CN100516111C - Method of synthesizing poly p-dioxycyclohexanone and reaction apparatus thereof - Google Patents
Method of synthesizing poly p-dioxycyclohexanone and reaction apparatus thereof Download PDFInfo
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- CN100516111C CN100516111C CNB2007100484103A CN200710048410A CN100516111C CN 100516111 C CN100516111 C CN 100516111C CN B2007100484103 A CNB2007100484103 A CN B2007100484103A CN 200710048410 A CN200710048410 A CN 200710048410A CN 100516111 C CN100516111 C CN 100516111C
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Abstract
The invention discloses a method to synthesize poly-p-dioxide nadone, which comprises the following steps: allocating poly-p-dioxide nadone and tape water agent with volumetric ratio at 1 : 3-5 in reacting device with dehydrator; azeotropic refluxing 0.5-3 h; protecting with inert gas; stirring; dipping activator with mole ratio at 1 : 550-5000 against poly-p-dioxide at the same time; reacting under 60-100 deg.c at 0.5-48 h; getting depositing product; taking-up depositing product; drying; getting the final product. This invention also discloses a device fit for this method. The invention possesses short de-watering cycle and stable property, which can acquire small block, particulate or powdered poly-p-dioxide.
Description
Technical field
The invention belongs to the preparation method and the device technique field of PPDO, be specifically related to a kind of mode of dewatering needed anhydrous and oxygen-free effect when reaching to the polymerization of dioxy pimelinketone by simple possible, and the synthetic method and the reaction unit thereof of the final form of may command institute synthetic PPDO.
Background technology
Along with the enhancing of people's environmental consciousness, reduce white pollution, research and development and use biodegradable polymeric have become a kind of common recognition.Aliphatic polyester because it has favorable mechanical performance and higher use temperature, has obtained domestic and international investigator's favor as a kind of biodegradable polyester, in medical material and all development to some extent of general purpose material field.
A kind of as in the aliphatic polyester of PPDO except having above-mentioned advantage, owing to contain unique ehter bond in its molecular chain, also gives its good kindliness, enlarged its use range.At present, the high-molecular weight PPDO successfully applies to the medical material field, as suture line, screw, mosquito forceps and orthopaedics immobilization material etc.But the synthetic method to the dioxy pimelinketone that generally adopts is ring-opening polymerization at present, and this method reaction conditions is very harsh, and is very high to the requirement of water and oxygen.
At present for the ring-opening polymerization to the dioxy pimelinketone, be essentially anhydrous and oxygen-free in order to make its polymerization atmosphere, what generally adopt is that dewater the again mode of distill repeatedly of hydrolith is carried out (Macromol.Chem.Phys.1998,199,1089-1097; Macromolecules 2000,33,6982-6986; Macromol.Rapid Commun.2000,21,1063-1071).Obviously, this mode cycle that dewaters is longer, and cost is higher, and environment has very strong dependency to external world, and the humidity size of surrounding environment and changes of seasons etc. are all having a strong impact on the effect that dewaters, and finally influence the performance of PPDO synthetic product.What in addition, traditional synthetic method adopted always is the mass polymerization mode.Because in mass polymerization, carrying out along with reaction, product viscosity can constantly increase, cause stirring very difficult, finish finally only can obtain blocky polymerisate down to reaction, this produces not only for further expansion and has brought very big difficulty, its suitability for industrialized production also so is always failed accomplished, and, make that the cost of PPDO is high because of the harshness of synthesis condition and the difficulty of big block product postprocessing, limited its application aspect general purpose material.
Summary of the invention
Primary and foremost purpose of the present invention is the defective that exists at the conventional polymeric mode, a kind of synthetic method of fairly simple feasible PPDO newly is provided, this method can be controlled the final form of product, thereby provides condition for PPDO further enlarges production.
Still a further object of the present invention provides a kind of reaction unit that is applicable to above-mentioned PPDO synthetic method.
For reaching the synthetic method of the PPDO that primary and foremost purpose of the present invention provides; this method is will be that 1: 3～5 proportioning azeotropic in the reaction unit of special band water eliminator refluxed 0.5～3 hour by volume to dioxy pimelinketone and band aqua earlier; then under the protection of rare gas element; drip while stirring and the catalyzer that to dioxy pimelinketone mol ratio is 1: 550～5000; and can obtain precipitated product in 0.5～48 hour in 60～100 ℃ of reactions, promptly get final polymerisate after taking out the precipitated product drying.
