CN1651509A - Polypara dioxocyclohexanone / montmorillonite nano-composite material and its preparation method - Google Patents
Polypara dioxocyclohexanone / montmorillonite nano-composite material and its preparation method Download PDFInfo
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- CN1651509A CN1651509A CN 200410081645 CN200410081645A CN1651509A CN 1651509 A CN1651509 A CN 1651509A CN 200410081645 CN200410081645 CN 200410081645 CN 200410081645 A CN200410081645 A CN 200410081645A CN 1651509 A CN1651509 A CN 1651509A
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Abstract
A poly-p-dioxycyclohexanone/montmorillonite nano-composition is prepared from poly-P-dioxycyclohexanone and montmorillonite nanoparticles through proportionally mixing, stirring, heating, adding catalyst and reacting. Another preparing process is also disclosed. Said nano-composition features high mechanical and thermal performance, low reaction condition and high molecular weight.
Description
One, technical field
The invention belongs to polymkeric substance and inorganic nano-filler matrix material and preparing technical field thereof, be specifically related to a kind of PPDO/Nanometer Composite Material Of Montmorillonite And Its Preparation Method.
Two, background technology
PPDO (PPDO) not only has excellent biodegradability, Bioabsorbable and biocompatibility, and have good snappiness, and be used for bio-medical material, have vast potential for future development.But it to be applied the but bigger obstacle of existence as general-purpose plastics: the one, the monomer whose price is higher, and production cost is comparatively expensive; The 2nd, synthesize high-molecular weight PPDO with practical value, very high to monomer purity, catalyst activity and polymeric reaction condition requirement usually, and also polymerization time is long, and the polymerisate crystallization velocity is slow, and melt strength is low, the forming process difficulty.These stops limit its apply as general-purpose plastics.
Three, summary of the invention
The objective of the invention is in order to overcome the shortcoming that PPDO exists in synthetic and application, adopting montmorillonite carries out modification, so that a kind of PPDO/Nanometer Composite Material Of Montmorillonite And Its Preparation Method to be provided.
PPDO/Nano composite material of montmorillonite provided by the invention, comprise the PPDO body material, it is characterized in that also containing in this material nano level polynite, the nano level polynite that contains and the weight ratio of PPDO are 0.5～20: 100, the second-order transition temperature of this material is-15～-2 ℃, Tc is 40～60 ℃, and fusing point is 103～113 ℃, and hot temperature of initial decomposition is greater than 200 ℃.
The method of the above-mentioned PPDO/Nano composite material of montmorillonite of preparation provided by the invention; it is characterized in that this method be with weight ratio be 100: 0.5～20 to dioxy pimelinketone monomer and polynite; under the nitrogen atmosphere protection; stirred 2～5 hours down in 30～50 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warming up to 60～120 ℃ then; add catalyzer; catalyzer and monomeric mol ratio are 1: 250～1000; make dioxy pimelinketone monomer with the surface in-situ polymerization and intercalation polymeric is taken place between cheating engaging layer; react and got final product in 2～20 hours; or directly with PPDO and polynite; be 100: 0.5～20 ratio by weight; blend is even in homogenizer earlier, then blend is carried out melt blending with twin screw extruder and extrudes, and blending temperature is 100～140 ℃.
Used polynite is the H-polynite in the aforesaid method, the Na-polynite, and Mg-polynite or Ca-polynite, its cation exchange capacity is greater than 70meq/100g.
Used catalyzer is aluminum alkyls, alkoxy compound or stannous octoate in the aforesaid method.Preferred trimethyl aluminium of aluminum alkyls or triethyl aluminum, preferred aluminum isopropylate of alkoxy compound or butyl (tetra) titanate.
Used polynite can be without the processing that organises in the aforesaid method, also can be through the processing that organises.Polynite organised is treated to known technology, and concrete grammar is with the polynite of cationic exchange total volume greater than 70meq/100g, stirs 1 hour at dispersion medium distilled water or deionized water high speed, makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; 20～50 parts of (with respect to 100 parts of polynites) organic modification agent are dissolved in 10～500 parts of dispersion medium water; Above-mentioned filtrate is heated to 50～70 ℃, drips the organic modification agent solution, and stirred 10～20 hours, carry out ion-exchange at 50～70 ℃ of following constant temperature; Suction filtration then is washed with distilled water to repeatedly and does not contain till the agent of free organic modification; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.Wherein used organic modification agent is quaternary ammonium salt or hydroxyl ammonium salt.Specifically can select octadecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride for use, hexadecyldimethyl benzyl ammonium hydroxyethyl brometo de amonio, hexadecyl methyl dihydroxy ethyl brometo de amonio etc.
