantly higher than former binary polymer, and second-order transition temperature significantly raises.For the industrial applications of carbon dioxide plastic has been opened up new approach.
Embodiment
The adding of 1g load binary zine carboxylate catalyst is furnished with in the 0.5L autoclave of agitator, whole reaction system is connected with vacuum system, will put into 80 ℃ of following vacuum-drying 24h of autoclave of load weighted catalyzer in advance then.Behind dry the end, drop to room temperature, inject a certain proportion of propylene oxide and epoxy cyclohexane in autoclave, and feed carbonic acid gas, heating starts and stirs, and adjustings pressure carbon dioxide is 5.2Mpa, and reaction system was reacted 40 hours down 5.2Mpa and 60 ℃.After reaction finishes, release of carbon dioxide, and with heavy-gravity mixture taking-up in the still.This mixture is dissolved in the chloroform, removes catalyzer in the system, and give a baby a bath on the third day after its birth time with distilled water with 5% dilute hydrochloric acid solution.After then the chloroformic solution of the co-polymer of gained being adjusted to finite concentration, precipitate with ethanol, the white precipitate product of gained is terpolymer lined polymethyl ethylene-cyclohexalene carbonic ether (PPCHC).Treat to put into vacuum drying oven 80 ℃ of following bakings more than 48 hours after the trichloromethane volatilization in the white precipitate product to weight.Then polymkeric substance is put into vulcanizing press and pressed down the 5min straight forming at 160 ℃.The standard batten that the terpolymer of gained moulding is cut into 25mm * 1mm * 4mm carries out performance test.
According to above-mentioned preparation method, adjust the ratio of epoxy cyclohexane and propylene oxide, carry out the preparation of terpolymer poly methyl ethylene cyclo hexamethylene carbonate, shown in embodiment 1～6.The consumption molar percentage and the performance of epoxy cyclohexane and propylene oxide are as shown in table 1.
The relation of the performance of table 1, terpolymer poly methyl ethylene cyclo hexamethylene carbonate material and epoxy cyclohexane consumption
| The molar ratio of epoxy cyclohexane and propylene oxide | Second-order transition temperature Tg ℃ | Tensile strength, MPa | Young's modulus, MPa | Pyrolysis temperature TG -5％℃ | |
| Copolymer PPC | / | 38.24 | 33.09 | / | 233.00 |
| Embodiment 1 | 0.010 | 45.56 | 36.78 | 670.7 | 250.77 |
| Embodiment 2 | 0.025 | 46.86 | 38.22 | 721.1 | 250.86 |
| Embodiment 3 | 0.042 | 49.78 | 41.89 | 715.1 | 267.43 |
| Embodiment 4 | 0.057 | 50.31 | 40.67 | 703.4 | 258.72 |
| Embodiment 5 | 0.067 | 53.26 | 43.25 | 767.0 | 259.36 |
| Embodiment 6 | 0.091 | 50.27 | 49.61 | 820.3 | 257.58 |
As seen, gained terpolymer poly methyl ethylene cyclo hexamethylene carbonate material has physical strength and the modulus that is significantly higher than former binary polymer, and second-order transition temperature significantly raises.
Claims (6)
1, a kind of poly methyl ethylene cyclo hexamethylene carbonate material, its chemical structure are as (I) formula:
2, the preparation method of the described poly methyl ethylene cyclo hexamethylene carbonate material of a kind of claim 1, as follows: as to put into catalyzer, with propylene oxide and epoxy cyclohexane is reactant, and the feeding carbonic acid gas fully reacts and can synthesize poly methyl ethylene cyclo hexamethylene carbonate.
3, preparation method according to claim 2 is characterized in that described preparation method is: catalyzer is added in the autoclave, whole reaction system is connected with vacuum system, the autoclave that will put into catalyzer then is 80 ℃ of following vacuum-dryings; Behind dry the end, cooling, injection ring Ethylene Oxide and epoxy cyclohexane are in autoclave, and the feeding carbonic acid gas, and heating starts and stirs, and regulates pressure carbon dioxide, and reaction system is reacted under setting pressure and design temperature; After reaction finishes, release of carbon dioxide, and with heavy-gravity mixture taking-up in the still; This mixture is dissolved in the chloroform, removes catalyzer in the system, and clean with distilled water with 5% dilute hydrochloric acid solution; With the chloroformic solution of gained co-polymer, precipitate with ethanol then, the white precipitate product of gained is a poly methyl ethylene cyclo hexamethylene carbonate.
