CN107540770A - A kind of preparation method of the excellent polyvinyl chloride resin of thermal stability - Google Patents
A kind of preparation method of the excellent polyvinyl chloride resin of thermal stability Download PDFInfo
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Abstract
A kind of preparation method of the excellent polyvinyl chloride resin of thermal stability, belongs to polyvinyl chloride resin synthesis technical field.1）Polymeric kettle is vacuumized, 100 ~ 150 parts of raw material deionized water is added, triggers 100 parts of 0.01 ~ 0.2 part of system, 0.03 ~ 0.5 part of dispersion, 0.001 ~ 0.03 part of pH adjusting agent and vinyl chloride, stir 2 ~ 10 minutes, be warming up to 35 ~ 65 DEG C, polymerization starts timing；2）By rare earth thermal stabilizer, 0.05 ~ 1 part is pumped into polymeric kettle with whole polymerization process constant speed；3）When reaching polymerization terminal, 0.001 ~ 0.3 part of terminator is added to stop reaction, stirring draws off slurry for 2 ~ 10 minutes, centrifugation, dries, produces.The shortcomings that preparation method of the excellent polyvinyl chloride resin of thermal stability of the invention can obtain the excellent polyvinyl chloride resin of thermal stability, and resin thermal stability prepared by the existing polymerization technique of improvement is poor.
Description
Technical field
The invention belongs to polyvinyl chloride resin synthesis technical field, and in particular to a kind of system of the excellent polyvinyl chloride resin of thermal stability
Preparation Method.
Background technology
Corvic（PVC）It is to realize the universal thermoplastic of industrialization time earliest, Ye Shishi in the world
The second large-tonnage resin of boundary, because its is cheap, excellent performance, thus be widely applied in each field.
Chemically analyzed in structure, preferable vinyl chloride-base polymer strand is strict head-tail structure, up to 300
DEG C when do not remove small molecule, non-degradable, keep color and luster and mechanical stability, substantially exceed 170 ~ 220 DEG C of processing temperature area；And
The temperature that the degraded beginning of polyvinyl chloride resin is industrialized in reality is far below processing temperature, only 80 DEG C.Because actually it polymerize
Various side reactions in journey cause the PVC molecular chain structures of synthesis anomaly sxtructure occur in individual sites, such as branched, unsaturated
Key, unstable chlorine, initiator residue, oxygen-containing group, the chemical imperfection structure of head-head or tail-tail, these defect sturctures are to cause
The initiation point that polyvinyl chloride resin heat endurance declines.Research shows in PVC strand defect sturctures that internal allyl chloride is least
Stable, easily substituted, next to that tertiary chlorine, the allyl chloride of end, secondary chlorine.Under heat, light, mechanical stress effect, strand
On contain or played adjacent to allyl chloride, tertiary chlorine " active group " of one hydrogen chloride of removing and act on, the shape on PVC chains immediately
Into a undersaturated double bond, in being so that adjacent chlorine atom activation.This adjacent chlorine atom closes pi-allyl in structure
Chlorine is the same, promotes two chlorination hydrogen molecules then to remove.This process continuously repeats progress, just forms a kind of polyene structure.In
It is that only under a little higher than 80 DEG C of heat effects aging phenomenon is occurring for polyvinyl chloride resin in practice, and when reaching 180 DEG C of processing temperature i.e.
There is obvious problem of aging, show a series of characteristic color-colourless → yellowish → Huang → yellow orange → blood orange → red → brown.
So PVC is heat sensitivity polymer, compared with other thermoplastic polymers, PVC is to thermoae unstable polymer.
The shortcomings that to improve PVC heat endurance differences, PVC industry improve PVC trees in polymerization technique and processing technology respectively
The ageing-resistant performance of fat, for example improve material purity, using chemical addition agent, polymerization technique optimization, process equipment improvement, compounding
Some row means of process optimization.In today of PVC industry comparative maturities, each resin generation producer and product processing producer exist
Higher level is all reached in terms of material purity, polymerization technique and process equipment, compounding process optimization, and has changed in polymerization technique
Then respectively there is its feature in terms of learning additive and compounding auxiliary agent selection, this embodies a concentrated reflection of terminator functionalization and rare earth thermal stabilizer
In terms of Non-toxic.