Since montmorillonite layer the polymerization of PPDO or with it in the blend by all or part of peeling off after, being nano-scale is dispersed in the PPDO matrix, its nanometer size effect (one dimension is less than 100 nanometers at least) can produce very strong interface interaction power between PPDO segment and montmorillonite layer, thereby not only can improve the mechanical property and the thermal characteristics of PPDO material, and its crystallization rate is accelerated, the melt strength increase is bigger in the forming process, thereby can overcome the defective that pure PPDO can not blowfilm shaping.The more important thing is and adopt the PPDO nano composite material of this method preparation to require lower monomer and reaction conditions, and just can obtain the polymerisate of the close molecular weight that could obtain in the long period in the short period of time with prior art, production cycle also shortens dramatically, and method is simple, is easy to control.
Four, description of drawings
Fig. 1 obtains the X diffractogram of part matrix material for the polynite and the embodiment of the invention; Fig. 2 is the differential scanning calorimeter figure of PPDO homopolymer and matrix material; Fig. 3 is the thermogravimetric analysis figure of PPDO homopolymer and matrix material; Fig. 4 is PPDO homopolymer and the matrix material increase change of molecular weight figure with the reaction times.
Five, embodiment
Provide embodiment below so that the present invention is further specified; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field still belongs to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention makes.
Embodiment 1
(1) be that the 20g Na-polynite of 100meq/100g places 500ml distilled water or deionized water with the cationic exchange total volume, high-speed stirring 1 hour makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; The 4g octadecyl trimethyl ammonium chloride is dissolved in the 25ml distilled water; Above-mentioned filtrate is heated to 50 ℃, drips octadecyl trimethyl ammonium chloride solution, and stirred 10 hours, carry out ion-exchange at 50 ℃ of following constant temperature; Naturally cool to room temperature then, suction filtration, and repeatedly with distilled water wash repeatedly, extremely with till the no chlorion in the silver nitrate solution detection filtrate of 1mol/L; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.
(2) will be to the organo montmorillonite 3g of dioxy pimelinketone monomer 100g and above-mentioned preparation; add in the reaction flask that the nitrogen atmosphere protection is arranged successively; stirred 2 hours down at 30 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warmed up to 60 ℃ then; adding and monomer mole ratio are 1: 1000 triethyl aluminum toluene solution again; make dioxy pimelinketone monomer in-situ polymerization and intercalation polymeric reaction is taken place after 3 hours between cheating engaging layer or surface, promptly obtain PPDO/Nano composite material of montmorillonite.
Embodiment 2
(1) be that the 20gH-polynite of 80meq/100g places 500ml distilled water or deionized water with the cationic exchange total volume, high-speed stirring 1 hour makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; The 4g octadecyl trimethyl ammonium chloride is dissolved in the 25ml distilled water; Above-mentioned filtrate is heated to 60 ℃, drips octadecyl trimethyl ammonium chloride solution, and stirred 20 hours, carry out ion-exchange at 60 ℃ of following constant temperature; Naturally cool to room temperature then, suction filtration, and repeatedly with distilled water wash repeatedly, extremely with till the no chlorion in the silver nitrate solution detection filtrate of 1mol/L; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.
(2) will be to the organo montmorillonite 5g of dioxy pimelinketone monomer 100g and above-mentioned preparation; add in the reaction flask that the nitrogen atmosphere protection is arranged successively; stirred 3 hours down at 40 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warmed up to 70 ℃ then; adding and monomer mole ratio are 1: 500 trimethyl aluminium toluene solution again; make dioxy pimelinketone monomer in-situ polymerization and intercalation polymeric reaction is taken place after 5 hours between cheating engaging layer or surface, promptly obtain PPDO/Nano composite material of montmorillonite.
