CN1168750C - Suspension polymerization process of preparing polyvinyl chloride resin with high molecular weight - Google Patents
Suspension polymerization process of preparing polyvinyl chloride resin with high molecular weight Download PDFInfo
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- CN1168750C CN1168750C CNB021122229A CN02112222A CN1168750C CN 1168750 C CN1168750 C CN 1168750C CN B021122229 A CNB021122229 A CN B021122229A CN 02112222 A CN02112222 A CN 02112222A CN 1168750 C CN1168750 C CN 1168750C
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Abstract
The present invention relates to a suspended polymerization method for preparing polyvinyl chloride resin with high molecular weight. High alcoholysis degree and low viscosity PVA (I) and proper amount of low alcoholysis degree and low viscosity PVA (II) are combined according to a certain proportion, and are matched with stirring conditions. The shapes of prepared polyvinyl chloride resin particles with high molecular weight are regular and loose. Resin particle diameters are distributed in a concentrative mode, residual monomers (the residual quantity of vinyl chloride is low) are easy to eliminate, and the number of fish eyes are fewer. The prepared polyvinyl chloride resin particles have the advantages of high porosity, proper apparent density which is kept, favorable plasticization performance and simple production process and process. Equipment does not need to be changed; meanwhile, polymer bonding matters in a polymerization kettle are fewer. A sticky kettle phenomenon is reduced, and the equipment is easy to flush.
Description
Technical field
The present invention relates to the preparation method of polyvinyl chloride (PVC) RESINS, relate in particular to and adopt suspension polymerization to prepare the method for polyvinyl chloride (PVC) RESINS, particularly adopt suspension polymerization to prepare the dispersion agent of polyvinyl chloride (PVC) RESINS.
Background technology
High molecular weight pvc is meant that mean polymerisation degree is more than 1700 or intermolecular polyvinyl chloride (PVC) RESINS with hinge arrangement.Polyvinyl chloride resin with high molecular weight, because its molecular mass height, molecular chain length and crimp tendency are big, molecule interchain entanglement point increases, the also more universal polyvinyl chloride (PVC) RESINS height of degree of crystallinity, thus make the molecule interchain reactive force of polychloroethylene with high polymerization degree resin strengthen molecule interchain slippage difficulty; Simultaneously, again because the polychloroethylene with high polymerization degree resin can absorb more softening agent, so its soft goods is intensity height, good heat resistance not only, and bounce impact elasticity is good, the compression permanentset is also little, wear-resisting, winter hardiness is excellent, hardness is little to temperature sensitivity, and the characteristics with thermoplastic elastomer have excellent series of advantages such as sense of touch, Extinction Characteristic and tinctorial property again.The polychloroethylene with high polymerization degree resin is widely used in auto parts machinery, sealing material, electric wire and heat-resisting, pressure hose or aspects such as " to mould for glue ".Therefore, the polychloroethylene with high polymerization degree resin is in world developed country and domesticly all be developed.
Make polyvinyl chloride resin with high molecular weight two kinds of different processing methodes are arranged in the world: low temperature process and chainextender method.But one of key problem in technology that uses above-mentioned two kinds of methods all is a choose reasonable dispersion system how, makes excellent polyvinyl chloride resin with high molecular weight to improve the resin overall quality.Dispersion agent has very large influence to the forming process and the particle form of polyvinyl chloride (PVC) RESINS particle; dispersion agent in the suspension polymerization plays the interfacial tension that reduces between monomer and the water; promote the dispersion of vinyl chloride monomer, on the interface, play the protective membrane effect again simultaneously, suppress excessive cohesion.This shows the vital role that dispersion agent is presented in producing this resin process.