Wherein the used band aqua of this method is a normal hexane, hexanaphthene, tetracol phenixin, benzene, toluene, dimethylbenzene, any in the methyl-phenoxide.
Used catalyzer is aluminum alkyls, alkoxy compound or stannous octoate in this method.Aluminum alkyls specifically can be any in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three hexyl aluminium, the aluminium diethyl monochloride, preferred trimethylammonium or triethyl aluminum; Alkoxy compound specifically can be any in aluminum isopropylate, lanthanum isopropoxide, tetrabutyl titanate, isopropyl titanate, germanic acid four butyl esters, preferred aluminum isopropylate or lanthanum isopropoxide.
For reaching a kind of reaction unit that is applicable to above-mentioned PPDO synthetic method that still a further object of the present invention provides, this device is made up of reaction vessel, water eliminator, water cooler, moisture eliminator, and water eliminator, water cooler, moisture eliminator are installed in the reaction vessel top successively.Reaction vessel is existing popular response container, as three-necked bottle commonly used in the testing laboratory, single neck bottle of being with inflation inlet, reactor etc.The water eliminator stage casing is the open cylinder in a top, the bottom surface has an aperture, molecular sieve is housed in the cylinder, cylinder bottom surface below have one with the gas-liquid thrust-augmenting nozzle of reaction vessel Link Port internal diameter coupling, cylinder top extend to form one with the Link Port of water cooler coupling end external diameter coupling, also have a parallel gas flow side pipe in cylinder one side, these side pipe two ends communicate with gas-liquid thrust-augmenting nozzle and cylinder top respectively.Water cooler is existing conventional condenser, as serpentine condenser.Moisture eliminator is a bend pipe, and wherein end coupling is inserted on the water cooler, and soft rubber ball with holes is laid in the other end end, places siccative in the pipe.
Wherein the aperture of used molecular sieve is in this device water eliminator
During use, after will adding reaction vessel by proportioning to dioxy pimelinketone and band aqua, heat temperature raising, when reaction vessel is heated when reaching band aqua boiling point, moisture contained in the air to dioxy pimelinketone and reaction vessel just evaporates with the band aqua, gas rises and along the air-flow side pipe of water eliminator one side from the gas-liquid thrust-augmenting nozzle, water eliminator cylinder top enters in the water cooler, drip back in the water eliminator after the condensation, the molecular sieve that moisture is equipped with in the cylinder absorbs, the aperture that the band aqua then has from the cylinder bottom surface drips back the reaction vessel and recycles, thereby realizes monomeric removal process.
Synthetic method provided by the invention and reaction unit have the following advantages:
1, because the present invention adopts the azeotropic backflow to prepare PPDO except that water law, thereby not only can make system moisture and oxygen divide content to be reduced to the polymerization requirement quickly and easily, greatly shorten and dewater the cycle, and can avoid being subjected to external environment humidity size and changes of seasons etc. to influence, guarantee the repeatability of obtained product viscosity and stablizing of end article performance.
2, owing to contain the band aqua in the reaction system of the present invention, thereby not only can avoid increasing too fast can't the stirring because of viscosity in the bulk polymerisation process of prior art, cause final product can only be big blocky shortcoming, but also can be little bulk, particulate state or pulverous PPDO by regulating the stirring dynamics and selecting different types of catalyzer to obtain outward appearance as required.
3, owing to contain the band aqua in the reaction system of the present invention, and can be little bulk, particulate state or pulverous PPDO by regulating the stirring dynamics and selecting different types of catalyzer to obtain outward appearance, not only avoided the difficulty of the big block product postprocessing of prior art, and further expansion is produced for possibility, therefore its suitability for industrialized production also can be expected to realize.
4, because method and apparatus provided by the invention can solve the problem of prior art synthesis condition harshness and big block product postprocessing difficulty, thereby the cost of PPDO is greatly reduced, for having established basis of price in the application aspect the general purpose material.
