CN110054846A - A kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material and preparation method - Google Patents
A kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material and preparation method Download PDFInfo
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Abstract
The invention belongs to technical field of high-molecule composite preparation, in particular to a kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material and preparation method, the composite material is made of rare earth-doped titanium dioxide and polyvinyl chloride, and the master batch as obtained by in-situ polymerization and polyvinyl chloride melting mixing are made；It is more preferable to be dispersed in effect in titania solution compared to the later period by rare earth doped element during titanium dioxide synthesis for rare earth oxide, while rare earth and titanium dioxide have synergistic effect, therefore the material prepared has the steady light stability energy of more excellent heat；Rare earth-doped titanium dioxide is added during in-situ polymerization polyvinyl chloride, the interface binding power between inorganic filler and high molecular material can be dramatically increased, be more advantageous to dispersion of the rare earth-doped titanium dioxide in polyvinyl chloride composite materials；Preparation method of the invention is simple and practical, is suitable for large-scale industrial production and application.
Description
Technical field
The invention belongs to technical field of high-molecule composite preparation, in particular to a kind of rare earth-doped titanium dioxide is modified
Polyvinyl chloride composite materials and preparation method.
Background technique
PVC is widely applied in today's society as a kind of plastics that processing performance is excellent.But its is heat-resisting and resistance to
Ageing properties are poor, and heat distortion temperature is lower, constrain it in the application of numerous areas.At present to PVC heat-resisting ageing-resisting performance
Research be concentrated mainly on by the methods of adding auxiliary agent, inorganic rigid particle during processing and crosslinking.It is modified
Though agent modified polyvinyl chloride can be obviously improved vicat temperature, price costly, compared to polyvinyl chloride itself, is modified cost
It is higher.PVC crosslinking technological can be obviously improved its thermal deformation and thermal decomposition temperature, and technological difficulties are more in preparation process, uncomfortable
For large-scale industrial production.Stiff differential equations modified polyvinyl-chloride composite material, preparation method are simply easily realized.
There are a variety of effects when substance is in nanoscale, obtained using nanoscale inorganic filler modified high-molecular wide
General concern.Since surface can be very high, general manufacturing process is difficult to disperse it in high molecular material material of nanoscale
Uniformly, and general inorganic nano-filler, surface nature differ larger with macromolecule, the inorganic nano-filler in mixed process
It is easy itself and forms larger-size aggregate, make its scale in material much larger than nanoscale, lose the effect of nanoscale
Fruit.
Summary of the invention
The present invention solves the above-mentioned technical problems in the prior art, and it is modified poly- to provide a kind of rare earth-doped titanium dioxide
Vinyl chloride composite material and preparation method.
To solve the above problems, technical scheme is as follows:
The preparation method of rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch, comprising the following steps:
Step 1 prepares rare earth-doped titanium dioxide powder；
Titanate esters are dissolved in alcohols material by step 1.1, and solution A is made；
Rare earth oxide is dispersed alcohols material by step 1.2, sufficiently filters after ultrasonic agitation and B solution is made；
Under the conditions of step 1.3, ultrasonic agitation, dark place ageing is put in after dropwise addition B solution into solution A and is made rear-earth-doped
TiO 2 sol；
The rare earth-doped titanium dioxide colloidal sol drying and moulding is placed on Muffle furnace by step 1.4, and setting temperature 300~
600 DEG C are calcined 1~4 hour, and rare earth-doped titanium dioxide powder is made after physical grinding；
The preparation of step 2, rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch
By in rare earth-doped titanium dioxide powder disperse water obtained in step 1.4, suspension C is made；It will be described suspended
Liquid C, which is added in polyvinyl chloride suspension polymerization system, to be polymerize, and discharging prepares rare earth-doped titanium dioxide original position after the completion of polymerization
Polymeric polyvinyl chloride master batch.
Preferably, the titanate esters are butyl titanate or isopropyl titanate；The alcohols material is methanol, second
Any one in alcohol, isopropanol；The rare earth oxide is lanthana or cerium oxide.
Preferably, in the step 1.1, the volume ratio of titanate esters and alcohols material is 1:1~10.
Preferably, in the step 1.2, rare-earth oxidation amount of substance and alcohols material volume ratio are 1g:40mL.
Preferably, in the step 1.3, A, B solution volume ratio are 1:1~10.