In recent years, along with suspension polymerization dispersant specification and kind, it mainly is the continuous increase of polyvinyl alcohol (PVA) and Vltra tears (HPMC) kind, by using means such as specific compound dispersing agent or employing conversion dispersion agent adding mode further to improve the quality of polyvinyl chloride (PVC) RESINS, and technology is simple, and investment cost is few, and equipment does not need repacking to wait the measure advantage, promote the development of domestic and international polyvinyl chloride resin production technology, greatly improved resin quality.So in the case, prepare polyvinyl chloride resin with high molecular weight, further improve the overall quality and the product properties of resin, satisfy the needs in market by selecting suitable dispersion agent.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of suspension polymerization that adopts compound dispersing agent prepares polyvinyl chloride resin with high molecular weight, make the polyvinyl chloride resin with high molecular weight particle form that makes regular, loose, the resin centralized particle diameter, easily remove residual monomer (the vinylchlorid residual quantity is low), " flake " number is few, has higher porosity, and keep suitable apparent density, plasticizing capacity preferably, technology is simple in process of production, and is basic identical with general production process of resin, and equipment need not changed, simultaneously few in polymeric kettle interpolymer adhesive, " sticking still " phenomenon is lighter, is easy to advantages such as equipment flushing.
Technical conceive of the present invention is such:
When suspension polymerization of VC, monomer droplet is scattered in the water under stirring action, and dispersant adsorption is in the monomer droplet top layer, in stirring dispersion and sticking and the process that influences drop together.Alcoholysis degree, viscosity with dispersion agent, difference etc. rerum natura, cause final high molecular weight pvc particulate generation type and result also to have huge difference,, adjust the dispersion-guarantor's glue ability between water-liquid phase by the conversion dispersion system, suitably control the resin particle diameter, primary particle and aggregate diameter thereof are more little in the resin, the easy more vinylchlorid that removes, and resin particle has one deck dispersion agent epithelium outward, epithelium is thin more, also helps removing vinylchlorid.Just may make prepared polyvinyl chloride resin with high molecular weight particle form regular, loose by adjusting, improve dispersant dosage and coupling, the resin centralized particle diameter, be easy to remove residual monomer, it is low to demonstrate the resin monomer residual quantity, " flake " number is few, have higher porosity, plasticizing capacity preferably, and keep suitable apparent density.
The technical problem that will solve required for the present invention realizes by the following technical solutions:
Polyvinyl chloride resin with high molecular weight of the present invention is meant that the polymerization degree is 2500 or 2250, and apparent density is 0.40～0.50g/cm
3, 100g resin plasticizer specific absorption is more than 30g, and particle form is regular, resin centralized particle diameter, residual vinyl chloride in the resin≤5 μ g/g ,≤10/400cm of " flake " number
2, the polyvinyl chloride resin with high molecular weight of median size between 130～190 μ m.
The present invention is a kind of method of suspension polymerization polyvinyl chloride resin with high molecular weight.Under dispersion agent and stirring action, the vinyl chloride monomer drop carries out coalescence and dispersion in water medium, forms polymer particle.More than used dispersion agent can be the polyvinyl alcohol of partial alcoholysis, methylcellulose gum, ethyl cellulose, Vltra tears, a kind of and composition thereof in polyacrylic acid or the gelatin etc.
Wherein use polyvinyl alcohol (PVA) class best as dispersant effect.
The present invention is with a kind of high alcoholysis degree, low viscosity PVA (I) and an amount of low alcoholysis level, and low viscosity PVA (II) makes up with certain proportioning with two kinds of dispersion agents, is complementary with agitation condition, makes said polyvinyl chloride resin with high molecular weight.
Wherein:
High alcoholysis degree, the consumption of low viscosity PVAC polyvinylalcohol (I) is 0.03～0.20% of a vinyl chloride monomer weight, is the main dispersant of reaction;
Low alcoholysis level, low viscosity, the consumption of the water-soluble poval PVA (II) of low polymerization degree is 0.006～0.07% of a vinyl chloride monomer, is preferably 0.01～0.05%.Dispersion aids for reaction.
The high alcoholysis degree of being addressed, alcoholysis degree 〉=70% (molar fraction) of low viscous PVAC polyvinylalcohol (I) is preferably 70～75%.Alcoholysis degree is too low, and protection vinyl chloride monomer ability is not enough, and coalescence is frequent, makes the particle form irregularity, and the resin sedimentation is not enough.The viscosity of PVA (I) is 0.5～25mPa.s, is preferably 3.5～6mPa.s, (measuring during 20 ℃ times 4% concentration), viscosity is low, helps drop and disperses, and is difficult for coalescence, and particle form is regular, loose, and particle diameter is reasonable, helps vinylchlorid to remove; Viscosity is too high, makes the system dispersive ability not enough, makes the particle chap easily, and epidermis is hard, and crystal is many, is unfavorable for removing of vinylchlorid.