5,, thereby can further reduce production costs owing to the band aqua and the molecular sieve that use in the reaction system of the present invention all can recycle and recycle.
6, the inventive method is simple, and processing condition are easy to control, and the PPDO molecular weight that obtains can match in excellence or beauty with the traditional technology products therefrom.
7, condensation is reclaimed the partial design that dewaters and is skillfully constructed in the reaction unit provided by the invention, and is simple in structure, and mostly is conventional using appts greatly, and cost is low.
Description of drawings
Fig. 1 is the structural representation of a kind of reaction unit of the present invention;
Fig. 2 is the structural representation of the another kind of reaction unit of the present invention;
Fig. 3 is the structural representation of the third reaction unit of the present invention.
Embodiment
Provide the embodiment of reaction unit of the present invention below at first in conjunction with the accompanying drawings, next provides the embodiment of the inventive method, so that the invention will be further described.Be necessary to be pointed out that at this following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
As shown in Figure 1, the present embodiment reaction unit is made up of reaction vessel 1, water eliminator 4, water cooler 10, moisture eliminator 11, and water eliminator 4, water cooler 10, moisture eliminator 11 are installed in reaction vessel 1 top successively.Reaction vessel 1 wherein is placed with stirrer 2 for single neck bottle of laboratory band inflation inlet commonly used.Water eliminator 4 stage casings are the open cylinder in a top, the bottom surface has an aperture 5, molecular sieve 6 is housed in the cylinder, cylinder bottom surface below have one with the gas-liquid thrust-augmenting nozzle 7 of reaction vessel 1 Link Port internal diameter coupling, cylinder top extend to form one with the Link Port 8 of water cooler coupling end external diameter coupling, also have a parallel gas flow side pipe 9 in cylinder one side, these side pipe 9 two ends communicate with gas-liquid thrust-augmenting nozzle 7 and cylinder top respectively.The aperture of molecular sieve 6 is in the cylinder
High temperature materials such as water eliminator 4 useable glass, pottery are made.Water cooler 10 is existing conventional condenser, and present embodiment is a spiral condenser.Moisture eliminator 11 is a bend pipe, and wherein end coupling is inserted on the water cooler 10, and soft rubber ball with holes 12 is laid in the other end end, places siccative 13 in the pipe, as Calcium Chloride Powder Anhydrous.
As shown in Figure 2, the present embodiment reaction unit also is made up of reaction vessel 1, water eliminator 4, water cooler 10, moisture eliminator 11, and water eliminator 4, water cooler 10, moisture eliminator 11 are installed in reaction vessel 1 top successively.Reaction vessel 1 is laboratory three-necked bottle commonly used as different from Example 1, and agitator 3 is installed on the middle bottleneck, and water eliminator 4, water cooler 10, moisture eliminator 11 are installed in the top of a side bottleneck successively, and the opposite side bottleneck is as inflation inlet.Because the structure of water eliminator 4, water cooler 10, moisture eliminator 11 and annexation and embodiment 1 are identical, do not state so omit.
As shown in Figure 3, the present embodiment reaction unit also is made up of reaction vessel 1, water eliminator 4, water cooler 10, moisture eliminator 11, and water eliminator 4, water cooler 10, moisture eliminator 11 are installed in reaction vessel 1 top successively.Reaction vessel 1 is a reactor as different from Example 1, thereby water eliminator 4 can be attached thereto by the flange that gas-liquid thrust-augmenting nozzle 7 ends are provided with; Water cooler 10 is the tubulation water cooler, and it also is to be connected by flange with water eliminator 4.Because the structure and the embodiment 1 of water eliminator 4 are identical, do not state so omit.
Add 10.2g earlier to dioxy pimelinketone and 42.5ml hexanaphthene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 2.5 hours; recording it is 42ppm to dioxy pimelinketone water-content; the back is in 80 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and be 1: 550 catalyzer triethyl aluminum toluene solution to dioxy pimelinketone mol ratio; stir polymerase 10 .5 hour, and obtained granular disintegration.
Polyreaction is poured out hexanaphthene after finishing, and dries product, and PPDO is used acetone extracting 48 hours, to remove unreacted monomer, is dried to weight then and obtains 9.1g purifying thing in 40 ℃ of vacuum drying ovens, and monomer conversion is 89.3%.