4, according to claim 2 or 3 described preparation methods, the mol ratio that it is characterized in that described epoxy cyclohexane and propylene oxide is 0.01～0.10.
5,, it is characterized in that reaction conditions is: 60 ℃ of temperature, reaction pressure 5.2MPa according to claim 2 or 3 described preparation methods.
6,, it is characterized in that described catalyzer is the load binary zine carboxylate according to claim 2 or 3 described preparation methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510101885 CN1786045A (en) | 2005-11-30 | 2005-11-30 | Poly methyl ethylene cyclo hexamethylene carbonate material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510101885 CN1786045A (en) | 2005-11-30 | 2005-11-30 | Poly methyl ethylene cyclo hexamethylene carbonate material and its preparation method |
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| Publication Number | Publication Date |
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| CN1786045A true CN1786045A (en) | 2006-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200510101885 Pending CN1786045A (en) | 2005-11-30 | 2005-11-30 | Poly methyl ethylene cyclo hexamethylene carbonate material and its preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482483A (en) * | 2009-06-18 | 2012-05-30 | Sk新技术 | Polymeric thermoplastic compositions having excellent resistance to moisture and oxygen transmission and sheet which are made of these polymeric thermoplastic compositions |
| CN103154370A (en) * | 2010-09-01 | 2013-06-12 | Sk新技术株式会社 | Composition for paper coating |
| CN103842464A (en) * | 2011-08-18 | 2014-06-04 | Sk新技术株式会社 | Hot melt composition |
| CN103881078A (en) * | 2014-04-17 | 2014-06-25 | 中国科学院长春应用化学研究所 | Chlorinated polypropylene (propylene carbonate) and preparation method thereof |
| US9598603B2 (en) | 2011-11-23 | 2017-03-21 | Sk Innovation Co., Ltd. | Resin composition for high barrier paper-coating |
| CN112745496A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for improving thermal stability of polycarbonate |
| CN116102724A (en) * | 2023-02-25 | 2023-05-12 | 中化泉州石化有限公司 | Carbon dioxide-based terpolymer and preparation method thereof |
-
2005
- 2005-11-30 CN CN 200510101885 patent/CN1786045A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482483A (en) * | 2009-06-18 | 2012-05-30 | Sk新技术 | Polymeric thermoplastic compositions having excellent resistance to moisture and oxygen transmission and sheet which are made of these polymeric thermoplastic compositions |
| CN103154370A (en) * | 2010-09-01 | 2013-06-12 | Sk新技术株式会社 | Composition for paper coating |
| CN103154370B (en) * | 2010-09-01 | 2015-09-02 | Sk新技术株式会社 | For the composition of paper coating |
| CN103842464A (en) * | 2011-08-18 | 2014-06-04 | Sk新技术株式会社 | Hot melt composition |
| US9598603B2 (en) | 2011-11-23 | 2017-03-21 | Sk Innovation Co., Ltd. | Resin composition for high barrier paper-coating |
| CN103881078A (en) * | 2014-04-17 | 2014-06-25 | 中国科学院长春应用化学研究所 | Chlorinated polypropylene (propylene carbonate) and preparation method thereof |
| CN103881078B (en) * | 2014-04-17 | 2016-02-03 | 中国科学院长春应用化学研究所 | Chlorination polypropylene carbonate and preparation method thereof |
| CN112745496A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for improving thermal stability of polycarbonate |
| CN112745496B (en) * | 2019-10-30 | 2023-05-16 | 中国石油化工股份有限公司 | Method for improving thermal stability of polycarbonate |
| CN116102724A (en) * | 2023-02-25 | 2023-05-12 | 中化泉州石化有限公司 | Carbon dioxide-based terpolymer and preparation method thereof |
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