Preferably, in the step 1.3, drop rate is 0.01~1ml per second, and digestion time is 24~168h.
Preferably, include monomer in the polyvinyl chloride suspension polymerization system, deionized water, oil-soluble initiator, divide
Powder, chain terminating agent and pH adjusting agent；The monomer is vinyl chloride；The oil-soluble initiator is peroxide acyl class, peroxide
Esters, peroxy dicarbonates or azo；The dispersing agent is polyvinyl alcohol or cellulose ethers；The chain termination
Agent is acetone semicarbazone thiocarbamide；The pH adjusting agent is ammonium hydrogen carbonate, ammonium hydroxide, sodium hydroxide, sodium carbonate, sodium phosphate, hydrogen-oxygen
Change any one or a few in calcium.
Preferably, vinyl chloride, deionized water, dispersing agent, rear-earth-doped two in the polyvinyl chloride suspension polymerization system
Titanium oxide suspension C, pH adjusting agent, the mass fraction ratio of initiator and chain terminating agent are 1400:1400:4:1~15:0.5:
1.5:3.5.
Preferably, in the step 2, discharging prepares rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride after the completion of polymerization
The specific steps of master batch are as follows:
It discharges, is placed in the baking oven that temperature is 40~60 DEG C after drying through single screw extrusion machine melting mixing after the completion of polymerization
After discharge, rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch can be prepared after water cooling granulated and dried.
Preferably, the polymerization technique in the step 2 are as follows:
Deionized water, dispersing agent, rare earth-doped titanium dioxide suspension C, pH adjusting agent are successively put into and are gathered by step 2.1
Kettle is closed, initiator is added, capping vacuumizes, 30~60min of pressure maintaining；
Vinyl chloride monomer is put under step 2.2, stirring condition, after being sufficiently mixed uniformly, 50~75 DEG C is warming up to, starts to gather
Close reaction；
Step 2.3, when reacting kettle inner pressure is down to -0.1MPa, be added chain terminating agent, nitrogen purging after discharge.
Preferably, the stirring condition in the step 2.2 are as follows: 100~700r/min of revolving speed.
A kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material, including
0.1~10 mass parts of rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch；
90~99.9 mass parts of polyvinyl chloride.
The preparation method of above-mentioned rare earth-doped titanium dioxide modified polyvinyl-chloride composite material, comprising the following steps:
(1) rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch, polyvinyl chloride are weighed according to the weight ratio, and will
The material weighed up, which is put into super mixer, to be sufficiently mixed；
(2) material obtained step (1) is sent into double screw extruder, by double screw extruder melting extrusion,
Middle processing temperature is 180~200 DEG C, and screw speed is 150~300r/min, by tie rod, cooling, pelletizing, drying process, system
Obtain the rare earth-doped titanium dioxide modified polyvinyl-chloride composite material.
Compared with the existing technology, advantages of the present invention is as follows,
1, the present invention rare earth doped element during titanium dioxide synthesis, disperses rare earth oxide compared to the later period
Effect is more preferable in titania solution, while rare earth and titanium dioxide have synergistic effect, therefore the material prepared has more
Add the steady light stability energy of excellent heat.
2, rare earth-doped titanium dioxide is added during in-situ polymerization polyvinyl chloride, inorganic filler and high score can be dramatically increased
Interface binding power between sub- material is more advantageous to dispersion of the rare earth-doped titanium dioxide in polyvinyl chloride composite materials.
3, preparation method of the invention is simple and practical, is suitable for large-scale industrial production and application.
Specific embodiment
Polyvinyl chloride employed in embodiment is commercially available universal Corvic.
