CN110054846B - Rare earth doped titanium dioxide modified polyvinyl chloride composite material and preparation method thereof - Google Patents
Rare earth doped titanium dioxide modified polyvinyl chloride composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polymer composite material preparation, and particularly relates to a rare earth doped titanium dioxide modified polyvinyl chloride composite material and a preparation method thereof, wherein the composite material consists of rare earth doped titanium dioxide and polyvinyl chloride, and is prepared by melting and banburying master batches and polyvinyl chloride obtained by in-situ polymerization; the rare earth element is doped in the titanium dioxide synthesis process, the effect is better compared with the effect of dispersing the rare earth oxide in the titanium dioxide solution in the later period, and simultaneously, the rare earth and the titanium dioxide have synergistic effect, so that the prepared material has more excellent thermal stability and light stability; the rare earth doped titanium dioxide is added in the process of in-situ polymerization of polyvinyl chloride, so that the interface binding force between the inorganic filler and the high polymer material can be remarkably increased, and the dispersion of the rare earth doped titanium dioxide in the polyvinyl chloride composite material is facilitated; the preparation method is simple and practical, and is suitable for large-scale industrial production and application.
Description
Technical Field
The invention belongs to the technical field of preparation of polymer composite materials, and particularly relates to a rare earth doped titanium dioxide modified polyvinyl chloride composite material and a preparation method thereof.
Background
PVC is widely applied in the current society as a plastic with excellent processing performance. But the heat resistance and the aging resistance are poor, the heat distortion temperature is low, and the application of the heat-resistant and aging-resistant composite material in various fields is limited. At present, the research on the heat resistance and aging resistance of PVC mainly focuses on the methods of adding an auxiliary agent, inorganic rigid particles, crosslinking and the like in the processing process. Although the Vicat temperature can be obviously improved by modifying polyvinyl chloride with the modifier, the price is high, and compared with the polyvinyl chloride, the modification cost is higher. The PVC cross-linking technology can obviously improve the thermal deformation and thermal decomposition temperature, has more technical difficulties in the preparation process, and is not suitable for large-scale industrial production. The rigid inorganic particle modified polyvinyl chloride composite material has simple and easily realized preparation method.
When the material is in the nanometer scale, the material has various effects, and the nanometer inorganic filler is used for modifying the polymer to gain wide attention. The nano-scale material has high surface energy, so that the nano-scale material is difficult to be uniformly dispersed in a high molecular material by a common processing means, and the surface property of the common inorganic nano-filler is greatly different from that of a high molecular material, so that the inorganic nano-filler is easy to form aggregates with larger size in the mixing process, the size of the inorganic nano-filler in the material is far larger than the nano-scale, and the nano-scale effect is lost.
Disclosure of Invention
The invention solves the technical problems in the prior art and provides a rare earth doped titanium dioxide modified polyvinyl chloride composite material and a preparation method thereof.
In order to solve the problems, the technical scheme of the invention is as follows:
the preparation method of the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch comprises the following steps:
step 1, preparing rare earth doped titanium dioxide powder;
step 1.1, dissolving titanate in alcohol substances to prepare solution A;
step 1.2, dispersing the rare earth oxide in an alcohol substance, fully stirring by ultrasonic waves, and filtering to obtain a solution B;
step 1.3, under the condition of ultrasonic stirring, dropwise adding the solution B into the solution A, and then aging in a dark place to obtain rare earth doped titanium dioxide sol;
step 1.4, drying and molding the rare earth doped titanium dioxide sol, placing the dried and molded rare earth doped titanium dioxide sol in a muffle furnace, calcining the sol for 1 to 4 hours at the set temperature of 300 to 600 ℃, and physically grinding the sol to obtain rare earth doped titanium dioxide powder;
step 2, preparation of rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch
Dispersing the rare earth doped titanium dioxide powder obtained in the step 1.4 in water to prepare suspension C; and adding the suspension C into a polyvinyl chloride suspension polymerization system for polymerization, and discharging after the polymerization is finished to prepare the rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch.
Preferably, the titanate is tetrabutyl titanate or isopropyl titanate; the alcohol substance is any one of methanol, ethanol and isopropanol; the rare earth oxide is lanthanum oxide or cerium oxide.
Preferably, in the step 1.1, the volume ratio of the titanate to the alcohol substance is 1: 1-10.