(1) be that the 20gMg-polynite of 120meq/100g places 500ml distilled water or deionized water with the cationic exchange total volume, high-speed stirring 1 hour makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; The 4g octadecyl trimethyl ammonium chloride is dissolved in the 25ml distilled water; Above-mentioned filtrate is heated to 70 ℃, drips octadecyl trimethyl ammonium chloride solution, and stirred 15 hours, carry out ion-exchange at 70 ℃ of following constant temperature; Naturally cool to room temperature then, suction filtration, and repeatedly with distilled water wash repeatedly, extremely with till the no chlorion in the silver nitrate solution detection filtrate of 1mol/L; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.
(2) will be to the organo montmorillonite 10g of dioxy pimelinketone monomer 100g and above-mentioned preparation; add in the reaction flask that the nitrogen atmosphere protection is arranged successively; stirred 4 hours down at 50 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warmed up to 80 ℃ then; adding and monomer mole ratio are 1: 750 stannous octoate toluene solution again; make dioxy pimelinketone monomer in-situ polymerization and intercalation polymeric reaction is taken place after 20 hours between cheating engaging layer or surface, promptly obtain PPDO/Nano composite material of montmorillonite.
Embodiment 4
(1) be that the 20gNa-polynite of 75meq/100g places 500ml distilled water or deionized water with the cationic exchange total volume, high-speed stirring 1 hour makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; The 4g octadecyl trimethyl ammonium chloride is dissolved in the 25ml distilled water; Above-mentioned filtrate is heated to 70 ℃, drips octadecyl trimethyl ammonium chloride solution, and stirred 20 hours, carry out ion-exchange at 70 ℃ of following constant temperature; Naturally cool to room temperature then, suction filtration, and repeatedly with distilled water wash repeatedly, extremely with till the no chlorion in the silver nitrate solution detection filtrate of 1mol/L; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.
(2) will be to the organo montmorillonite 20g of dioxy pimelinketone monomer 100g and above-mentioned preparation; add in the reaction flask that the nitrogen atmosphere protection is arranged successively; stirred 5 hours down at 35 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warmed up to 100 ℃ then; adding and monomer mole ratio are 1: 250 aluminum isopropylate toluene solution again; make dioxy pimelinketone monomer in-situ polymerization and intercalation polymeric reaction is taken place after 10 hours between cheating engaging layer or surface, promptly obtain PPDO/Nano composite material of montmorillonite.
(1) be that the 20gCa-polynite of 100meq/100g places 500ml distilled water or deionized water with the cationic exchange total volume, high-speed stirring 1 hour makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; 4g hexadecyldimethyl benzyl ammonium hydroxyethyl brometo de amonio is dissolved in the 25ml distilled water; Above-mentioned filtrate is heated to 50 ℃, drips hexadecyldimethyl benzyl ammonium hydroxyethyl brometo de amonio solution, and stirred 10 hours, carry out ion-exchange at 50 ℃ of following constant temperature; Naturally cool to room temperature then, suction filtration, and repeatedly with distilled water wash repeatedly, extremely with till the no chlorion in the silver nitrate solution detection filtrate of 1mol/L; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.
(2) will be to the organo montmorillonite 1g of dioxy pimelinketone monomer 100g and above-mentioned preparation; add in the reaction flask that the nitrogen atmosphere protection is arranged successively; stirred 2 hours down at 30 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warmed up to 120 ℃ then; adding and monomer mole ratio are 1: 250 trimethyl aluminium toluene solution again; make dioxy pimelinketone monomer in-situ polymerization and intercalation polymeric reaction is taken place after 15 hours between cheating engaging layer or surface, promptly obtain PPDO/Nano composite material of montmorillonite.
Embodiment 6
To be 80meq/100gNa-polynite 3g to dioxy pimelinketone 100g and cationic exchange total volume; add in the reaction flask that the nitrogen atmosphere protection is arranged successively; stirred 4 hours down at 40 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warmed up to 70 ℃ then; adding and monomer mole ratio are 1: 1000 triethyl aluminum toluene solution again; make dioxy pimelinketone monomer in-situ polymerization and intercalation polymeric reaction is taken place after 15 hours between cheating engaging layer or surface, promptly obtain PPDO/Nano composite material of montmorillonite.