Embodiment 1:
The present embodiment provides a kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material preparation method, including it is following
Step:
The preparation of rare earth-doped titanium dioxide powder:
A. 10ml butyl titanate is dissolved in 10ml ethyl alcohol, ultrasonic agitation obtains solution A after being uniformly dispersed；
B. 0.5g lanthana is weighed again to be dispersed in 20mL ethanol solution, sufficiently obtains B solution after ultrasonic agitation filtering；
C. it is stirred by ultrasonic, continues to be put in dark place ageing after slowly into solution A after dropwise addition 20mLB solution for 24 hours i.e. at room temperature
Rare earth-doped titanium dioxide colloidal sol can be obtained, wherein rate of addition is 0.01ml per second；
D. drying and moulding is placed on Muffle furnace, is arranged 300 DEG C of temperature and calcines 4 hours, rare earth can be obtained after physical grinding and is mixed
Miscellaneous titania powder；
The preparation of rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch:
In deionized water by rare earth-doped titanium dioxide powder obtained dispersion, suspension C is made in ultrasonic disperse, cleaning
After reaction kettle, by deionized water quantitative as shown in table 1, dispersing agent, rare earth-doped titanium dioxide suspension C, pH adjusting agent
Reaction kettle is successively put into, finally initiator is added in polymeric kettle, after feeding intake, capping is vacuumized, pressure maintaining 30min, registration
After significant change, next step experiment is carried out；Starting stirring, setting revolving speed are 700r/min, put into vinyl chloride monomer, sufficiently mixed
After closing uniformly, 50 DEG C are warming up to, starts polymerization reaction；When reacting kettle inner pressure is down to -0.1MPa, fully reacting is regarded as,
Chain terminating agent is added, discharges after nitrogen purging.
Table 1: each component mass fraction
| Raw material | Mass fraction |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and the addition of cellulose equal proportion) | 4 |
| Lanthanum oxide doping titanium dioxide suspension C | 1 |
| PH adjusting agent (ammonium hydrogen carbonate and the addition of ammonium hydroxide equal proportion) | 0.5 |
| Chain initiator (dibenzoyl peroxide) | 1.5 |
| Chain terminating agent (acetone semicarbazone thiocarbamide) | 3.5 |
It is placed in the baking oven that temperature is 60 DEG C and discharges after single screw extrusion machine melting mixing after drying, water cooling granulated and dried
After can prepare rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch.
The preparation of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material:
(1) prepare raw material, the raw material includes (according to weight ratio): rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride
Master batch 0.1%, polyvinyl chloride 99.9%；
(2) raw material described in step (1) is put into super mixer and is sufficiently mixed 5min and obtains mixture A；
(3) mixture A described in step (2) is sent into double screw extruder through main feeding, passes through twin-screw extrusion
Machine melting extrusion, wherein processing temperature is 180 DEG C, screw speed 300r/min；
(4) modified poly- to get a kind of rare earth-doped titanium dioxide of the invention by tie rod, cooling, pelletizing, drying process
Vinyl chloride composite material.
Embodiment 2:
The present embodiment provides a kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material preparation method, including it is following
Step:
The preparation of rare earth-doped titanium dioxide powder:
A. 10ml isopropyl titanate is dissolved in 100ml ethyl alcohol, ultrasonic agitation obtains solution A after being uniformly dispersed；
B. it weighs 27.5g cerium oxide again to be dispersed in 1100mL ethanol solution, it is molten sufficiently to obtain B after ultrasonic agitation filtering
Liquid；
C. it is stirred by ultrasonic, continues to be put in dark place ageing 168h after 1100mL B solution is slowly added dropwise into solution A at room temperature
Rare earth-doped titanium dioxide colloidal sol can be obtained, wherein rate of addition is 1ml per second；
D. drying and moulding is placed on Muffle furnace, is arranged 600 DEG C of temperature and calcines 1 hour, rare earth can be obtained after physical grinding and is mixed
Miscellaneous titania powder；
The preparation of rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch:
In deionized water by rare earth-doped titanium dioxide powder obtained dispersion, suspension C is made in ultrasonic disperse, cleaning
After reaction kettle, by deionized water quantitative as shown in table 2, dispersing agent, rare earth-doped titanium dioxide suspension C, pH adjusting agent
Reaction kettle is successively put into, finally initiator is added in polymeric kettle, after feeding intake, capping is vacuumized, pressure maintaining 60min, registration
After significant change, next step experiment is carried out；Starting stirring, setting revolving speed are 500r/min, put into vinyl chloride monomer, sufficiently mixed
After closing uniformly, 75 DEG C are warming up to, starts polymerization reaction；When reacting kettle inner pressure is down to -0.1MPa, fully reacting is regarded as,
Chain terminating agent is added, discharges after nitrogen purging.