Preferably, in the step 1.2, the volume ratio of the rare earth oxide substance to the alcohol substance is 1g:40 mL.
Preferably, in the step 1.3, the A, B solution volume ratio is 1:1 to 10.
Preferably, in the step 1.3, the dropping rate is 0.01-1 ml per second, and the aging time is 24-168 hours.
Preferably, the polyvinyl chloride suspension polymerization system comprises monomers, deionized water, an oil-soluble initiator, a dispersant, a chain terminator and a pH regulator; the monomer is chloroethylene; the oil-soluble initiator is peroxyacyl, peroxyester, peroxydicarbonate or azo; the dispersant is polyvinyl alcohol or cellulose ethers; the chain terminator is acetone thiosemicarbazone; the pH regulator is one or more of ammonium bicarbonate, ammonia water, sodium hydroxide, sodium carbonate, sodium phosphate and calcium hydroxide.
Preferably, the mass fraction ratio of vinyl chloride, deionized water, a dispersing agent, a rare earth doped titanium dioxide suspension C, pH regulator, an initiator and a chain terminator in the polyvinyl chloride suspension polymerization system is 1400: 1400: 4: 1-15: 0.5: 1.5: 3.5.
preferably, in the step 2, the discharging after the polymerization is completed to prepare the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch comprises the following specific steps:
and discharging after polymerization, drying in an oven at the temperature of 40-60 ℃, melting and mixing by a single-screw extruder, discharging, and performing water-cooling, granulating and drying to prepare the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch.
Preferably, the polymerization process in step 2 is:
step 2.1, sequentially putting deionized water, a dispersing agent and a rare earth doped titanium dioxide suspension C, pH regulator into a polymerization kettle, adding an initiator, sealing a cover, vacuumizing, and maintaining the pressure for 30-60 min;
2.2, adding vinyl chloride monomer under the stirring condition, fully and uniformly mixing, heating to 50-75 ℃, and starting a polymerization reaction;
and 2.3, adding a chain terminator when the pressure in the reaction kettle is reduced to-0.1 MPa, and discharging after nitrogen purging.
Preferably, the stirring conditions in step 2.2 are: the rotation speed is 100 to 700 r/min.
A rare earth doped titanium dioxide modified polyvinyl chloride composite material comprises
0.1-10 parts by mass of the rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch;
90-99.9 parts by mass of polyvinyl chloride.
The preparation method of the rare earth doped titanium dioxide modified polyvinyl chloride composite material comprises the following steps:
(1) weighing rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch and polyvinyl chloride according to the weight ratio, and putting the weighed materials into a high-speed mixer for fully mixing;
(2) and (2) feeding the material obtained in the step (1) into a double-screw extruder, performing melt extrusion through the double-screw extruder, wherein the processing temperature is 180-200 ℃, the screw rotating speed is 150-300 r/min, and then performing bracing, cooling, grain-sized dicing and drying treatment to obtain the rare earth doped titanium dioxide modified polyvinyl chloride composite material.
Compared with the prior art, the invention has the advantages that,
1. according to the invention, rare earth elements are doped in the titanium dioxide synthesis process, the effect is better compared with the effect of dispersing rare earth oxides in a titanium dioxide solution in the later period, and simultaneously, the rare earth and the titanium dioxide have a synergistic effect, so that the prepared material has more excellent thermal stability and light stability.
2. The rare earth doped titanium dioxide is added in the process of in-situ polymerization of polyvinyl chloride, so that the interface bonding force between the inorganic filler and the high polymer material can be remarkably increased, and the dispersion of the rare earth doped titanium dioxide in the polyvinyl chloride composite material is facilitated.
3. The preparation method is simple and practical, and is suitable for large-scale industrial production and application.
Detailed Description
The polyvinyl chloride used in the examples was a general-purpose polyvinyl chloride resin commercially available.
