CN102120819B - Borneol diene/carbon monoxide (CO) polyketone resin and preparation method thereof - Google Patents
Borneol diene/carbon monoxide (CO) polyketone resin and preparation method thereof Download PDFInfo
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- CN102120819B CN102120819B CN201110027085.9A CN201110027085A CN102120819B CN 102120819 B CN102120819 B CN 102120819B CN 201110027085 A CN201110027085 A CN 201110027085A CN 102120819 B CN102120819 B CN 102120819B
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Abstract
The invention discloses a borneol diene/carbon monoxide (CO) polyketone resin and a preparation method thereof. In the borneol diene/ CO polyketone resin, the molecular formula is [C10H14.(CO)]n and D is equal to 2.09. The borneol diene/ CO polyketone resin is insoluble in benzene and methanol and is soluble in tetrahydrofuran. The preparation method comprises the following steps of: dissolving the borneol diene into the benzene; placing the solution into a high-pressure reaction kettle; adding palladium chloride; introducing CO gas under the pressure of 2.0 to 5.0 MPa; reacting at the temperature of between 40 and 70 DEG C for 2 to 12 hours; cooling to room temperature; emptying pressure; adding the methanol to precipitate polymer out; filtering; washing with the methanol; and performing vacuum drying at the temperature of 60 DEG C for 24 hours to obtain the borneol diene/ CO polyketone resin. The borneol diene/ CO polyketone resin has the characteristics of high melting point, high glass transition temperature, excellent mechanical performance, high wear resistance, capacity of performing surface modification and molecular structure modification and the like, and can meet the application in the fields of preparation of high-performance thermoplastic plastic, super engineering plastic, degradable plastic, high-temperature-resistant plastic and the like. Raw materials for the preparation have wide sources and are readily available; and the preparation method is simple, easy to operate and high in yield and has a small number of steps.
Description
Technical field
The present invention relates to a kind of polyketone macromolecule organic and preparation method thereof, be specifically related to a kind of borneol diene/CO polyketone resin and preparation method thereof.
Background technology
Due to the shortage of world resource and the deterioration of environmental aspect, make C
1the research of chemistry more and more becomes the focus that people pay close attention to.CO is the byproduct of Coal Chemical Industry and petrochemical complex, and its source is abundant, and cheap and easy to get.It is not only the platform organic compound of the Chemicals such as synthesizing methanol, ethanol, but also can be used as the compound generation copolyreaction such as comonomer and alkene, cycloolefin, formaldehyde and amine, prepares the multiple macromolecular materials such as polymeric amide, polyester and polyketone.Polyolefine is the important functional high molecule material of a class, and its functionalization research of studying Showed Very Brisk, especially polyolefine material attracts people's attention.Abundant and cheap and easy to get CO and olefin-copolymerization are a kind of effective ways of preparing Functional Polyolefine material.CO and one or more double bond containing unsaturated monomers carry out alternating copolymerization can prepare polyketone polymer (Polyketone is called for short PK) material.Polyketone macromolecular material not only has that fusing point is high, mechanical property is good, wear resistance, chemical proofing, barrier and the good physicochemical property such as gas permeability is low, and the carbonyl chromophore of main chain given the light degradation property of polyketone polymer uniqueness, can be in physical environment slowly and degradable be ketone, alkene class and CO
2deng small molecules.In polymkeric substance, carbonyl has very active functional group's character, can obtain tens kinds of functional high molecule materials such as polyalcohols, polythiol, polymeric amide, poly-oxime, polynitriles, poly-bis-phenol, poly-ammonia by the modifications such as hydrogenation, mercaptan, ammonification and chemically modified.Its premium properties is just attracting domestic and international scientific circles and industry member researchist's extensive concern, and its synthetic method, structure sexual intercourse and industrial application have become the focus of basis and applied basic research.Researching and developing high performance polyketone macromolecular material is of great practical significance and vast potential for future development.