Table 2: each component mass fraction
| Raw material | Mass fraction |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and the addition of cellulose equal proportion) | 4 |
| Cerium oxide-doped titanium dioxide suspension C | 4 |
| PH adjusting agent (ammonium hydrogen carbonate and the addition of ammonium hydroxide equal proportion) | 0.5 |
| Chain initiator (azo-bis-isobutyl cyanide and dilauroyl peroxide equal proportion) | 1.5 |
| Chain terminating agent (acetone semicarbazone thiocarbamide) | 3.5 |
It is placed in the baking oven that temperature is 40 DEG C and discharges after single screw extrusion machine melting mixing after drying, water cooling granulated and dried
After can prepare rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch.
The preparation of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material:
(1) prepare raw material, the raw material includes (according to weight ratio): rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride
Master batch 10%, polyvinyl chloride 90%；
(2) raw material described in step (1) is put into super mixer and is sufficiently mixed 10min and obtains mixture A；
(3) mixture A described in step (2) is sent into double screw extruder through main feeding, passes through twin-screw extrusion
Machine melting extrusion, wherein processing temperature is 200 DEG C, screw speed 150r/min；
(4) modified poly- to get a kind of rare earth-doped titanium dioxide of the invention by tie rod, cooling, pelletizing, drying process
Vinyl chloride composite material.
Embodiment 3:
The present embodiment provides a kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material preparation method, including it is following
Step:
The preparation of rare earth-doped titanium dioxide powder:
A. 20ml butyl titanate is dissolved in 50ml methanol, ultrasonic agitation obtains solution A after being uniformly dispersed；
B. 8.75g lanthana is weighed again to be dispersed in 350mL ethanol solution, sufficiently obtains B solution after ultrasonic agitation filtering；
C. it is stirred by ultrasonic, continues to be put in dark place ageing 72h i.e. after 350mL B solution is slowly added dropwise into solution A at room temperature
Rare earth-doped titanium dioxide colloidal sol can be obtained, wherein rate of addition is 0.5ml per second；
D. drying and moulding is placed on Muffle furnace, is arranged 400 DEG C of temperature and calcines 3 hours, rare earth can be obtained after physical grinding and is mixed
Miscellaneous titania powder；
The preparation of rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch:
In deionized water by rare earth-doped titanium dioxide powder obtained dispersion, suspension C is made in ultrasonic disperse, cleaning
After reaction kettle, by deionized water quantitative as shown in table 3, dispersing agent, rare earth-doped titanium dioxide suspension C, pH adjusting agent
Reaction kettle is successively put into, finally initiator is added in polymeric kettle, after feeding intake, capping is vacuumized, pressure maintaining 40min, registration
After significant change, next step experiment is carried out；Starting stirring, setting revolving speed are 500r/min, put into vinyl chloride monomer, sufficiently mixed
After closing uniformly, 60 DEG C are warming up to, starts polymerization reaction；When reacting kettle inner pressure is down to -0.1MPa, fully reacting is regarded as,
Chain terminating agent is added, discharges after nitrogen purging.
Table 3: each component mass fraction
| Raw material | Mass fraction |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and the addition of cellulose equal proportion) | 4 |
| Lanthanum oxide doping titanium dioxide suspension C | 15 |
| PH adjusting agent (calcium hydroxide and the addition of sodium hydroxide equal proportion) | 0.5 |
| Chain initiator (dibenzoyl peroxide) | 1.5 |
| Chain terminating agent (acetone semicarbazone thiocarbamide) | 3.5 |
It is placed in the baking oven that temperature is 60 DEG C and discharges after single screw extrusion machine melting mixing after drying, water cooling granulated and dried
After can prepare rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch.
The preparation of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material:
(1) prepare raw material, the raw material includes (according to weight ratio): rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride
Master batch 5%, polyvinyl chloride 95%；
(2) raw material described in step (1) is put into super mixer and is sufficiently mixed 7min and obtains mixture A；
(3) mixture A described in step (2) is sent into double screw extruder through main feeding, passes through twin-screw extrusion
Machine melting extrusion, wherein processing temperature is 190 DEG C, screw speed 200r/min；
(4) modified poly- to get a kind of rare earth-doped titanium dioxide of the invention by tie rod, cooling, pelletizing, drying process
Vinyl chloride composite material.