With the PPDO that obtains, with phenol/1,1,2, (2: 3/w: w) mixing solutions is made solvent to the 2-tetrachloroethane, uses dark type viscometer in 25 ℃ of waters bath with thermostatic control, the intrinsic viscosity that records PPDO is 2.1dL/g, by Mark-Houwink equation [η]=KM
v a(a=0.63, K=7.9*10
-4Cm
3g
-1) molecular weight that calculates this PPDO is 270,000.
Add 10.2g earlier to dioxy pimelinketone and 36.55ml toluene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 2 hours; recording it is 50ppm to dioxy pimelinketone water-content; the back is in 90 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and be 1: 550 catalyzer triethyl aluminum toluene solution to dioxy pimelinketone mol ratio; stir polymerization 1 hour, obtain powdery product.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 8.56g purifying thing, monomer conversion is 84.2%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.2dL/g, and calculating molecular weight is 110,000.
Add 10.2g earlier to dioxy pimelinketone and 35ml hexanaphthene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 3 hours; recording it is 63ppm to dioxy pimelinketone water-content; the back is in 80 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and be 1: 550 catalyzer trimethyl aluminium toluene solution to dioxy pimelinketone mol ratio; stir polymerization 2 hours, obtain granular disintegration.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 8.87g purifying thing, monomer conversion is 87%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.87dL/g, and calculating molecular weight is 230,000.
Add 10.2g earlier to dioxy pimelinketone and 40ml hexanaphthene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 0.5 hour; recording it is 112ppm to dioxy pimelinketone water-content; the back is in 80 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and be 1: 550 catalyzer trimethyl aluminium toluene solution to dioxy pimelinketone mol ratio; stir polymerase 10 .5 hour, and obtained granular disintegration.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 9.1g purifying thing, monomer conversion is 89.1%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.58dL/g, and calculating molecular weight is 17.3 ten thousand.
Add 10.2g earlier to dioxy pimelinketone and 38.25ml hexanaphthene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 3 hours; recording it is 40ppm to dioxy pimelinketone water-content; the back is in 80 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and be 1: 700 catalyzer triethyl aluminum toluene solution to dioxy pimelinketone mol ratio; stir polymerization 4 hours, obtain granular disintegration.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 9.2g purifying thing, monomer conversion is 90.2%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.69dL/g, and calculating molecular weight is 19.4 ten thousand.
Add 10.2g earlier to dioxy pimelinketone and 40ml dimethylbenzene in the reaction vessel 1 of the shown device shown in Fig. 1 of the present invention or 2, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 3 hours; recording it is 50ppm to dioxy pimelinketone water-content; the back is in 90 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and the octoate catalyst Asia tin toluene solution that to dioxy pimelinketone mol ratio is 1: 8000; stir polymerization 48 hours, obtain little block product.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 8.1g purifying thing, monomer conversion is 79%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.1dL/g, and calculating molecular weight is 9.5 ten thousand.
Add 20.4g earlier to dioxy pimelinketone and 60ml toluene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 3 hours; recording it is 78ppm to dioxy pimelinketone water-content; the back is in 100 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and be 1: 750 catalyzer aluminum isopropylate toluene solution to dioxy pimelinketone mol ratio; stir polymerization 18 hours, obtain little block product.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 16.3g purifying thing, monomer conversion is 80%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.04dL/g, and calculating molecular weight is 90,000.
Add 20.4g earlier to dioxy pimelinketone and 64.6ml benzene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 1 hour; recording it is 89ppm to dioxy pimelinketone water-content; the back is in 60 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and the octoate catalyst Asia tin toluene solution that to dioxy pimelinketone mol ratio is 1: 5000; stir polyase 13 6 hours, and obtained powdery product.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 15.3g purifying thing, monomer conversion is 75%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.11dL/g, and calculating molecular weight is 9.9 ten thousand.
Add 20.4g earlier to dioxy pimelinketone and 54.4ml dimethylbenzene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 2.5 hours; recording it is 86ppm to dioxy pimelinketone water-content; the back is in 100 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and be 1: 900 catalyzer trimethyl aluminium toluene solution to dioxy pimelinketone mol ratio; stir polymerization 8 hours, obtain powdery product.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 18.2g purifying thing, monomer conversion is 89%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.54dL/g, and calculating molecular weight is 16.7 ten thousand.