From nineteen forty-one, first report CO and olefin-copolymerization is prepared after random copolymers, the high molecular research of polyketone, exploitation just constantly make progress with application.Du Pont company report is used superoxide to cause copolymerization, and Brubaker etc. has studied the free-radical polymerized of CO and ethene and other alkene in great detail subsequently.Japan Takizawa company and U.S. Brookhaven laboratory are 130 ℃ in temperature of reaction, under pressure 20.3 MPa, use
60co has successfully caused copolymerization, but due to above two kinds of method severe reaction conditions, and reaction product is without rock steady structure, and above-mentioned research is without substantial progress.Nineteen fifty-one, Reppe and Magin K
2[Ni (CN)
4] as catalyzer, make ethene and CO polymerization.Subsequently, Iashzta Rh
4(CO)
12in acetic acid and methyl alcohol, catalyzed ethylene reacts with CO and has to low-molecular-weight polymeric product.
20 century 70s, the research of palladium catalyst obtains good achievement, have many reports to adopt transition metal complex catalysis CO and olefin-copolymerization, but its part only limits to unidentate ligand.20th century, the mid-80 take scientist that the Drent of SHELL chemical company is representative with palladium phosphine coordination compound catalysis CO and ethylene copolymer in the presence of strong acid, made the high molecular Remarkable Progress On Electric Artificial progress of polyketone.So far, accelerated the industrialization step of polyketone Polymeric Industry.
Within 1996, Shell chemical company commercially produces hemicrystalline engineering thermoplasties---Carilon in the factory of Britain Carington, in the U.S., Geismar Louisiana has set up Carilon factory, the throughput that industrial scale in 1999 reaches 25 kt/a ，Qie Gai factories can be expanded to 50 kt/a; At the beginning of 1999, the Montell of the subsidiary/member companies polyolefins company of Shell chemical company is built up vapour phase polymerization pilot plant in Italy, and vapor phase process can be produced continuously, and do not need solvent recuperation and drying process, compare with slurry process, its operation is simpler, and production cost may be lower.
The POK fiber of current Dutch Acordis company Development and Production, carbonyl and ethylidene on molecular chain (or phenylene etc.) regularly arranged, its gel spinning technology is ripe, but production cost is higher.Polyketone is high molecular synthetic owing to must using precious metal palladium as Primary Catalysts, production cost is expensive, industrial applications and popularization have been restricted, greatly postponed its process of industrialization, but various countries large-size chemical company is all also trying to explore the breakthrough of low-cost synthetic technology, the present domestic high molecular manufacturing enterprise of polyketone that there is no.Current research mainly concentrates on finds novel catalyst to reducing production costs, and is beneficial to promote polyketone Polymeric Industry process.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of the invention is, adopting borneol diene and CO is raw material, prepare a kind of borneol diene/CO polyketone resin, this resin has the novel high-performance polyketone macromolecular material that fusing point is high, second-order transition temperature is high, mechanical property is good, wear resistance is good, degradable, can also carry out as required the characteristics such as finishing and molecular structure modification.Another object of the present invention is to provide the preparation method of above-mentioned borneol diene/CO polyketone resin.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is:
/ CO polyketone resin, molecular formula is [C
10h
14﹒ (CO)] n; Structural formula is:
；
A kind of method of preparing above-mentioned borneol diene/CO polyketone resin: weigh 0.01mol borneol diene and be dissolved in 10ml benzene, put into the autoclave with stirring velocity control and auto temperature controlled system, add 0.003mol Palladous chloride, pass into the high-purity CO gas of 2.0 ~ 5.0MPa, at 40 ~ 70 ℃, react 2 ~ 12h, after finishing, reaction is cooled to room temperature, the unreacted CO of emptying, add appropriate methanol extraction to go out polymkeric substance, after filtering by methanol wash 3 times, vacuum-drying 24h at 60 ℃, obtain faint yellow transparent solid, obtain product, yield is 91%, and sampling detects and characterizes.
In reaction conditions, the preferred 4.0MPa of pressure; Preferably 60 ℃ of temperature; Preferred 10h of time.
The reaction formula of aforesaid method is:
Above-mentioned borneol diene/CO polyketone resin, application that can be in preparing high-performance thermoplastics, Super Engineering plastics, photodegradable plastics and high-temperature resistance plastice.