Embodiment 4:
The present embodiment provides a kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material preparation method, including it is following
Step:
The preparation of rare earth-doped titanium dioxide powder:
A. 10ml isopropyl titanate is dissolved in 10ml isopropanol, ultrasonic agitation obtains solution A after being uniformly dispersed；
B. 4g cerium oxide is weighed again to be dispersed in 160mL ethanol solution, sufficiently obtains B solution after ultrasonic agitation filtering；
C. it is stirred by ultrasonic, continues to be put in dark place ageing 96h i.e. after 160mL B solution is slowly added dropwise into solution A at room temperature
Rare earth-doped titanium dioxide colloidal sol can be obtained, wherein rate of addition is 1ml per second；
D. drying and moulding is placed on Muffle furnace, is arranged 400 DEG C of temperature and calcines 1 hour, rare earth can be obtained after physical grinding and is mixed
Miscellaneous titania powder；
The preparation of rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch:
In deionized water by rare earth-doped titanium dioxide powder obtained dispersion, suspension C is made in ultrasonic disperse, cleaning
After reaction kettle, by deionized water quantitative as shown in table 4, dispersing agent, rare earth-doped titanium dioxide suspension C, pH adjusting agent
Reaction kettle is successively put into, finally initiator is added in polymeric kettle, after feeding intake, capping is vacuumized, pressure maintaining 60min, registration
After significant change, next step experiment is carried out；Starting stirring, setting revolving speed are 400r/min, put into vinyl chloride monomer, sufficiently mixed
After closing uniformly, 60 DEG C are warming up to, starts polymerization reaction；When reacting kettle inner pressure is down to -0.1MPa, fully reacting is regarded as,
Chain terminating agent is added, discharges after nitrogen purging.
Table 4: each component mass fraction
| Raw material | Mass fraction |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and the addition of cellulose equal proportion) | 4 |
| Cerium oxide-doped titanium dioxide suspension C | 10 |
| PH adjusting agent (ammonium hydrogen carbonate and the addition of ammonium hydroxide equal proportion) | 0.5 |
| Chain initiator (dibenzoyl peroxide) | 1.5 |
| Chain terminating agent (acetone semicarbazone thiocarbamide) | 3.5 |
It is placed in the baking oven that temperature is 40 DEG C and discharges after single screw extrusion machine melting mixing after drying, water cooling granulated and dried
After can prepare rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch.
The preparation of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material:
(1) prepare raw material, the raw material includes (according to weight ratio): rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride
Master batch 8%, polyvinyl chloride 92%；
(2) raw material described in step (1) is put into super mixer and is sufficiently mixed 8min and obtains mixture A；
(3) mixture A described in step (2) is sent into double screw extruder through main feeding, passes through twin-screw extrusion
Machine melting extrusion, wherein processing temperature is 185 DEG C, screw speed 250r/min；
(4) modified poly- to get a kind of rare earth-doped titanium dioxide of the invention by tie rod, cooling, pelletizing, drying process
Vinyl chloride composite material.
Comparative example 1:
This comparative example provides a kind of titania modified polyvinyl chloride composite materials preparation method, comprising the following steps:
The preparation of titania powder:
A. 20ml butyl titanate is dissolved in 50ml methanol, ultrasonic agitation obtains solution A after being uniformly dispersed, after be put in it is dark
Place ageing 72h can obtain TiO 2 sol；
B. drying and moulding is placed on Muffle furnace, is arranged 400 DEG C of temperature and calcines 3 hours, titanium dioxide can be obtained after physical grinding
Titanium powder；
The preparation of titanium dioxide in-situ polymerization polyvinyl chloride master batch:
In deionized water by titania powder obtained dispersion, suspension C is made in ultrasonic disperse, cleans reaction kettle
Afterwards, deionized water quantitative as shown in table 5, dispersing agent, titanium dioxide suspension C, pH adjusting agent are successively put into reaction kettle,
Finally initiator is added in polymeric kettle, after feeding intake, capping is vacuumized, pressure maintaining 40min, after registration is without significant change, into
Row is tested in next step；Starting stirring, setting revolving speed are 500r/min, put into vinyl chloride monomer, after being sufficiently mixed uniformly, are warming up to
60 DEG C, start polymerization reaction；When reacting kettle inner pressure is down to -0.1MPa, fully reacting is regarded as, chain terminating agent, nitrogen is added
Air-blowing discharges after sweeping.