Example 1:
the embodiment provides a preparation method of a rare earth doped titanium dioxide modified polyvinyl chloride composite material, which comprises the following steps:
preparation of rare earth doped titanium dioxide powder:
A. dissolving 10ml of butyl titanate in 10ml of ethanol, and performing ultrasonic stirring and uniform dispersion to obtain a solution A;
B. then 0.5g of lanthanum oxide is weighed and dispersed in 20mL of ethanol solution, and the solution B is obtained after sufficient ultrasonic stirring and filtration;
C. ultrasonically stirring, continuously and slowly dripping 20mLB solution into the solution A at room temperature, and then aging in the dark for 24 hours to obtain rare earth doped titanium dioxide sol, wherein the dripping speed is 0.01ml per second;
D. drying, molding, placing in a muffle furnace, calcining at 300 ℃ for 4 hours, and physically grinding to obtain rare earth doped titanium dioxide powder;
preparing rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch:
dispersing the prepared rare earth doped titanium dioxide powder in deionized water, performing ultrasonic dispersion to prepare a suspension C, cleaning a reaction kettle, sequentially adding deionized water, a dispersing agent and a rare earth doped titanium dioxide suspension C, pH regulator which are quantitatively shown in table 1 into the reaction kettle, finally adding an initiator into the polymerization kettle, sealing and vacuumizing after the feeding is finished, maintaining the pressure for 30min, and performing the next step of experiment after the readings are not obviously changed; starting stirring, setting the rotating speed at 700r/min, adding vinyl chloride monomer, fully and uniformly mixing, heating to 50 ℃, and starting polymerization reaction; when the pressure in the reaction kettle is reduced to-0.1 MPa, the reaction is determined to be complete, a chain terminator is added, and the material is discharged after nitrogen purging.
Table 1: the mass parts of each component
| Raw materials | Parts by mass |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and cellulose added in equal proportion) | 4 |
| Lanthanum oxide doped titanium dioxide suspension C | 1 |
| PH regulator (ammonium bicarbonate and ammonia water are added in equal proportion) | 0.5 |
| Chain initiator (dibenzoyl peroxide) | 1.5 |
| Chain terminator (acetone thiosemicarbazone) | 3.5 |
And (3) drying in an oven at the temperature of 60 ℃, melting and mixing by using a single-screw extruder, discharging, and performing water-cooling, granulation and drying to prepare the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch.
Preparing a rare earth doped titanium dioxide modified polyvinyl chloride composite material:
(1) preparing raw materials, wherein the raw materials comprise (by weight): 0.1% of rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch and 99.9% of polyvinyl chloride;
(2) putting the raw materials in the step (1) into a high-speed mixer, and fully mixing for 5min to obtain a mixture A;
(3) feeding the mixture A in the step (2) into a double-screw extruder through a main feed, and performing melt extrusion through the double-screw extruder, wherein the processing temperature is 180 ℃, and the screw rotating speed is 300 r/min;
(4) and (3) bracing, cooling, granulating and drying to obtain the rare earth doped titanium dioxide modified polyvinyl chloride composite material.
Example 2:
the embodiment provides a preparation method of a rare earth doped titanium dioxide modified polyvinyl chloride composite material, which comprises the following steps:
preparation of rare earth doped titanium dioxide powder:
A. dissolving 10ml of isopropyl titanate in 100ml of ethanol, and performing ultrasonic stirring and uniform dispersion to obtain a solution A;
B. weighing 27.5g of cerium oxide, dispersing in 1100mL of ethanol solution, and fully and ultrasonically stirring and filtering to obtain a solution B;
C. ultrasonically stirring, continuously and slowly dripping 1100mL of B solution into the A solution at room temperature, and then aging in a dark place for 168 hours to obtain the rare earth doped titanium dioxide sol, wherein the dripping speed is 1mL per second;
D. drying, molding, placing in a muffle furnace, calcining at 600 ℃ for 1 hour, and physically grinding to obtain rare earth doped titanium dioxide powder;
preparing rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch:
dispersing the prepared rare earth doped titanium dioxide powder in deionized water, performing ultrasonic dispersion to prepare a suspension C, cleaning a reaction kettle, sequentially adding deionized water, a dispersing agent and a rare earth doped titanium dioxide suspension C, pH regulator which are quantitatively shown in table 2 into the reaction kettle, finally adding an initiator into the polymerization kettle, sealing and vacuumizing after the feeding is finished, maintaining the pressure for 60min, and performing the next step of experiment after the readings are not obviously changed; starting stirring, setting the rotating speed at 500r/min, adding vinyl chloride monomer, fully and uniformly mixing, heating to 75 ℃, and starting polymerization reaction; when the pressure in the reaction kettle is reduced to-0.1 MPa, the reaction is determined to be complete, a chain terminator is added, and the material is discharged after nitrogen purging.