The low alcoholysis level of being addressed, the alcoholysis degree of the PVAC polyvinylalcohol of low polymerization degree (II) is preferably in 28～60% (molar fractions), the polymerization degree preferably 100～400, and be water miscible.
Dispersion aids can make the surface tension of system suitably reduce; play the guarantor's glue ability of coordination system and the effect of dispersive ability; make polymerization system when keeping certain protection drop ability; suitably take into account dispersive ability; thereby increase the interior porosity of resin particle; and eliminated macrobead and fine particle, kept its good vinylchlorid to take off absorption energy and low residual amt.
More than two kinds of dispersion agents cooperate with certain proportion, form the dispersion system of polymerization of vinyl choride monomer jointly, influence the particle characteristics of resin and with the prepared plastics performance of this resin.The adding mode of these two kinds of dispersion agents can be to begin preceding adding in polymerization; Also can be to add before after adding monomer, heating up; Or a part begin preceding adding in polymerization, another part adds with volume pump after polymerization begins certain hour.Adopt which kind of adding mode should be by the specific requirement of resin overall quality and resin performance is decided actually.And the dispersion system of being mentioned among employing the present invention can directly add dispersion agent in the polymeric kettle before polymerization begins; Add with volume pump before also can heating up after adding monomer, the polymerization that heats up after adding can make resin overall quality polyvinyl chloride resin with high molecular weight preferably.
The stirring system plays an important role to formation and quality, the heat-removal capability etc. of polyvinyl chloride resin particle in the chloroethylene polymerization process.Especially blade form, rotating speed etc. have close ties with quality product.
The shape and the structure of the polymeric kettle that uses among the present invention are not particularly limited, and can use the polymeric kettle that uses traditionally.Agitating vane can be used oar formula stirring rake, the Fa Edela oar, and cloth Shandong Makin stirring rake, three leaf swept-back stirring rakes etc. preferably use oar formula stirring rake in above-mentioned stirring rake.Plate washer preferably is set in the polymeric kettle, and form is unrestricted, and power of agitator is preferably in 0.6～1.8KW/M
3In the scope.Power of agitator is too small, causes drop fully not disperse, and polymeric size can not circulate, and easily precipitates, and the most dangerous is that certain heat of polymerization can not pass very soon, causes implode easily, and the also corresponding increase of dispersant dosage, and the production cost volume increases; Power of agitator increases, and particle attenuates, and the also corresponding minimizing of dispersant dosage is favourable to resin quality, but power of agitator is excessively big, causes drop coalescence bonding easily, is difficult for disperseing, and average particle size rises again.
In the suspension polymerization of VC process, telo merization speed mainly is to rely on initiator.Therefore in order to accelerate polymerization rate, the rate of decomposition of choose reasonable initiator, activity, consumption etc. seem extremely important.The initiator that is added in the polyreaction must be middle and high active initiator, can be according to conveniently selecting organic peroxide evocating agent for use, initiator can be peroxyesters, peroxy dicarbonates etc., can be single using or several compound use, its add-on be generally 0.03～0.30% (with respect to the weight percent of vinyl chloride monomer).Initiator can be just throwing or vinyl chloride monomer add the back with aqueous dispersant in Preparation tank under the agitation condition, be mixed with homogenized liquid by even matter emulsification pump, and then join in the polymeric kettle with volume pump, polymerization then heats up, initiator homodisperse very easily in polymerization system like this, the resin of producing " flake " is few, and is favourable to resin quality.
Polyreaction also need add de-salted water, and water plays the effect that moves heat and conduct dispersion small droplets carrier.The desalination water yield that adds, promptly water-oil ratio (weight ratio of de-salted water and vinyl chloride monomer) can be 1.3～2.8/1, preferably 1.6～2.1/1, water-oil ratio is too small, and polyreaction occurs unstable, heat of polymerization shifts out and encounters difficulties, and occurs " temperature runaway " phenomenon easily, increases dangerous; If water-oil ratio is excessive, then production efficiency is low, and the cost volume increases.