The polymerization of the current vinyl chloride for having industrialized large-scale application and its copolymer includes polymerisation in bulk, emulsion
Polymerization, four kinds of modes of micro suspension and suspension polymerisation, but mechanism of polymerization are all the radical polymerization used.In suspension polymerization of VC
In course of reaction, after monomer conversion is more than 80%, the increase of disproportionation termination between macromolecular radical, easily generate it is more
Branched structure, influence the thermostable type and processing characteristics of product, and rate of polymerization can become very low, thus from production efficiency and
The consideration of resin performance perspective itself, conversion ratio more than 65%（I.e. there is obvious pressure drop in polymerization reaction system）To in the range of 90%,
When polymerization later stage pressure drop reaches 0.1 ~ 0.15MPa, it should stop reacting at once.Chain terminating agent adds polymerization system, makes unreacted
Initiator free radical, macromolecular radical reaction, so as to stop or slow down completely reaction.In chloroethylene polymerization production technology
The terminator used has ASTC（Acetone semicarbazone thiocarbamide）、DEHA（Diethyl hydroxylamine）, antioxidant class is as having hindered phenol structure
Bisphenol-A（2,2- bis-（4- hydroxy phenyls）Propane）、1076（The hydroxy-phenylpropionic acid octadecanol ester of 3,5- di-t-butyl -4）、
264（2,6- di-tert-butyl-4-methy phenols）、BHA（Tertiary butyl-4-hydroxy anisole）、245（Triethylene-glycol pair β-
（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Propionic ester]）With the DLTDP of thioesters class（Dilauryl thiodipropionate）、DSTP
（Distearyl thiodipropionate）.These terminators use solution mode, or using the Aqueous dispersions close to stable form
Liquid mode adds.But there are some shortcomings in chloroethylene polymerization terminating party face：Or termination efficiency is satisfied but resin heat endurance changes
Enter unobvious, or high volatility causes to lose greatly during chance heating operation, or poorly water-soluble, prepare dispersion soln difficulty and be difficult to make
With, or terminate polymerization efficiency it is relatively low, or there is certain toxicity.More obviously, when the chlorine for individually using these terminators
Ethene polymers slurry is right when carrying out industrial process operation such as in the last handling process of monomer flash distillation, stripping and heat drying
It is limited in the improvement effect of product heat endurance.
In order to terminate radical reaction while improve resin thermal stability, there have been the functionalization in technique now for this
Compound terminator technique.The result of study published proves that the decomposition of vinyl chloride-base polymer has radical reaction
Feature, in the presence of light, heat, ray, stress, initiator, the molecular link at polymer molecular structure weak link occurs disconnected
Split, produce free radical.This free radical with the free radical in the polymerization process under the conditions of vinyl chloride thermal initiation with
Similar feature, therefore, there is the antioxidant for neutralizing free radical can provide certain polymer thermostable effect and polymerization instead
Effect should be terminated.As the method for improving vinyl chloride-base polymer thermal stability result, it has been proposed that many patents, such as patent
CN1053198C proposes a kind of emulsion for chloroethylene polymerization termination, is made up of aqueous phase and oil phase two parts, poly-
Close when reaction reaches target conversion and use.It is characterized in that use antioxidant, UV absorbers, rare earth thermal stabilizer, solvent
And the mixture of fluorescent whitening agent composition is prepared through emulsifying emulsification pretreatment technique, the rare earth thermal stabilizer employs metal
Soap and organotin rare earth thermal stabilizer.As a result of Hinered phenols antioxidant, this emulsion is in terms of polymerisation terminates effect
It is obvious relatively low, it is undesirable up to the dynamic thermal stability in plasticizing instrument in Bradley sheet, and due to having used hydro carbons, aromatic hydrocarbon and increasing