Embodiment 7
To be 100meq/100gH-polynite 5g to dioxy pimelinketone 100g and cationic exchange total volume; add in the reaction flask that the nitrogen atmosphere protection is arranged successively; stirred 3 hours down at 40 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warmed up to 80 ℃ then; adding and monomer mole ratio are 1: 750 aluminum isopropylate toluene solution again; make dioxy pimelinketone monomer in-situ polymerization and intercalation polymeric reaction is taken place after 10 hours between cheating engaging layer or surface, promptly obtain PPDO/Nano composite material of montmorillonite.
To be 120meq/100gMg-polynite 10g to dioxy pimelinketone 100g and cationic exchange total volume; add in the reaction flask that the nitrogen atmosphere protection is arranged successively; stirred 2 hours down at 50 ℃; make the abundant swelling of polynite; allow dioxy pimelinketone monomer is entered between cheating engaging layer; be warmed up to 90 ℃ then; adding and monomer mole ratio are 1: 500 stannous octoate toluene solution again; make dioxy pimelinketone monomer in-situ polymerization and intercalation polymeric reaction is taken place after 5 hours between cheating engaging layer or surface, promptly obtain PPDO/Nano composite material of montmorillonite.
Embodiment 9
(1) be that the 20gNa-polynite of 75meq/100g places 500ml distilled water or deionized water with the cationic exchange total volume, high-speed stirring 1 hour makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; The 4g octadecyl trimethyl ammonium chloride is dissolved in the 25ml distilled water; Above-mentioned filtrate is heated to 50 ℃, drips octadecyl trimethyl ammonium chloride solution, and stirred 16 hours, carry out ion-exchange at 50 ℃ of following constant temperature; Naturally cool to room temperature then, suction filtration, and repeatedly with distilled water wash repeatedly, extremely with till the no chlorion in the silver nitrate solution detection filtrate of 1mol/L; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.
(2) with intrinsic viscosity be the PPDO 100g of 1.6dL/g and the organo montmorillonite 20g of above-mentioned preparation, blend is even in homogenizer earlier, then blend being carried out melt blending with twin screw extruder extrudes, promptly obtain PPDO/Nano composite material of montmorillonite, blending temperature is 100～140 ℃.
(1) be that the 20gMg-polynite of 100meq/100g places 500ml distilled water or deionized water with the cationic exchange total volume, high-speed stirring 1 hour makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; 4g hexadecyldimethyl benzyl ammonium hydroxyethyl brometo de amonio is dissolved in the 25ml distilled water; Above-mentioned filtrate is heated to 50 ℃, drips hexadecyldimethyl benzyl ammonium hydroxyethyl brometo de amonio solution, and stirred 16 hours, carry out ion-exchange at 50 ℃ of following constant temperature; Naturally cool to room temperature then, suction filtration, and repeatedly with distilled water wash repeatedly, extremely with till the no chlorion in the silver nitrate solution detection filtrate of 1mol/L; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.
(2) with intrinsic viscosity be the PPDO 100g of 1.6dL/g and the organo montmorillonite 5g of above-mentioned preparation, blend is even in homogenizer earlier, then blend being carried out melt blending with twin screw extruder extrudes, promptly obtain PPDO/Nano composite material of montmorillonite, blending temperature is 100～140 ℃.
Embodiment 11
(1) be that the 20gH-polynite of 90meq/100g places 500ml distilled water or deionized water with the cationic exchange total volume, high-speed stirring 1 hour makes it to form stable suspension; Left standstill then 0.5 hour, and suspension was filtered, obtain filtrate with 400 order filter clothes, standby; The 4g octadecyl trimethyl ammonium chloride is dissolved in the 25ml distilled water; Above-mentioned filtrate is heated to 50 ℃, drips octadecyl trimethyl ammonium chloride solution, and stirred 16 hours, carry out ion-exchange at 50 ℃ of following constant temperature; Naturally cool to room temperature then, suction filtration, and repeatedly with distilled water wash repeatedly, extremely with till the no chlorion in the silver nitrate solution detection filtrate of 1mol/L; 50 ℃ of following vacuum-dryings 20 hours, until the polynite constant weight, and the powder that grinds to form less than 100 microns got final product at last.
(2) with intrinsic viscosity be the PPDO 100g of 1.6dL/g and the organo montmorillonite 3g of above-mentioned preparation, blend is even in homogenizer earlier, then blend being carried out melt blending with twin screw extruder extrudes, promptly obtain PPDO/Nano composite material of montmorillonite, blending temperature is 100～140 ℃.