During suspension polymerization of VC, the pH value of system is influential to polymerization process system and rate of polymerization and dispersion agent dispersion effect, and the pH value of general system is controlled at neutrality or meta-alkalescence.Decomposite a part of HCL during chloroethylene polymerization, the pH value of system is descended, present acidity, thereby the pH value that needs a certain amount of buffer reagent of adding to regulate polymerization system, sodium hydroxide, sodium bicarbonate, bicarbonate of ammonia, SODIUM PHOSPHATE, MONOBASIC, ammoniacal liquor etc. all can be used as buffer reagent, can improve the resin particle form, are easy to improve take off the absorption energy, the vinylchlorid residual quantity is low, and is favourable to improving resin quality.
Other processing condition of the present invention are identical with traditional suspension polymerization of VC method, and temperature is 38～40 ℃, and the reaction times is 7～12 hours, and relevant technologies personnel can consult relevant patent and technical literature.
For adopting dispersion system of the present invention and agitation condition, the polyvinyl chloride resin with high molecular weight that is obtained, good quality, processing characteristics are good, and the dispersion agent that is adopted among the present invention has been commercial new variety, source and quality all can be guaranteed, the stirring system is not changed substantially, and processing condition are comparatively simple, can guarantee the resin particle degree again simultaneously, residual quantity is low, be easy to take off suction, higher porosity is arranged, can keep certain advantages such as apparent density.Therefore compare with the patent that polyvinyl chloride resin with high molecular weight is produced in other introduction, processing condition change few, and gained resin quality excellence has tangible technology and cost advantage.
Embodiment
Embodiment 1
Polyreaction is three layers of flat oar of two leaves in stirring, and volume is 7M
3The stainless steel polymeric kettle in carry out, in establish two inner cool tubes; Water-oil ratio is 2.0/1.Technological process is summarized as follows; Earlier with the 3840Kg de-salted water, 1.23Kg dispersion agent (PVAI), 0.3Kg (PVAII), the pH regulator agent drops in the polymeric kettle with pressed powder bicarbonate of ammonia 0.02Kg, cover manhole, after the pressure testing deoxygenation vacuumizes, adding is through the vinyl chloride monomer 1920Kg of metering, before heating up, polymerization adds 2.0kg initiator (peroxidation neodecanoic acid isopropyl benzene ester) with volume pump, the startup mixing speed is 180rpm, be warmed up to 38.0 ℃ of polymerization temperatures, keep polymerization temperature to the polymerization pressure pressure drop the heat-resisting terminator HEO of adding 1.3Kg behind the 0.1Mpa with double effects, this HEO is a kind of light yellow or light brown clear liquid, be Hangzhou permanent letter auxiliary chemicals company limited product, push back certainly to receive and carry out 85 ℃ of thermovacuums-450MPa behind the unconverted monomer and reclaim the 1.5hr discharging; Slurry carries out cyclone drying after centrifuge dehydration; Dry gained resin is carried out the sampling analysis test.
Test result is as follows:
The polymerization degree is 2480; Apparent density is 0.41g/ml; The 100gPVC resin plasticizer is absorbed as 36g; Sieving rate: 0.25mm sieve aperture, 65 orders are 98.9%, and 0.063mm sieve aperture, 250 orders are 0.5%; Median size is 180 μ m, and particle diameter distribution width is 0.669; Ageing whiteness be 83% (160 ℃, 10Min); Fusion time is 84 seconds; The vinyl chloride monomer residual quantity is 0.15ppm." flake " number is 0/400cm
2Example 1 obtained resin particle shape is regular, loose, and particle diameter distributes and concentrates, good in thermal property, and the vinylchlorid residual quantity is low.
Above dispersion agent (PVAI) is alcoholysis degree 72% (molar fraction), and viscosity is 5.8mPa.s (20 ℃, under the 4% strength of solution condition); Dispersion agent (PVAII) is alcoholysis degree 50% (molar fraction), and viscosity is the polyvinyl alcohol of 4.0mPa.s (20 ℃, under the 4% strength of solution condition).Specifically see Table 1.