Agent class organic solvent is moulded, has also brought the chemical composition with health hazard into final products.Patent CN1250583C and CN
1219801C, which proposes use, can provide polymerization terminator of the nitroxide type stable free radical as free radical, for terminating by mistake
The technique for aoxidizing the chloroethylene polymerization process that dialkyl dicarbonate, the tertiary alkanoic acid ester of peroxidating and peroxidating two acyl trigger.It is used
Terminator is mainly diethyl hydroxylamine, though with preferably terminating effect, for final products heat endurance without substantially changing
Kind effect.Patent US 6433074B1, US 4619978 and US 5159032 provide improves chloroethene using hindered phenol antioxygen
The method of alkene polymer heat stabilization.Although this method provides certain resin heat endurance ameliorative way, but polymerize
Reaction terminating effect is weaker, and the dosage of hindered phenol antioxygen is larger, and thermal stability is reached on plasticizing instrument in dynamic Bradley sheet
Show undesirable.Patent ZL03809917.9 provides the method for improving vinyl chloride-base polymer heat stabilization, using with end
The method that the free nitroxyl compound that only acts on is used cooperatively with hindered phenol anti-oxidants, this method although provide compared with
High polymerization effect, its static heat stability can still, but thermal stability reaches plasticizing instrument upper table in dynamic Bradley sheet
It is existing undesirable.Patent CN102952219B, propose in suspension polymerization of VC reaction system, with two substituted hydroxylamines and with good
Good dispersity organo-tin compound prepares method of vinyl chloride resin and combinations thereof, had fast as feature terminator
Speed terminates effect and excellent heat stability energy, but organotin fancy price and high poison or part hypotoxicity limit it and apply model
Enclose.
The content of the invention
The technical problem to be solved in the present invention is：For the above-mentioned deficiency of prior art, there is provided a kind of thermal stability is excellent
The preparation method of good polyvinyl chloride resin, the preparation method of the excellent polyvinyl chloride resin of the thermal stability can prepare static burn in whiteness
（160 DEG C, 10min）The polyvinyl chloride resin being significantly increased with the dynamic aging stabilization time tested in instrument is plastified, improve existing poly-
The shortcomings that resin thermal stability prepared by conjunction technique is poor, it is a kind of method for synthesizing thermal stability high-quality polyvinyl chloride resin.
The present invention is achieved by the following technical solutions：The preparation method of the excellent polyvinyl chloride resin of the thermal stability, its
It is characterised by, comprises the following steps：
1）Polymeric kettle is vacuumized, adds raw material by weight：100 ~ 150 parts of deionized water, trigger system 0.01 ~ 0.2 part, point
Granular media is 0.03 ~ 0.5 part, 100 parts of 0.001 ~ 0.03 part of pH adjusting agent and vinyl chloride, stirs 2 ~ 10 minutes, is warming up to 35 ~ 65
DEG C, polymerization starts timing；
2）By rare earth thermal stabilizer, 0.05 ~ 1 part is pumped into polymeric kettle with whole polymerization process constant speed；
3）When reaching polymerization terminal in polymeric kettle, adding 0.001 ~ 0.3 part of terminator stops reaction, continues stirring 2 ~ 10
Slurry is drawn off after minute, will be pulp centrifuged, dry, produce polyvinyl chloride resin.
Step 2）It is described with whole polymerization process constant speed be pumped into for：0.05 ~ 1 part of constant speed of rare earth thermal stabilizer is pumped into,
65 ~ 100% that the time accounts for polymerization total used time are pumped into, it is step 1 to polymerize total used time）Polymerization starts timing to step 3）It polymerize terminal
Time used.
It polymerize total used time for 3 ~ 10 hours.
Step 2）Described rare earth thermal stabilizer starts to be pumped into the time as 5 ~ 10min after polymerization beginning timing.
Step 2）Described rare earth thermal stabilizer Lanthanum Stearate.
Step 3）Described polymerization terminal is step 3）Pressure drops to 0.08 ~ 0.12MPa of pressure difference in polymeric kettle.
Step 1）The described vacuum vacuumized is -0.09 ~ -0.05MPa.