Embodiment 12
With the 100g intrinsic viscosity is that PPDO and the 10g cationic exchange total volume of 1.6dL/g is the Ca-polynite of 100meq/100g, one at first in homogenizer blend even, then blend being carried out melt blending with twin screw extruder extrudes, promptly obtain PPDO/Nano composite material of montmorillonite, blending temperature is 100～140 ℃.
Embodiment 13
With the 100g intrinsic viscosity is that PPDO and the 1g cationic exchange total volume of 1.6dL/g is the Na-polynite of 100meq/100g, one at first in homogenizer blend even, then blend being carried out melt blending with twin screw extruder extrudes, promptly obtain PPDO/Nano composite material of montmorillonite, blending temperature is 100～140 ℃.
Embodiment 14
With the 100g intrinsic viscosity is that PPDO and the 15g cationic exchange total volume of 1.6dL/g is the H-polynite of 80meq/100g, blend is even in homogenizer earlier, then blend being carried out melt blending with twin screw extruder extrudes, promptly obtain PPDO/Nano composite material of montmorillonite, blending temperature is 100～140 ℃.
Mechanical property, thermal characteristics for PPDO/Nano composite material of montmorillonite of investigating the present invention preparation, and polynite in polyreaction to the influence of polymerization rate, the part matrix material and the PPDO homopolymer of gained carried out following performance test:
Measuring mechanical property: matrix material is carried out being prepared into batten after compressing tablet forms sheet material, press the GB1040-79 regulation and test its tensile strength and elongation at break, it the results are shown in Table 1.Can see that from table 1 tensile strength of matrix material provided by the invention and elongation at break all are greatly improved than the PPDO homopolymer.
X-ray diffraction (XRD) test: test condition is a Cu target K α spectral line (wavelength, 1.5406 ), 40kV/20mA.The gained collection of illustrative plates is seen Fig. 1.MTT-Na is meant the Na-polynite among the figure; PPDO is meant the PPDO homopolymer; MTT-OH is meant the polynite that organises and handle through octadecyl trimethyl ammonium chloride; MTT-1831 is meant the polynite that organises and handle through hexadecyldimethyl benzyl ammonium hydroxyethyl brometo de amonio.Spectral line from figure can be seen, the about 1.22nm of the interlamellar spacing of natural montmorillonite, the cheating engaging layer spacing that organises after handling is about 1.84～2.24nm, use the polynite of handling without organising in the matrix material, its interlamellar spacing increases than the existing of pure polynite, and the interlamellar spacing of the polynite that use is handled through organising then increases bigger, about 3.21～3.72nm, illustrate that polymkeric substance has entered between cheating engaging layer, has formed nano composite material.
Differential scanning calorimeter (DSC) test: adopt the dsc analysis instrument that sample is heated to 140 ℃ earlier, 5 fens kinds of constant temperature are eliminated thermal history, be cooled to-60 ℃ of 10 ℃/min, heat up with identical speed and scan 140 ℃ then.Test result is seen Fig. 2.(a) figure among Fig. 2 is the cooling scintigram, and (b) figure is the intensification scintigram.Can see that from test result matrix material is compared with the PPDO homopolymer, its Tc, second-order transition temperature and fusing point all increase.
Thermogravimetric analysis (TG) test: under nitrogen atmosphere, be warmed up to 400 ℃ with the temperature rise rate of 10 ℃/min from room temperature and test, the results are shown in Figure 3 with 50mL/min speed.Can see that from test result the heat decomposition temperature of matrix material compares with the PPDO homopolymer, be enhanced.
The rate of polymerization test: test result is seen Fig. 4.Test result shows in the presence of polynite, can obtain the product of higher molecular weight in the short time, illustrate that polynite played the effect of catalysis acceleration in polymerization process, can shorten polymerization time.
Table 1
| Embodiment | Intrinsic viscosity (dL/g) | Elongation at break (%) | Tensile strength (MPa) |
| ????PPDO | ????1.60 | ????205 | 29.3 |
| ????1 | ????1.15 | ????512 | 46.7 |
| ????2 | ????1.36 | ????593 | 55.5 |
| ????5 | ????1.62 | ????633 | 48.1 |
| ????6 | ????1.07 | ????573 | 56.1 |
| ????10 | ????1.60 | ????491 | 49.2 |
Claims (10)
1, a kind of PPDO/Nano composite material of montmorillonite, comprise the PPDO body material, it is characterized in that also containing in this material nano level polynite, the nano level polynite that contains and the weight ratio of PPDO are 0.5～20: 100, the second-order transition temperature of this material is-15～-2 ℃, Tc is 40～60 ℃, and fusing point is 103～113 ℃, and hot temperature of initial decomposition is greater than 200 ℃.