Add 30.6g earlier to dioxy pimelinketone and 76.5ml hexanaphthene in the reaction vessel 1 of Fig. 1 of the present invention or 2 shown devices, the adding aperture is in water eliminator 4
Molecular sieve; heating azeotropic then refluxed 2 hours; recording it is 80ppm to dioxy pimelinketone water-content; the back is in 70 ℃ constant temperature oil bath under the argon shield again; carry out powerful stir and dripping and be 1: 600 catalyzer lanthanum isopropoxide toluene solution to dioxy pimelinketone mol ratio; stir polymerization 12 hours, obtain granular disintegration.
After polyreaction finishes, handle product according to the method for embodiment 4, obtain 23.6g purifying thing, monomer conversion is 77%.With testing method and the calculation formula that embodiment 4 provides, the intrinsic viscosity that records PPDO is 1.08dL/g, and calculating molecular weight is 9.5 ten thousand.
Claims (5)
1; a kind of synthetic method of PPDO; this method is will be that 1: 3～5 proportioning azeotropic in the reaction unit of special band water eliminator refluxed 0.5～3 hour by volume to dioxy pimelinketone and band aqua earlier; then under the protection of rare gas element; drip while stirring and the catalyzer that to dioxy pimelinketone mol ratio is 1: 550～5000; and can obtain precipitated product in 0.5～48 hour in 60～100 ℃ of reactions; promptly get final polymerisate after taking out the precipitated product drying; the reaction unit of used special band water eliminator is by reaction vessel (1); water eliminator (4); water cooler (10); moisture eliminator (11) is formed; water eliminator (4); water cooler (10); moisture eliminator (11) is installed in reaction vessel (1) top successively; reaction vessel (1) is existing popular response container; water eliminator (4) stage casing is the open cylinder in a top; the bottom surface has an aperture (5); molecular sieve (6) is housed in the cylinder; cylinder bottom surface below have one with the gas-liquid thrust-augmenting nozzle (7) of reaction vessel (1) Link Port internal diameter coupling; cylinder top extend to form one with the Link Port (8) of water cooler (10) coupling end external diameter coupling; also has a parallel gas flow side pipe (9) in cylinder one side; this side pipe (9) two ends communicate with gas-liquid thrust-augmenting nozzle (7) and cylinder top respectively; water cooler (10) is existing conventional condenser, and moisture eliminator (11) is an existing conventional bent-tube boiler moisture eliminator.
2, the synthetic method of PPDO according to claim 1 is characterized in that band aqua used in this method is a normal hexane, hexanaphthene, tetracol phenixin, benzene, toluene, dimethylbenzene, any in the methyl-phenoxide.
3, the synthetic method of PPDO according to claim 1 and 2 is characterized in that catalyzer used in this method is aluminum alkyls, alkoxy compound or stannous octoate.
4, the synthetic method of PPDO according to claim 3 is characterized in that catalyzer aluminum alkyls used in this method is any in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three hexyl aluminium, the aluminium diethyl monochloride.
5, the synthetic method of PPDO according to claim 3 is characterized in that catalyzer alkoxy compound used in this method is any in aluminum isopropylate, lanthanum isopropoxide, tetrabutyl titanate, isopropyl titanate, germanic acid four butyl esters.
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| CNB2007100484103A CN100516111C (en) | 2007-02-06 | 2007-02-06 | Method of synthesizing poly p-dioxycyclohexanone and reaction apparatus thereof |
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| CNB2007100484103A CN100516111C (en) | 2007-02-06 | 2007-02-06 | Method of synthesizing poly p-dioxycyclohexanone and reaction apparatus thereof |
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| CN101824023B (en) * | 2009-03-06 | 2013-12-11 | 惠州华阳医疗器械有限公司 | Method for purifying sodium hydroxyethoxy acetate and p-dioxanone (PDO) monomers |
| CN108641068A (en) * | 2018-08-07 | 2018-10-12 | 威海威高富森医用材料有限公司 | A kind of PDO powder and preparation method thereof |
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