Step 2）Concrete operations be：By rare earth thermal stabilizer, 0.1 ~ 0.5 part is pumped into polymerization with whole polymerization process constant speed
In kettle.
Step 1）Described initiation system is free radical type initiator, and dispersion is polyvinyl alcohol dispersant and fiber
The compound system of plain ethers dispersant.
It is described as follows for the present invention：
Step 1）In, added with 100 ~ 150 parts of raw material deionized water, trigger 0.01 ~ 0.2 part of system, dispersion 0.03 ~ 0.5
100 parts of part, 0.001 ~ 0.03 part of pH adjusting agent and vinyl chloride.Wherein：Initiation system is free radical type initiator；Described freedom
Fundamental mode initiator can trigger chloroethylene polymerization.Preferably, initiation system is that azo-initiator and/or organic peroxy class are drawn
Agent is sent out, the initiation system can be used alone with certain proportion, or be made into compound system use.It is wherein preferable, azo
Initiator is at least one of azodiisobutyronitrile, ABVN, and organic peroxy class initiator is the carbon of peroxidating two
Dibutyl phthalate, diisobutyryl peroxide, dicetyl peroxydicarbonate two-（2- ethylhexyls）In ester, cumyl peroxyneodecanoate
At least one.It is further preferred that trigger system be dicetyl peroxydicarbonate two-（2- ethylhexyls）Ester and peroxidating neodecanoic acid
Isopropyl phenyl ester in mass ratio 1 ~ 3：1 compound.Dispersion is polyvinyl alcohol dispersant and cellulose ethers dispersant
Compound system, it is preferred that dispersion is high alcoholysis degree polyvinyl alcohol, polyvinyl alcohol with low alcoholysis level and hydroxypropyl methyl cellulose
By weight 3 ~ 4：1：1 ~ 2 compound.PH adjusting agent, it can be used according to the stability and particular/special requirement of polymerization system all kinds of
Alkaline conditioner；Preferably, pH adjusting agent is ammonium hydrogen carbonate.Preferably, step 1）Concrete operations be：Polymeric kettle is taken out very
Sky, raw material is added by weight：150 parts of deionized water, 0.07 ~ 0.09 part of the system that triggers, 0.08 ~ 0.1 part of dispersion, pH are adjusted
100 parts of 0.001 part of agent and vinyl chloride are saved, is stirred 2 ~ 10 minutes, is warming up to 45 ~ 60 DEG C, polymerization starts timing.Preferably, step
1）Also include molecular weight regulator in the raw material added, molecular weight regulator is to be decreased or increased according to what polymerization technique added
The auxiliary agent of molecular weight, i.e. chain-transferring agent or chain extender, can be added according to technique to be not added with.Step 1）Described vacuumizes it
Before, polymeric kettle interior flushing is clean, and coat anti-fouling agent.Step 1）Described heating mode follows to start chuck water-bath
Ring, polymeric kettle is heated, polymerization system in kettle is heated up.Step 1）Middle polymerisation starts timing ~ step 2）In, polymerisation
Temperature, pressure and time are routine techniques, it is preferred that the temperature of polymerisation is any steady temperature in 35 DEG C ~ 65 DEG C, is gathered
Conjunction reaction pressure is 0.8 ~ 0.9MPa, polymerize total 4 ~ 10 hours used times, should.