Table 2: the mass parts of each component
| Raw materials | Parts by mass |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and cellulose added in equal proportion) | 4 |
| Cerium oxide doped titanium dioxide suspension C | 4 |
| PH regulator (ammonium bicarbonate and ammonia water are added in equal proportion) | 0.5 |
| Chain initiator (azodiisobutyronitrile and lauroyl peroxide in equal proportion) | 1.5 |
| Chain terminator (acetone thiosemicarbazone) | 3.5 |
Drying in an oven at 40 ℃, melting and mixing by a single screw extruder, discharging, water-cooling, granulating and drying to prepare the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch.
Preparing a rare earth doped titanium dioxide modified polyvinyl chloride composite material:
(1) preparing raw materials, wherein the raw materials comprise (by weight): 10% of rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch and 90% of polyvinyl chloride;
(2) putting the raw materials in the step (1) into a high-speed mixer, and fully mixing for 10min to obtain a mixture A;
(3) feeding the mixture A in the step (2) into a double-screw extruder through a main feed, and performing melt extrusion through the double-screw extruder, wherein the processing temperature is 200 ℃, and the screw rotating speed is 150 r/min;
(4) and (3) bracing, cooling, granulating and drying to obtain the rare earth doped titanium dioxide modified polyvinyl chloride composite material.
Example 3:
the embodiment provides a preparation method of a rare earth doped titanium dioxide modified polyvinyl chloride composite material, which comprises the following steps:
preparation of rare earth doped titanium dioxide powder:
A. dissolving 20ml of butyl titanate in 50ml of methanol, and performing ultrasonic stirring and uniform dispersion to obtain a solution A;
B. weighing 8.75g of lanthanum oxide, dispersing in 350mL of ethanol solution, and fully and ultrasonically stirring and filtering to obtain a solution B;
C. ultrasonically stirring, continuously and slowly dripping 350mL of the solution B into the solution A at room temperature, and then aging in a dark place for 72 hours to obtain rare earth doped titanium dioxide sol, wherein the dripping speed is 0.5mL per second;
D. drying, molding, placing in a muffle furnace, calcining at the set temperature of 400 ℃ for 3 hours, and physically grinding to obtain rare earth doped titanium dioxide powder;
preparing rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch:
dispersing the prepared rare earth doped titanium dioxide powder in deionized water, performing ultrasonic dispersion to prepare a suspension C, cleaning a reaction kettle, sequentially adding deionized water, a dispersing agent and a rare earth doped titanium dioxide suspension C, pH regulator which are quantitatively shown in table 3 into the reaction kettle, finally adding an initiator into the polymerization kettle, sealing and vacuumizing after the feeding is finished, maintaining the pressure for 40min, and performing the next step of experiment after the readings are not obviously changed; starting stirring, setting the rotating speed at 500r/min, adding vinyl chloride monomer, fully and uniformly mixing, heating to 60 ℃, and starting polymerization reaction; when the pressure in the reaction kettle is reduced to-0.1 MPa, the reaction is determined to be complete, a chain terminator is added, and the material is discharged after nitrogen purging.
Table 3: the mass parts of each component
| Raw materials | Parts by mass |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and cellulose added in equal proportion) | 4 |
| Lanthanum oxide doped titanium dioxide suspension C | 15 |
| PH regulator (calcium hydroxide and sodium hydroxide are added in equal proportion) | 0.5 |
| Chain initiator (dibenzoyl peroxide) | 1.5 |
| Chain terminator (acetone thiosemicarbazone) | 3.5 |
And (3) drying in an oven at the temperature of 60 ℃, melting and mixing by using a single-screw extruder, discharging, and performing water-cooling, granulation and drying to prepare the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch.
Preparing a rare earth doped titanium dioxide modified polyvinyl chloride composite material:
(1) preparing raw materials, wherein the raw materials comprise (by weight): 5% of rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch and 95% of polyvinyl chloride;
(2) putting the raw materials in the step (1) into a high-speed mixer, and fully mixing for 7min to obtain a mixture A;
(3) feeding the mixture A in the step (2) into a double-screw extruder through a main feed, and performing melt extrusion through the double-screw extruder, wherein the processing temperature is 190 ℃, and the screw rotating speed is 200 r/min;
(4) and (3) bracing, cooling, granulating and drying to obtain the rare earth doped titanium dioxide modified polyvinyl chloride composite material.