Table 5: each component mass fraction
| Raw material | Mass fraction |
| Vinyl chloride | 1400 |
| Deionized water | 1400 |
| Dispersing agent (polyvinyl alcohol and the addition of cellulose equal proportion) | 4 |
| Titanium dioxide suspension C | 15 |
| PH adjusting agent (calcium hydroxide and the addition of sodium hydroxide equal proportion) | 0.5 |
| Chain initiator (dibenzoyl peroxide) | 1.5 |
| Chain terminating agent (acetone semicarbazone thiocarbamide) | 3.5 |
It is placed in the baking oven that temperature is 60 DEG C and discharges after single screw extrusion machine melting mixing after drying, water cooling granulated and dried
After can prepare titanium dioxide in-situ polymerization polyvinyl chloride master batch.
The preparation of titania modified polyvinyl chloride composite materials:
(1) prepare raw material, the raw material includes (according to weight ratio): titanium dioxide in-situ polymerization polyvinyl chloride master batch 5%,
Polyvinyl chloride 95%；
(2) raw material described in step (1) is put into super mixer and is sufficiently mixed 7min and obtains mixture A；
(3) mixture A described in step (2) is sent into double screw extruder through main feeding, passes through twin-screw extrusion
Machine melting extrusion, wherein processing temperature is 190 DEG C, screw speed 200r/min；
(4) by tie rod, cooling, pelletizing, drying process to get a kind of titania modified polyvinyl chloride composite materials.
Comparative example 2:
This comparative example provides a kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material preparation method, including following
Step:
The preparation of rare earth-doped titanium dioxide powder:
A. 10ml isopropyl titanate is dissolved in 10ml isopropanol, ultrasonic agitation obtains solution A after being uniformly dispersed；
B. 4g cerium oxide is weighed again to be dispersed in 160mL ethanol solution, sufficiently obtains B solution after ultrasonic agitation filtering；
C. it is stirred by ultrasonic, continues to be put in dark place ageing 96h after 160mLB solution is slowly added dropwise into solution A at room temperature
Rare earth-doped titanium dioxide colloidal sol is obtained, wherein rate of addition is 1ml per second；
D. drying and moulding is placed on Muffle furnace, is arranged 400 DEG C of temperature and calcines 1 hour, rare earth can be obtained after physical grinding and is mixed
Miscellaneous titania powder；
The preparation of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material:
(1) prepare raw material, the raw material includes (according to weight ratio): rare earth-doped titanium dioxide powder 0.5%, polychlorostyrene second
Alkene 99.5%；
(2) raw material described in step (1) is put into super mixer and is sufficiently mixed 8min and obtains mixture A；
(3) mixture A described in step (2) is sent into double screw extruder through main feeding, passes through twin-screw extrusion
Machine melting extrusion, wherein processing temperature is 185 DEG C, screw speed 250r/min；
(4) multiple to get a kind of rare earth-doped titanium dioxide modified polyvinyl chloride by tie rod, cooling, pelletizing, drying process
Condensation material.
Application Example 1
Rare earth-doped titanium dioxide modified polyvinyl-chloride composite material obtained by embodiment 1-4, comparative example 1-2 is carried out
Test, wherein aging retention is retention of the sample through 1200h degradation post-tensioning performance, and experimental result is as shown in table 6.
Table 6
As can be seen from the above table, rare earth-doped titanium dioxide modified polyvinyl chloride is added, the items of PVC are remarkably improved
Comprehensive performance.The promotion of vicat softening temperature, it is meant that modified polyvinyl chloride composite materials application range can be further
It widens, gives full play to the mechanical property of PVC.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (10)
1. the preparation method of rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch, which comprises the following steps:
Step 1 prepares rare earth-doped titanium dioxide powder；
Titanate esters are dissolved in alcohols material by step 1.1, and solution A is made；
Rare earth oxide is dispersed alcohols material by step 1.2, sufficiently filters after ultrasonic agitation and B solution is made；
Under the conditions of step 1.3, ultrasonic agitation, dark place ageing is put in after dropwise addition B solution into solution A and is made to obtain rear-earth-doped dioxy
Change titanium colloidal sol；
The rare earth-doped titanium dioxide colloidal sol drying and moulding is placed on Muffle furnace by step 1.4, is arranged 300~600 DEG C of temperature
Rare earth-doped titanium dioxide powder is made in calcining 1~4 hour after physical grinding；
The preparation of step 2, rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch
By in rare earth-doped titanium dioxide powder disperse water obtained in step 1.4, suspension C is made；The suspension C is added
Enter and polymerize in polyvinyl chloride suspension polymerization system, it is poly- to prepare rare earth-doped titanium dioxide in-situ polymerization for discharging after the completion of polymerization
Vinyl chloride master batch.