Applicant has found under study for action：In existing PVC industry, the conventional application of rare earth thermal stabilizer is processed in resin
It is added in mixed ingredients and uses in journey, traditional stabilizer will not be added in practical application in polymerization system, because
Traditional stabilizer such as lead salt stabilizer, metal soap stabilizer, organic tin stabilizer can cause bad to polymerization system
Influence, such as inhibition or polymerization system loss of stability；Furthermore subsequent working-up stages are to the performance requirement of raw material polyvinyl chloride resin
Bigger difference is had, and different stabilizers can cause the influence of different performance to material resin.So in order to adapt to PVC trees
The extensive processed and applied of fat, other performance of the stabilizer reply resin added in the polymerization technique stage in addition to ageing properties
Influence the smaller the better, such as light transmittance, mist degree, processing rheological property.Lead salt stabilizer thermal stability is excellent, but product
It is opaque and poisonous, the stabilizer being eliminated is belonged in resin processing industry；Metal soap stabilizer performance be worse than lead salt and
Organic tin, but its this kind of heavy metal of Ba, Cd contained also has stronger toxicity, and application is limited；Organic tin stabilizer
The characteristics of being generally believed by industrial quarters with efficient heat endurance, weatherability, the transparency and asepsis environment-protecting, but this kind of stabilizer
Cost is too high, and its cost is more expensive than conventional lead salt stabilizer big 4 times, average expensive 2 ~ 3 times than conventional barium-cadmium system, more
In functional group organotin process easily with the intermolecular formation cross-linked structures of PVC.
Applicant has found under study for action：Because existing polyvinyl chloride resin processing temperature needs to reach 180 DEG C, far above its aging
Decomposition temperature, to enable polyvinyl chloride resin to plastify into a kind of product for having practical use, rare earth heat is added surely in system before plasticizing
It is indispensable important technique measure in PVC industry to determine agent.Rare earth thermal stabilizer have prevent from deviating from chlorination in PVC strands
The effect of hydrogen, or can at least prevent this reaction.Upper used rare earth thermal stabilizer presses its chemical group in PVC industry at present
Into lead salt stabilizer, metal soap stabilizer, organic tin stabilizer and rare-earth stabilizer can be divided into.First two stabilizer pair
PVC has good heat stabilization and lower price, but this kind of heavy metal of lead, cadmium can ooze out from product, and toxicity is very big；State
Outside with organotin rare earth thermal stabilizer substitute lead salt rare earth thermal stabilizer, heat endurance is good, a small number of kinds are nontoxic, but price compared with
Height, and all irritant smell during processing.In recent years, as people are to health and the growing interest of environment, match somebody with somebody using PVC is nontoxic
The cry of side is more and more high.China is the big country of rare earth resources reserves, and domestic and international experts and scholars are successively to rare earth organic compounds
A large amount of fruitful research work have been done in the application of PVC industrial circles.Applicant it has been investigated that：Rare earth organic compounds
There is good heat stabilization and nontoxic pollution-free to PVC.Rare earth thermal stabilizer is based on rare earth oxide and chloride
Single compound or complex.Rare earth element ion has 4f, 5d sky electron orbit, its unoccupied orbital energy extreme difference very little, outside
Under the hot oxygen effect in boundary, outer layer or secondary outer-shell electron are intensified, and the chlorine atom of ligand can be subjected to PVC strands（Cl）Match somebody with somebody
Position, makes it be not easy to slough, and can form co-ordination complex with the HCl of abjection, so as to prevent or delay hydrogen chloride
Automatic elimination reaction, plays heat stabilization.
Applicant it has been investigated that：In the course of the polymerization process, rare-earth stabilizer is added into polymerization system（It is preferred that stearic acid
Lanthanum）, the excellent polyvinyl chloride resin of thermal stability can be obtained.Rare earth thermal stabilizer effect is good, has a long-term thermal stability, and with
There is extensive cooperative effect between other class stabilizers, there is good tolerance, do not polluted by sulphur, stable storing, and
Asepsis environment-protecting, it is inexpensive efficiently, gradually approved by market, and China's rare earth resources enrich, and are made in polymerization using rare earth thermal stabilizer
Meet requirement of the people to " green product " to improve the technical matters of resin ageing properties.Rare earth thermal stabilizer can effectively be kept away
Exempt from problems as mentioned above, a small amount of rare-earth stabilizer Lanthanum Stearate is added in polymerization system in the present invention, because being mixed with resin
Resin heat resistance energy is evenly effectively improved, while does not influence polymerization process, to resin processing characteristics and products appearance
Also have no adverse effects.Applicant is further discovered that under study for action：0.05 ~ 1 part of the addition of rare earth thermal stabilizer is optimum amount,
When step 2）In rare-earth stabilizer using non-constant velocity add when, being normally carried out for polymerization process can be influenceed, even if having obtained PVC
Resin, its thermal stability are also undesirable.Only when rare earth thermal stabilizer concomitant polymerization process adds in a manner of constant speed is pumped into
When in polymerization system, polymerisation is not interfered with not only, and the thermal stability performance of gained polyvinyl chloride resin is excellent.In order to further
The optimal addition time in the course of the polymerization process of rare earth thermal stabilizer is determined, applicant is through determining：By rare earth thermal stabilizer
When being pumped into the time and accounting for the 65 ~ 100% of polymerization total used time, gained polyvinyl chloride resin thermal stability is optimal, by for rare earth thermostabilization
The control of parts by weight that agent is pumped into the time and is pumped into, it is controllable that the constant speed of rare earth thermal stabilizer, which is pumped into speed,.Preferably,
Step 2）Rare earth thermal stabilizer is pumped into by flow pump.