Example 4:
the embodiment provides a preparation method of a rare earth doped titanium dioxide modified polyvinyl chloride composite material, which comprises the following steps:
preparation of rare earth doped titanium dioxide powder:
A. dissolving 10ml of isopropyl titanate in 10ml of isopropanol, and obtaining solution A after ultrasonic stirring and uniform dispersion;
B. weighing 4g of cerium oxide, dispersing in 160mL of ethanol solution, and fully and ultrasonically stirring and filtering to obtain a solution B;
C. ultrasonically stirring, continuously and slowly dripping 160mL of the solution B into the solution A at room temperature, and then aging in the dark for 96h to obtain the rare earth doped titanium dioxide sol, wherein the dripping speed is 1mL per second;
D. drying, molding, placing in a muffle furnace, calcining at the set temperature of 400 ℃ for 1 hour, and physically grinding to obtain rare earth doped titanium dioxide powder;
preparing rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch:
dispersing the prepared rare earth doped titanium dioxide powder in deionized water, performing ultrasonic dispersion to prepare a suspension C, cleaning a reaction kettle, sequentially adding deionized water, a dispersing agent and a rare earth doped titanium dioxide suspension C, pH regulator which are quantitatively shown in Table 4 into the reaction kettle, finally adding an initiator into the polymerization kettle, sealing and vacuumizing after the feeding is finished, maintaining the pressure for 60min, and performing the next step of experiment after the readings are not obviously changed; starting stirring, setting the rotating speed at 400r/min, adding vinyl chloride monomer, fully and uniformly mixing, heating to 60 ℃, and starting polymerization reaction; when the pressure in the reaction kettle is reduced to-0.1 MPa, the reaction is determined to be complete, a chain terminator is added, and the material is discharged after nitrogen purging.
Table 4: the mass parts of each component
| Raw materials | Parts by mass |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and cellulose added in equal proportion) | 4 |
| Cerium oxide doped titanium dioxide suspension C | 10 |
| PH regulator (ammonium bicarbonate and ammonia water are added in equal proportion) | 0.5 |
| Chain initiator (dibenzoyl peroxide) | 1.5 |
| Chain terminator (acetone thiosemicarbazone) | 3.5 |
Drying in an oven at 40 ℃, melting and mixing by a single screw extruder, discharging, water-cooling, granulating and drying to prepare the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch.
Preparing a rare earth doped titanium dioxide modified polyvinyl chloride composite material:
(1) preparing raw materials, wherein the raw materials comprise (by weight): 8% of rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch and 92% of polyvinyl chloride;
(2) putting the raw materials in the step (1) into a high-speed mixer, and fully mixing for 8min to obtain a mixture A;
(3) feeding the mixture A in the step (2) into a double-screw extruder through a main feed, and performing melt extrusion through the double-screw extruder, wherein the processing temperature is 185 ℃, and the screw rotating speed is 250 r/min;
(4) and (3) bracing, cooling, granulating and drying to obtain the rare earth doped titanium dioxide modified polyvinyl chloride composite material.
Comparative example 1:
the comparative example provides a preparation method of a titanium dioxide modified polyvinyl chloride composite material, which comprises the following steps:
preparation of titanium dioxide powder:
A. dissolving 20ml of butyl titanate in 50ml of methanol, ultrasonically stirring and uniformly dispersing to obtain a solution A, and then aging in a dark place for 72 hours to obtain titanium dioxide sol;
B. drying, molding, placing in a muffle furnace, calcining at the set temperature of 400 ℃ for 3 hours, and physically grinding to obtain titanium dioxide powder;
preparing titanium dioxide in-situ polymerization polyvinyl chloride master batch:
dispersing the prepared titanium dioxide powder in deionized water, performing ultrasonic dispersion to prepare a suspension C, cleaning a reaction kettle, sequentially adding deionized water, a dispersing agent and a titanium dioxide suspension C, pH regulator which are quantitatively shown in table 5 into the reaction kettle, finally adding an initiator into the polymerization kettle, sealing and vacuumizing after the feeding is finished, maintaining the pressure for 40min, and performing the next experiment after the readings are not obviously changed; starting stirring, setting the rotating speed at 500r/min, adding vinyl chloride monomer, fully and uniformly mixing, heating to 60 ℃, and starting polymerization reaction; when the pressure in the reaction kettle is reduced to-0.1 MPa, the reaction is determined to be complete, a chain terminator is added, and the material is discharged after nitrogen purging.