2; a kind of method for preparing the described PPDO/Nano composite material of montmorillonite of claim 1; it is characterized in that this method be with weight ratio be 100: 0.5～20 to dioxy pimelinketone monomer and polynite; under the nitrogen atmosphere protection; stirred 2～5 hours down in 30～50 ℃; be warming up to 60～120 ℃ then; add catalyzer; catalyzer and monomeric mol ratio are 1: 250～1000; reacted 2～20 hours; get final product; or with PPDO and polynite; be 100: 0.5～20 ratio by weight; blend is even in homogenizer earlier, then blend is carried out melt blending with twin screw extruder and extrudes, and blending temperature is 100～140 ℃.
3, the preparation method of PPDO/Nano composite material of montmorillonite according to claim 2, it is characterized in that used polynite is the H-polynite, the Na-polynite, Mg-polynite or Ca-polynite, its cation exchange capacity is greater than 70meq/100g.
4,, it is characterized in that used polynite is to handle through organising according to the preparation method of claim 2 or 3 described PPDO/Nano composite material of montmorillonite.
5,, it is characterized in that used catalyzer is aluminum alkyls, alkoxy compound or stannous octoate according to the preparation method of claim 2 or 3 described PPDO/Nano composite material of montmorillonite.
6, the preparation method of PPDO/Nano composite material of montmorillonite according to claim 4 is characterized in that used catalyzer is aluminum alkyls, alkoxy compound or stannous octoate.
7, the preparation method of PPDO/Nano composite material of montmorillonite according to claim 5 is characterized in that aluminum alkyls selects trimethyl aluminium or triethyl aluminum for use.
8, the preparation method of PPDO/Nano composite material of montmorillonite according to claim 6 is characterized in that aluminum alkyls selects trimethyl aluminium or triethyl aluminum for use.
9, the preparation method of PPDO/Nano composite material of montmorillonite according to claim 5 is characterized in that alkoxy compound selects aluminum isopropylate or butyl (tetra) titanate for use.
10, the preparation method of PPDO/Nano composite material of montmorillonite according to claim 6 is characterized in that used alkoxy compound selects aluminum isopropylate or butyl (tetra) titanate for use.
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| CN100336844C (en) * | 2006-03-14 | 2007-09-12 | 四川大学 | Polytetrahydrofuran and poly-p-dioxanone triblock copolymer and its preparation method and use |
| CN100460442C (en) * | 2006-08-29 | 2009-02-11 | 四川大学 | Method of preparing poly p-dioxanone and montmorillonite nano composite material thereof by microwave radiation |
| CN101831157A (en) * | 2010-05-14 | 2010-09-15 | 四川大学 | Composite material of poly(p-dioxanone)/inorganic nano-fiber and preparation method thereof |
| CN101831157B (en) * | 2010-05-14 | 2012-07-25 | 四川大学 | Composite material of poly(p-dioxanone)/inorganic nano-fiber and preparation method thereof |
| CN103965661A (en) * | 2014-05-15 | 2014-08-06 | 南京林业大学 | Preparation method and application of secondary modified layered double hydroxide |
| CN103965661B (en) * | 2014-05-15 | 2015-06-17 | 南京林业大学 | Preparation method and application of secondary modified layered double hydroxide |
| CN104829860A (en) * | 2015-05-29 | 2015-08-12 | 北京理工大学 | Melamine cyanurate and montmorillonite nano-composite and preparation method thereof |
| CN104829860B (en) * | 2015-05-29 | 2017-08-04 | 北京理工大学 | A kind of melamine cyanurate and montmorillonite nano complex and preparation method thereof |
| CN112694728A (en) * | 2020-12-31 | 2021-04-23 | 通源塑料包装(苏州)有限公司 | Plastic bag with poly (p-dioxanone) as substrate and preparation method thereof |
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| CN1300231C (en) | 2007-02-14 |
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