Heretofore described polymerization system is the whole polymerization reaction system in polymeric kettle, comprising it is all be added into it is poly-
Close the composition in kettle.Step 1）It is middle stirring 2 ~ 10 minutes be stirring at normal temperature（5~28℃）, it is by the original of addition polymeric kettle that it, which is acted on,
Material uniformly mixing at normal temperatures, prepares, stir speed (S.S.) is existing conventional value for subsequent heat heating.Step 3）In, the present invention
Described in polymerization terminal metering method, be this area in, chloroethylene polymerization reaction generation Corvic technique routine
It polymerize terminal metering method.Described pressure difference（It is abbreviated as △ P）For step 1）Polymerization starts the polymeric kettle pressure and step during timing
Rapid 3）The absolute value of the difference of polymeric kettle pressure during polymerization.Step 1）Polymerization starts polymeric kettle pressure polymerization during timing
Reaction pressure, preferably 0.8 ~ 0.9MPa.Terminator is existing single terminator, or, be functionalization compound terminator.Eventually
Only agent, which is added in polymerization system, can make polymerisation stop completely or drastically slow down, and reach the suitable mesh of control depth of cure
, this invention is to terminator without particular/special requirement.Preferably, terminator is diethyl hydroxylamine.Preferably, step 3）Described draws off
Also include before slurry：Discharge unreacted vinyl chloride in polymeric kettle.Step 3）Described drying is to use the slurry after centrifugation
Ebullated bed, 1 ~ 2h is dried at 80 ~ 110 DEG C.
Compared with prior art, possessed by a kind of preparation method of the excellent polyvinyl chloride resin of thermal stability of the invention
Beneficial effect is：The preparation method of the excellent polyvinyl chloride resin of the thermal stability can prepare static burn in whiteness（160 DEG C,
10min）The polyvinyl chloride resin being significantly increased with the dynamic aging stabilization time tested in instrument is plastified, improve existing polymerization technique
The shortcomings that resin thermal stability of preparation is poor, it is a kind of method for synthesizing high-quality polyvinyl chloride resin.It is proposed by the present invention to incite somebody to action
The rare earth thermal stabilizer Lanthanum Stearate used in polyvinyl chloride resin process, it is added to conventional polyvinyl chloride resin as reagent and additive in polymerization and gathers
Close in formula, prepare the outstanding polyvinyl chloride resin of thermal stability, small, easy implementation is changed to existing PVC synthesizers technique,
Use can be widely popularized on commercial plant.Outstanding thermal stability disclosure satisfy that resin processes producer to PVC raw material trees
Fat thermal stability requires to reach nonhazardous, green requirement during high, process and use possess practicality.
Prove that there is good thermal stability by baking oven anti-aging test and the experiment of Brabender torque rheometers, can be extensive
Applied in each model polyvinyl chloride resin synthesis technique.
Embodiment
Embodiment 1 ~ 13 is a kind of specific embodiment party of the preparation method of the excellent polyvinyl chloride resin of thermal stability of the present invention
Formula.Wherein embodiment 1 is most preferred embodiment.Comparative example 1 ~ 2 is that applicant is imitated to contrast technical scheme and technology
Fruit and the comparative example designed.