Table 5: the mass parts of each component
| Raw materials | Parts by mass |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| DispersingAgent (polyvinyl alcohol and cellulose added in equal proportion) | 4 |
| Titanium dioxide suspension C | 15 |
| PH regulator (calcium hydroxide and sodium hydroxide are added in equal proportion) | 0.5 |
| Chain initiator (dibenzoyl peroxide) | 1.5 |
| Chain terminator (acetone thiosemicarbazone) | 3.5 |
Drying in a drying oven at 60 ℃, melting and mixing by a single screw extruder, discharging, water-cooling, granulating and drying to prepare the titanium dioxide in-situ polymerized polyvinyl chloride master batch.
Preparing a titanium dioxide modified polyvinyl chloride composite material:
(1) preparing raw materials, wherein the raw materials comprise (by weight): 5% of titanium dioxide in-situ polymerization polyvinyl chloride master batch and 95% of polyvinyl chloride;
(2) putting the raw materials in the step (1) into a high-speed mixer, and fully mixing for 7min to obtain a mixture A;
(3) feeding the mixture A in the step (2) into a double-screw extruder through a main feed, and performing melt extrusion through the double-screw extruder, wherein the processing temperature is 190 ℃, and the screw rotating speed is 200 r/min;
(4) and (3) bracing, cooling, granulating and drying to obtain the titanium dioxide modified polyvinyl chloride composite material.
Comparative example 2:
the comparative example provides a preparation method of a rare earth doped titanium dioxide modified polyvinyl chloride composite material, which comprises the following steps:
preparation of rare earth doped titanium dioxide powder:
A. dissolving 10ml of isopropyl titanate in 10ml of isopropanol, and obtaining solution A after ultrasonic stirring and uniform dispersion;
B. weighing 4g of cerium oxide, dispersing in 160mL of ethanol solution, and fully and ultrasonically stirring and filtering to obtain a solution B;
C. ultrasonically stirring, continuously and slowly dripping 160mLB solution into the solution A at room temperature, and then aging in the dark for 96 hours to obtain the rare earth doped titanium dioxide sol, wherein the dripping speed is 1ml per second;
D. drying, molding, placing in a muffle furnace, calcining at the set temperature of 400 ℃ for 1 hour, and physically grinding to obtain rare earth doped titanium dioxide powder;
preparing a rare earth doped titanium dioxide modified polyvinyl chloride composite material:
(1) preparing raw materials, wherein the raw materials comprise (by weight): 0.5 percent of rare earth doped titanium dioxide powder and 99.5 percent of polyvinyl chloride;
(2) putting the raw materials in the step (1) into a high-speed mixer, and fully mixing for 8min to obtain a mixture A;
(3) feeding the mixture A in the step (2) into a double-screw extruder through a main feed, and performing melt extrusion through the double-screw extruder, wherein the processing temperature is 185 ℃, and the screw rotating speed is 250 r/min;
(4) and (3) bracing, cooling, granulating and drying to obtain the rare earth doped titanium dioxide modified polyvinyl chloride composite material.
Application example 1
The rare earth doped titanium dioxide modified polyvinyl chloride composite materials prepared in examples 1-4 and comparative examples 1-2 were tested, wherein the aging retention rate is the retention rate of the tensile property of the sample after 1200h aging test, and the test results are shown in table 6.