Embodiment 2
Change the add-on of dispersion agent (PVAI) into 1.3Kg; Dispersion agent (PVAII) add-on changes 0.26Kg into.Other processing condition are with embodiment 1, and gained resin quality analytical results is as follows under this condition:
The polymerization degree is 2460; Apparent density is 0.42g/ml; The 100gPVC resin plasticizer is absorbed as 37g; Sieving rate: 0.25mm sieve aperture, 65 orders are 98.0%, and 0.063mm sieve aperture, 250 orders are 0.8%; Median size is 158 μ m, and particle diameter distribution width is 0.665; Ageing whiteness be 82% (160 ℃, 10Min); Fusion time is 76 seconds; The vinyl chloride monomer residual quantity is 0.07ppm." flake " number is 0/400cm
2
Embodiment 3
Change the add-on of dispersion agent (PVAI) into 1.41Kg; Dispersion agent (PVAII) add-on changes 0.22Kg into.Other processing condition are the same with embodiment 1, and gained resin quality analytical results is as follows under this condition:
The polymerization degree is 2456; Apparent density is 0.42g/ml; The 100gPVC resin plasticizer is absorbed as 36g; Sieving rate: 0.25mm sieve aperture, 65 orders are 98.7%, and 0.063mm sieve aperture, 250 orders are 0.6%; Median size is 152 μ m, and particle diameter distribution width is 0.673; Ageing whiteness be 81% (160 ℃, 10Min); Fusion time is 81 seconds; The vinyl chloride monomer residual quantity is 0.54ppm." flake " number is 1/400cm
2
Embodiment 4
With 0.3Kg alcoholysis degree 80% (molar fraction), viscosity is (20 ℃ of 48mPa.s, under the 4% strength of solution condition) PVA and 0.92Kg methoxyl group substitution value be 29.5%, the hydroxypropyl substitution value is 8.0%, viscosity is that the HPMC of 48mPa.s (20 ℃, under the 4% strength of solution condition) comes the dispersion agent (PVAI) of alternative embodiment 1; Other processing condition are with embodiment 1, and gained resin quality analytical results is as follows under this condition:
The polymerization degree is 2524; Apparent density is 0.41g/ml; The 100gPVC resin plasticizer is absorbed as 34g; Sieving rate: 0.25mm sieve aperture, 65 orders are 97.8%, and 0.063mm sieve aperture, 250 orders are 0.9%; Median size is 188 μ m, and particle diameter distribution width is 0.763; Ageing whiteness be 75% (160 ℃, 10Min); Fusion time is 166 seconds; The vinyl chloride monomer residual quantity is 4.5ppm." flake " number is 2/400cm
2
Comparative Examples 1
When polymerization, add the dispersion agent of 0.3Kg and with 0.3Kg alcoholysis degree 48% (molar fraction), viscosity is that the dispersion aids PVA of 1400mPa.s (20 ℃, under the 4% strength of solution condition) replaces (PVAII); And the HPMC of 0.92Kg, other processing condition are with embodiment 1, and gained resin quality analytical results is as follows under its condition: the polymerization degree is 2501; Apparent density is 0.42g/ml; The 100gPVC resin plasticizer is absorbed as 35g; Sieving rate: 0.25mm sieve aperture, 65 orders are 96.8%, and 0.063mm sieve aperture, 250 orders are 0.9%; Median size is 186 μ m, and particle diameter distribution width is 0.782; Ageing whiteness be 77% (160 ℃, 10Min); Fusion time is 182 seconds; The vinyl chloride monomer residual quantity is 5.7ppm." flake " number is 3/400cm
2Specifically see Table 1.