Embodiment 1
It is made up of the raw material of following parts by weight：100 parts of vinyl chloride, 150 parts of deionized water, trigger 0.07 part of system, dispersion
0.08 part, 0.001 part of PH conditioning agents, 0.05 part of rare earth thermal stabilizer, 0.01 part of terminator；
Wherein, dispersion be high alcoholysis degree polyvinyl alcohol, polyvinyl alcohol with low alcoholysis level and hydroxypropyl methyl cellulose by weight
Than 3：1：1 compound；Initiation system be dicetyl peroxydicarbonate two-（2- ethylhexyls）Ester and cumyl peroxyneodecanoate
In mass ratio 3：1 compound.PH conditioning agents are ammonium hydrogen carbonate.Terminator is diethyl hydroxylamine.Rare earth thermal stabilizer is tristearin
Sour lanthanum.
Preparation method, comprise the following steps：
1）Polymeric kettle is rinsed well, anti-fouling agent is coated, after being evacuated to vacuum -0.09 ~ -0.05, according to polymerization formula
Add deionized water, trigger system, dispersion, PH conditioning agents and vinyl chloride, while start chuck water-bath circulation, control polymerization
When system temperature reaches 56.5 ~ 57.5 DEG C of setting value steadily in kettle, reaction starts timing；
2）When reaction temperature reaches 56.5 ~ 57.5 DEG C of setting value, open Lanthanum Stearate and be pumped into system, by 0.05 part of Lanthanum Stearate with
Whole polymerization process constant speed is pumped into polymeric kettle；
3）Polyase 13 .5h, polymerization system pressure drop △ P add terminator when reaching 0.12MPa, stirring reclaims unreacted after 5 minutes
Monomer, emptying discharging is pulp centrifuged, boiled bed drying, produces polyvinyl chloride resin.
Embodiment 2
Rare earth thermal stabilizer Lanthanum Stearate addition is 0.10 part, and other raw materials and preparation method are same as Example 1.
Embodiment 3
Rare earth thermal stabilizer addition is 0.15 part, and other raw materials and preparation method are same as Example 1.
Embodiment 4
Rare earth thermal stabilizer addition is 0.20 part, and other raw materials and preparation method are same as Example 1.
Embodiment 5
Rare earth thermal stabilizer addition is 0.30 part, and other raw materials and preparation method are same as Example 1.
Embodiment 6
Rare earth thermal stabilizer addition is 0.40 part, and other raw materials and preparation method are same as Example 1.
Embodiment 7
Rare earth thermal stabilizer addition is 0.50 part, and other raw materials and preparation method are same as Example 1.
Embodiment 8
Rare earth thermal stabilizer addition is 0.75 part, and other raw materials and preparation method are same as Example 1.
Embodiment 9
Rare earth thermal stabilizer addition is 1.0 parts, and other raw materials and preparation method are same as Example 1.
Comparative example 1
This comparative example compares with embodiment 1-9.Rare earth thermal stabilizer, other raw materials and preparation method and embodiment 1 are not added
It is identical.
Embodiment 10
It is made up of the raw material of following parts by weight：100 parts of vinyl chloride, 150 parts of deionized water, trigger 0.09 part of system, dispersion
0.1 part, PH conditioning agents, 0.001 part, 0.05 part of rare earth thermal stabilizer, 0.015 part of terminator；
Wherein, dispersion be high alcoholysis degree polyvinyl alcohol, polyvinyl alcohol with low alcoholysis level and hydroxypropyl methyl cellulose by weight
Than 4：1：2 compound.Initiation system be dicetyl peroxydicarbonate two-（2- ethylhexyls）Ester and cumyl peroxyneodecanoate
In mass ratio 1：1 compound.PH conditioning agents are ammonium hydrogen carbonate.Terminator is diethyl hydroxylamine.Rare earth thermal stabilizer is tristearin
Sour lanthanum；
Preparation method, comprise the following steps：
1）Polymeric kettle is rinsed well, anti-fouling agent is coated, after being evacuated to vacuum -0.09 ~ -0.05, according to polymerization formula
Add deionized water, trigger system, dispersion, PH conditioning agents and vinyl chloride, while start chuck water-bath circulation, control polymerization
When system temperature reaches 49.5 ~ 50.5 DEG C of setting value steadily in kettle, reaction starts timing；
2）When reaction temperature reaches 49.5 ~ 50.5 DEG C of setting value, open Lanthanum Stearate and be pumped into system, by 0.05 part of Lanthanum Stearate with
Whole polymerization process constant speed is pumped into polymeric kettle；
3）It polymerize 5h, polymerization system pressure drop △ P add terminator when reaching 0.08MPa, stirring reclaims unreacted list after 5 minutes
Body, emptying discharging is pulp centrifuged, boiled bed drying, produces polyvinyl chloride resin.