2. preparation method as described in claim 1, which is characterized in that the titanate esters are butyl titanate or metatitanic acid isopropyl
Ester；The alcohols material is methanol, ethyl alcohol, any one in isopropanol；The rare earth oxide is lanthana or oxidation
Cerium.
3. preparation method as described in claim 1, which is characterized in that in the step 1.1, the body of titanate esters and alcohols material
Product is than being 1:1~10；In the step 1.2, rare-earth oxidation amount of substance and alcohols material volume ratio are 1g:40mL.
4. preparation method as described in claim 1, which is characterized in that in the step 1.3, A, B solution volume ratio are 1:1
~10, drop rate is 0.01~1ml per second, and digestion time is 24~168h.
5. preparation method as described in claim 1, which is characterized in that comprising single in the polyvinyl chloride suspension polymerization system
Body, deionized water, oil-soluble initiator, dispersing agent, chain terminating agent and pH adjusting agent；The monomer is vinyl chloride；Described
Oil-soluble initiator is peroxide acyl class, peroxide esters, peroxy dicarbonates or azo；The dispersing agent is polyethylene
Alcohol or cellulose ethers；The chain terminating agent is acetone semicarbazone thiocarbamide；The pH adjusting agent be ammonium hydrogen carbonate, ammonium hydroxide,
Sodium hydroxide, sodium carbonate, sodium phosphate, in calcium hydroxide in any one or a few.
6. preparation method as claimed in claim 5, which is characterized in that chloroethene in the polyvinyl chloride suspension polymerization system
Alkene, deionized water, dispersing agent, rare earth-doped titanium dioxide suspension C, pH adjusting agent, the quality point of initiator and chain terminating agent
Number ratio is 1400:1400:4:1~15:0.5:1.5:3.5.
7. preparation method as described in claim 1, which is characterized in that in the step 2, discharging prepares rare earth after the completion of polymerization
The specific steps of titania-doped in-situ polymerization polyvinyl chloride master batch are as follows:
It discharges after the completion of polymerization, is placed in the baking oven that temperature is 40~60 DEG C to go out after single screw extrusion machine melting mixing after drying
Expect, rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch can be prepared after water cooling granulated and dried.
8. preparation method as described in claim 1, which is characterized in that the polymerization technique in the step 2 are as follows:
Deionized water, dispersing agent, rare earth-doped titanium dioxide suspension C, pH adjusting agent are successively put into polymeric kettle by step 2.1,
Initiator is added, capping vacuumizes, 30~60min of pressure maintaining；
Vinyl chloride monomer is put under step 2.2, stirring condition, after being sufficiently mixed uniformly, is warming up to 50~75 DEG C, it is anti-to start polymerization
It answers；
Step 2.3, when reacting kettle inner pressure is down to -0.1MPa, be added chain terminating agent, nitrogen purging after discharge.
Preferably, the stirring condition in the step 2.2 are as follows: 100~700r/min of revolving speed.
9. a kind of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material, which is characterized in that including
0.1~10 mass parts of rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch described in claim 1；
90~99.9 mass parts of polyvinyl chloride.
10. the preparation method of rare earth-doped titanium dioxide modified polyvinyl-chloride composite material as claimed in claim 9, feature
It is, comprising the following steps:
(1) rare earth-doped titanium dioxide in-situ polymerization polyvinyl chloride master batch, polyvinyl chloride are weighed according to the weight ratio, and will be weighed up
Material put into super mixer and be sufficiently mixed；
(2) material for obtaining step (1) is sent into double screw extruder, by double screw extruder melting extrusion, wherein plus
Work temperature is 180~200 DEG C, and screw speed is 150~300r/min, and by tie rod, cooling, pelletizing, drying process, institute is made
State rare earth-doped titanium dioxide modified polyvinyl-chloride composite material.
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