Beneficial effect: borneol diene/CO polyketone resin of the present invention, for faint yellow transparent solid, be a kind ofly there is good thermal stability, second-order transition temperature is high, mechanical property is good, wear resistance is good, degradable, can also carry out as required the high performance polyketone macromolecular material of the characteristics such as finishing and molecular structure modification.The raw materials of borneol diene/CO polyketone resin is borneol diene and CO, α-the firpene of borneol diene in turps is synthetic, turps source is wide, easily obtain, preparation method is simple, easily operation, borneol diene/CO polyketone resin of preparing can meet multi-field application such as preparing high-performance thermoplastics, Super Engineering plastics, high-temperature resistance plastice and photodegradable plastics.
Accompanying drawing explanation
Fig. 1 adopts AVA TAR360 type Fourier transform infrared spectrometer, and the IR of the borneol diene obtaining by liquid film method and borneol diene/CO polyketone resin schemes, and contrasts their spectrogram, and borneol diene/CO polyketone resin is 1740cm at wavelength
-1having strong an absorption, is the stretching vibration absorption peak of carbonyl.
Fig. 2 is product thermogravimetric analysis (TG) figure that adopts TG/DSC/DTA simultaneous thermal analysis instrument to obtain, and from TG curve, in the time of 379 ℃, product starts weightlessness, and fusing point is higher, has good thermostability; Tg=171 ℃ of borneol diene/CO polyketone resin, second-order transition temperature is high.
Embodiment
The medicine that the present embodiment is used and requirement are as follows:
Borneol diene: laboratory self-control, concrete preparation method is shown in CN101870635A or the inventor disclosed journal of writings before, GC purity is more than 98%; CO:99.99%, Ning Yan chemical plant, Nanjing produces; PdCl
2: analytical pure, Aladdin reagent company produces; Benzene and methyl alcohol: analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group produces, standby after distillation dewaters; Other pharmaceutical chemicals using is conventional product.
A kind of method of preparing borneol diene/CO polyketone resin: weigh 0.01mol borneol diene and be dissolved in 10ml benzene, put into the autoclave with stirring velocity control and auto temperature controlled system, add 0.003mol Palladous chloride, pass into the high-purity CO gas of 4.0MPa, at 60 ℃, react 10h, after finishing, reaction is cooled to room temperature, the unreacted CO of emptying, add appropriate methanol extraction to go out polymkeric substance, after filtering, by methanol wash 3 times, vacuum-drying 24h at 60 ℃, obtains faint yellow transparent solid, after calculating, yield is about 91%, and sampling detects and characterizes.
The calculation formula of yield is:
This preparation method's reaction formula is:
Characterization result is as follows: second-order transition temperature and thermogravimetric analysis adopt TG/DSC/DTA simultaneous thermal analysis instrument to analyze, and Tg=171 ℃, do not exist crystallizing field, and borneol diene/CO polyketone resin starts weightless at 379 ℃, good thermal stability; Uv-absorbing adopts the purple ultraviolet of UV-365 type/visible spectrophotometer to measure, and the uv-absorbing wavelength of borneol diene/CO polyketone resin is 290nm; Infrared absorption is used AVA TAR360 type Fourier transform infrared spectrometer to measure, and adopts liquid film method to obtain the IR figure of borneol diene and borneol diene/CO polyketone resin, and as shown in Figure 1, borneol diene/CO polyketone resin is 1740cm at wavelength
-1there is strong an absorption at place, is the stretching vibration absorption peak of carbonyl; Adopt Agilent 1100 type gel chromatographs to carry out molecular weight determination, column temperature is 25 ℃, THF(HPLC) makes solvent, flow velocity 1ml/min, HPLC pump is Waters 515, detector is Wyatt Optilab rEX, chromatographic column is three HR3, HR4 and HR5 Styragel Coupled columns, PS
make standard specimen, record molecular weight and be
,
, D=2.1; Ultimate analysis is used Elementar Vario EL III to detect, Anal. Found:C, 80.78%; H, 8.82%; O, 10.4%; Calcd. C
10h
14(CO)
1: C, 81.48%; H, 8.64%; O, 9.87%, infer that thus the structural formula of borneol diene/CO polyketone resin is:
Dissolubility test result is: be insoluble to methyl alcohol and benzene, be soluble in tetrahydrofuran (THF).