Comparative Examples 2
The dispersion agent PVA that when polymerization, adds 0.25Kg
0Dispersion agent PVA with 0.25Kg
1And the HPMC of 1.04Kg, other processing condition are with embodiment 1, and gained resin quality analytical results is as follows under its condition:
The polymerization degree is 2492; Apparent density is 0.40g/ml; The 100gPVC resin plasticizer is absorbed as 36g; Sieving rate: 0.25mm sieve aperture, 65 orders are 97.4%, and 0.063mm sieve aperture, 250 orders are 0.7%; Median size is 192 μ m, and particle diameter distribution width is 0.779; Ageing whiteness be 76% (160 ℃, 10Min); Fusion time is 179 seconds; The vinyl chloride monomer residual quantity is 7.2ppm." flake " number is 4/400cm
2Specifically see Table 1.
Comparative Examples 3
Add dispersion agent PVA and the dispersion agent PVA of 0.2Kg and the HPMC of 1.15Kg of 0.2Kg when polymerization, other processing condition are with embodiment 1, and gained resin quality analytical results is as follows under its condition: the polymerization degree is 2469; Apparent density is 0.42g/ml; The 100gPVC resin plasticizer is absorbed as 35g; Sieving rate: 0.25mm sieve aperture, 65 orders are 97.2%, and 0.063mm sieve aperture, 250 orders are 0.5%; Median size is 184 μ m, and particle diameter distribution width is 0.764; Ageing whiteness be 77% (160 ℃, 10Min); Fusion time is 192 seconds; The vinyl chloride monomer residual quantity is 11.2ppm." flake " number is 3/400cm
2Specifically see Table 1.
Comparative Examples 4
Add dispersion agent PVA and the dispersion agent PVA of 0.2Kg and the HPMC of 0.67Kg of 0.67Kg when polymerization, other processing condition are with embodiment 1, and gained resin quality analytical results is as follows under its condition: the polymerization degree is 2481; Apparent density is 0.41g/ml; The 100gPVC resin plasticizer is absorbed as 34g; Sieving rate: 0.25mm sieve aperture, 65 orders are 96.1%, and 0.063mm sieve aperture, 250 orders are 0.8%; Median size is 202 μ m, and particle diameter distribution width is 0.801; Ageing whiteness be 76% (160 ℃, 10Min); Fusion time is 196 seconds; The vinyl chloride monomer residual quantity is 15.9ppm." flake " number is 4/400cm
2Specifically see Table 1.
Table 1
| Dispersion agent | Test result | |||||||||
| A (Wt％) | B (Wt％) | C (Wt％) | D (Wt％) | E (Wt％) | Median size (μ m) | Tile Width | Fusion time (second) | VC residual quantity (ppm) | " flake " number is (individual/400cm 2) | |
| Embodiment 1 | 0.064 | 0.016 | 180 | 0.669 | 84 | 0.15 | 0 | |||
| Embodiment 2 | 0.067 | 0.013 | 158 | 0.665 | 76 | 0.07 | 0 | |||
| Embodiment 3 | 0.069 | 0.011 | 152 | 0.673 | 81 | 0.54 | 1 | |||
| Embodiment 4 | 0.016 | 0.016 | 0.048 | 188 | 0.763 | 166 | 4.5 | 2 | ||
| Comparative example 1 | 0.016 | 0.016 | 0.048 | 186 | 0.782 | 182 | 5.7 | 3 | ||
| Comparative example 2 | 0.013 | 0.013 | 0.054 | 192 | 0.779 | 179 | 7.2 | 4 | ||
| Comparative example 3 | 0.010 | 0.010 | 0.060 | 184 | 0.764 | 192 | 11.2 | 3 | ||
| Comparative example 4 | 0.035 | 0.010 | 0.035 | 202 | 0.801 | 196 | 15.9 | 4 | ||
Annotate: Wt% represents the monomeric weight percent to VC.
A: alcoholysis degree is 72% (molar fraction), and viscosity is the PVA dispersion agent of 5.8mPa.s (20 ℃, under the 4% strength of solution condition);
B: alcoholysis degree is 50% (molar fraction), and viscosity is the PVA dispersion agent of 4.0mPa.s (20 ℃, under the 4% strength of solution condition).
C: alcoholysis degree is 80% (molar fraction), and viscosity is the PVA dispersion agent of 48mPa.s (20 ℃, under the 4% strength of solution condition).