TABLE 6
As can be seen from the table above, the addition of the rare earth doped titanium dioxide modified polyvinyl chloride can significantly improve various comprehensive properties of PVC. The increase of Vicat softening temperature means that the application range of the modified polyvinyl chloride composite material can be further widened, and the mechanical property of PVC can be fully exerted.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
Claims (10)
1. The preparation method of the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch is characterized by comprising the following steps:
step 1, preparing rare earth doped titanium dioxide powder;
step 1.1, dissolving titanate in alcohol substances to prepare solution A;
step 1.2, dispersing the rare earth oxide in an alcohol substance, fully stirring by ultrasonic waves, and filtering to obtain a solution B;
step 1.3, under the condition of ultrasonic stirring, dropwise adding the solution B into the solution A, and then aging in a dark place to obtain rare earth doped titanium dioxide sol;
step 1.4, drying and molding the rare earth doped titanium dioxide sol, placing the dried and molded rare earth doped titanium dioxide sol in a muffle furnace, calcining the sol for 1 to 4 hours at the set temperature of 300 to 600 ℃, and physically grinding the sol to obtain rare earth doped titanium dioxide powder;
step 2, preparation of rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch
Dispersing the rare earth doped titanium dioxide powder obtained in the step 1.4 in water to prepare suspension C; and adding the suspension C into a polyvinyl chloride suspension polymerization system for polymerization, and discharging after the polymerization is finished to prepare the rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch.
2. The process according to claim 1, wherein the titanate is tetrabutyl titanate or isopropyl titanate; the alcohol substance is any one of methanol, ethanol and isopropanol; the rare earth oxide is lanthanum oxide or cerium oxide.
3. The preparation method according to claim 1, wherein in the step 1.1, the volume ratio of titanate to alcohol is 1: 1-10; in the step 1.2, the volume ratio of the rare earth oxide substance to the alcohol substance is 1g:40 mL.
4. The method of claim 1, wherein in step 1.3, the A, B solution volume ratio is 1: 1-10, the dripping rate is 0.01-1 ml per second, and the aging time is 24-168 hours.
5. The method of claim 1, wherein the suspension polymerization system of polyvinyl chloride comprises monomers, deionized water, an oil-soluble initiator, a dispersant, a chain terminator, and a pH adjuster; the monomer is chloroethylene; the oil-soluble initiator is peroxyacyl, peroxyester, peroxydicarbonate or azo; the dispersant is polyvinyl alcohol or cellulose ethers; the chain terminator is acetone thiosemicarbazone; the pH regulator is one or more of ammonium bicarbonate, ammonia water, sodium hydroxide, sodium carbonate, sodium phosphate and calcium hydroxide.
6. The method of claim 5, wherein the mass fraction ratio of the vinyl chloride, the deionized water, the dispersant, the rare earth-doped titanium dioxide suspension C, pH modifier, the oil-soluble initiator, and the chain terminator is 1400: 1400: 4: 1-15: 0.5: 1.5: 3.5.
7. the preparation method of claim 1, wherein in the step 2, the discharging after the polymerization is completed to prepare the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch comprises the following specific steps:
and discharging after polymerization, drying in an oven at the temperature of 40-60 ℃, melting and mixing by a single-screw extruder, discharging, and performing water-cooling, granulating and drying to prepare the rare earth doped titanium dioxide in-situ polymerized polyvinyl chloride master batch.
8. The method according to claim 1, wherein the polymerization process in step 2 is:
step 2.1, sequentially putting deionized water, a dispersing agent and a rare earth doped titanium dioxide suspension C, pH regulator into a polymerization kettle, adding an initiator, sealing a cover, vacuumizing, and maintaining the pressure for 30-60 min;
2.2, adding vinyl chloride monomer under the stirring condition, fully and uniformly mixing, heating to 50-75 ℃, and starting a polymerization reaction;
step 2.3, adding a chain terminator when the pressure in the reaction kettle is reduced to-0.1 MPa, and discharging after nitrogen purging;
the stirring conditions in the step 2.2 are as follows: the rotation speed is 100 to 700 r/min.
9. A rare earth doped titanium dioxide modified polyvinyl chloride composite material is characterized by comprising
0.1-10 parts by mass of rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch prepared by the method of claim 1;
90-99.9 parts by mass of polyvinyl chloride.
10. The method for preparing the rare earth doped titanium dioxide modified polyvinyl chloride composite material according to claim 9, comprising the steps of:
(1) weighing rare earth doped titanium dioxide in-situ polymerization polyvinyl chloride master batch and polyvinyl chloride according to the weight ratio, and putting the weighed materials into a high-speed mixer for fully mixing;
(2) and (2) feeding the material obtained in the step (1) into a double-screw extruder, performing melt extrusion through the double-screw extruder, wherein the processing temperature is 180-200 ℃, the screw rotating speed is 150-300 r/min, and then performing bracing, cooling, grain-sized dicing and drying treatment to obtain the rare earth doped titanium dioxide modified polyvinyl chloride composite material.
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