Borneol diene/CO polyketone resin of the present invention is a kind of new functional macromolecule material, has that fusing point is high, mechanical property is good, wear resistance, chemical proofing, barrier, degradable property and a good physical properties such as gas permeability is low.The raw material CO of borneol diene/CO polyketone resin Polymer Synthesizing is cheap and easy to get, the carbonyl containing and unsaturated double-bond further chemically modified and modification for developing the functional high molecule material of other types, borneol diene/CO polyketone resin polymer photodegradation that also other conventional macromolecular materials of tool do not possess has good application in preparing high-performance thermoplastics, Super Engineering plastics and high-temperature resistance plastice.
Method is with embodiment 1, and wherein, the reaction times is respectively 2h, 4h, 6h, 8h and 12h, and as calculated, the yield of product borneol diene/CO polyketone resin is respectively: 57%, 70%, 71%, 75% and 90%.Result shows, within the scope of 10h, borneol diene/CO polyketone resin yield is along with the lengthening of time shows a rising trend, surpass 10h after yield substantially remain unchanged.
Embodiment 3
Method is with embodiment 1, and wherein, temperature of reaction is respectively 40 ℃, 50 ℃ and 70 ℃, and as calculated, the yield of product borneol diene/CO polyketone resin is respectively 48%, 71% and 76%.Result shows, borneol diene/CO polyketone resin yield is along with the rising of temperature shows a rising trend, but after arriving 60 ℃, yield no longer increase, and in the time of 70 ℃, decline on the contrary.
Embodiment 4
Method is with embodiment 1, and wherein, reaction pressure is respectively 2.0MPa, 3.0MPa and 5.0MPa, and as calculated, the yield of product borneol diene/CO polyketone resin is respectively 80%, 84% and 90%.Result shows, borneol diene/CO polyketone resin yield is along with the rising of temperature is slow rising tendency, and after pressure reaches 4.0MPa, yield remains unchanged substantially.
Claims (1)
1. a method of preparing borneol diene/CO polyketone resin, it is characterized in that: weigh 0.01mol borneol diene and be dissolved in 10ml benzene, put into the autoclave with stirring velocity control and auto temperature controlled system, add 0.003mol Palladous chloride, pass into the high-purity CO gas of 4.0MPa, at 60 ℃, react 10h, after finishing, reaction is cooled to room temperature, the unreacted CO of emptying, adds appropriate methanol extraction to go out polymkeric substance, after filtering, uses methanol wash 3 times, vacuum-drying 24h at 60 ℃, obtain faint yellow transparent solid, after calculating, yield is 91%, and sampling detects and sign;
The calculation formula of yield is:
This preparation method's reaction formula is:
Characterization result is as follows: second-order transition temperature and thermogravimetric analysis adopt TG/DSC/DTA simultaneous thermal analysis instrument to analyze, Tg=171 ℃, and without crystallizing field, borneol diene/CO polyketone resin starts weightless at 379 ℃, good thermal stability; Uv-absorbing adopts UV-365 type ultraviolet/visible spectrophotometer to measure, and the uv-absorbing wavelength of borneol diene/CO polyketone resin is 290nm; Infrared absorption is used AVA TAR360 type Fourier transform infrared spectrometer to measure, and adopts liquid film method to obtain the IR figure of borneol diene and borneol diene/CO polyketone resin, and borneol diene/CO polyketone resin is 1740cm at wavelength
-1there is strong an absorption at place, is the stretching vibration absorption peak of carbonyl; Adopt Agilent1100 type gel chromatograph to carry out molecular weight determination, column temperature is 25 ℃, THF makes solvent, flow velocity 1ml/min, HPLC pump is Waters515, detector is Wyatt Optilab rEX, chromatographic column is three HR3, HR4 and HR5Styragel Coupled columns, PS makes standard specimen, records molecular weight to be
d=2.1; Ultimate analysis is used Elementar Vario EL III to detect, Anal.Found:C, 80.78%; H, 8.82%; O, 10.4%; Calcd.C
10h
14(CO)
1: C, 81.48%; H, 8.64%; O, 9.87%, infer that thus the structural formula of borneol diene/CO polyketone resin is:
Dissolubility test result is: be insoluble to methyl alcohol and benzene, be soluble in tetrahydrofuran (THF).
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