D: alcoholysis degree is 48% (molar fraction), and viscosity is the PVA dispersion agent of 1400mPa.s (20 ℃, under the 4% strength of solution condition).
E: the methoxyl group substitution value is 29.5%, and the hydroxypropyl substitution value is 8.0%, and viscosity is the HPMC dispersion agent of 48mPa.s (20 ℃, under the 4% strength of solution condition).
Claims (10)
1. the method for polyvinyl chloride resin with high molecular weight is produced in a suspension polymerization, and the polymerization degree of described polyvinyl chloride resin with high molecular weight is 2500～2250, and apparent density is 0.40～0.50g/cm
3, it is characterized in that the dispersion agent that polymerization process adopts is:
(1) high alcoholysis degree, low viscosity PVAC polyvinylalcohol (I), its consumption is 0.03～0.20% of a vinyl chloride monomer weight;
(2) low alcoholysis level, low viscosity, the water-soluble poval PVA (II) of low polymerization degree, its consumption is 0.006～0.07% of a vinyl chloride monomer;
The high alcoholysis degree of being addressed, alcoholysis degree 〉=70% of low viscous PVAC polyvinylalcohol (I), molar fraction, the viscosity of 20 ℃ of following 4% concentration solution of PVA (I) is 0.5～6mPa.s;
The low alcoholysis level of being addressed, the alcoholysis degree of the PVAC polyvinylalcohol of low polymerization degree (II) is 28～60%, molar fraction, the polymerization degree are 100～400.
2. the method for claim 1 is characterized in that, low alcoholysis level, and low viscosity, the water-soluble poval PVA (II) of low polymerization degree, its consumption is 0.01～0.05% of a vinyl chloride monomer.
3. the method for claim 1 is characterized in that, the high alcoholysis degree of being addressed, and the alcoholysis degree of low viscous PVAC polyvinylalcohol (I) is 70～75%, molar fraction.
4. the method for claim 1 is characterized in that, the high alcoholysis degree of being addressed, and alcoholysis degree 〉=70% of low viscous PVAC polyvinylalcohol (I), molar fraction, the viscosity of 20 ℃ of following 4% concentration solution of PVA (I) is 3.5～6mPa.s.
5. the method for claim 1 is characterized in that, the low alcoholysis level of being addressed, and the PVAC polyvinylalcohol of low polymerization degree (II) is water miscible.
6. the method for claim 1 is characterized in that, dispersion agent adds in the polymeric kettle before polymerization begins.
7. the method for claim 1 is characterized in that, dispersion agent adds before heating up after adding monomer.
8. the method for claim 1 is characterized in that, the agitating vane of polymeric kettle is an oar formula stirring rake.
9. method as claimed in claim 8 is characterized in that, power of agitator is 0.6～1.8KW/M
3
10. as the arbitrary described method of claim 1～9, it is characterized in that polymerization temperature is 38～40 ℃, the reaction times is 7～12 hours.
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| US8252860B2 (en) * | 2008-06-16 | 2012-08-28 | Kuraray Co., Ltd. | Polyvinyl chloride resin composition and manufacturing method thereof |
| CN102443085A (en) * | 2011-10-31 | 2012-05-09 | 河北盛华化工有限公司 | Method for preparing polyvinyl chloride resin used for chlorination |
| CN102492066B (en) * | 2011-12-08 | 2013-10-16 | 内蒙古宜化化工有限公司 | Method for preparing polyvinyl chloride by suspension polymerization |
| CN106749793A (en) * | 2016-04-23 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of preparation method of Corvic |
| CN106749795A (en) * | 2016-07-17 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of preparation method of Corvic |
| CN107778394B (en) * | 2016-08-27 | 2019-12-27 | 中国石油化工股份有限公司 | Preparation method of porous structure polyvinyl chloride resin |
| CN107057216A (en) * | 2016-12-21 | 2017-08-18 | 马鞍山瑞美塑业有限公司 | A kind of PVC modified plastics |
| CN107236065A (en) * | 2017-06-06 | 2017-10-10 | 滁州市宏源喷涂有限公司 | One kind avoids the method that " flake " is produced in PVC Production Process |
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