Embodiment 11
Rare earth thermal stabilizer addition is 0.10 part, and other raw materials and preparation method are same as Example 1.
Embodiment 12
Rare earth thermal stabilizer addition is 0.50 part, and other raw materials and preparation method are same as Example 1.
Embodiment 13
Rare earth thermal stabilizer addition is 1.0 parts, and other raw materials and preparation method are same as Example 1.
Comparative example 2
This comparative example compares with embodiment 10 ~ 13.Rare earth thermal stabilizer, other raw materials and preparation method and embodiment are not added
10 is identical.
Performance test
It is resistance to old according to the baking oven in GB/T 15595-2008 respectively by embodiment 1 ~ 13 and the polyvinyl chloride resin of the gained of comparative example 1 ~ 2
Change experiment, test polyvinyl chloride resin ageing whiteness, reach plasticizing instrument using Bradley sheet respectively（That is Brabender torque rheometers）Test
Polyvinyl chloride resin dynamic heat-stable time, test result are shown in Table 1.
The performance test results of the polymerization process and gained polyvinyl chloride resin of the embodiment of table 1 and comparative example
。
In table 1, embodiment 1 ~ 9 and comparative example 1 use boardy product formula：100 parts of raw material polyvinyl chloride resin, 0.6 part of organotin,
0.3 part of 0.5 part of CaSt, OPE, 1.2 parts of paraffin, 10 parts of CPE, CaCO310 parts, 190 DEG C, 60r/min.
In table 1, embodiment 10 ~ 13 and comparative example 2 use soft goods formula：100 parts of raw material polyvinyl chloride resin, Ca-Zn RUP-
50 parts of 8 parts of 167C, DOP, 6 parts of clay, 15 parts of chlorinated paraffin, 0.5 part of paraffin, CaCO318 parts, 180 DEG C, 60r/min.
Static heat stability energy and dynamic thermal stability as table 1 to polyvinyl chloride resin obtained by embodiment and comparative example polymerization
It can be tested, can comprehensively react the thermal stability of gained polyvinyl chloride resin.It can will become apparent from by table 1：This hair
Bright middle added rare earth thermal stabilizer is added in resin system in the course of the polymerization process, the static burn in whiteness to sold resin
（160 DEG C, 10min）It is significantly increased with the dynamic aging stabilization time tested in instrument is plastified, improves existing polymerization technique
The shortcomings that resin thermal stability of preparation is poor, it is a kind of method for synthesizing high-quality polyvinyl chloride resin.The preparation method of the present invention
It is easy to implement in existing commercial plant, there is practicality, can in PVC industry large-scale application, improve polyvinyl chloride resin heat
Stability.
The above described is only a preferred embodiment of the present invention, be not the limitation for making other forms to invention, it is any
Those skilled in the art are changed or are modified as the equivalent of equivalent variations possibly also with the technology contents of the disclosure above
Embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is made to above example
Any simple modification, equivalent variations and remodeling, still fall within the protection domain of technical solution of the present invention.
Claims (9)
1. the preparation method of the excellent polyvinyl chloride resin of a kind of thermal stability, it is characterised in that comprise the following steps：
1）Polymeric kettle is vacuumized, adds raw material by weight：100 ~ 150 parts of deionized water, trigger system 0.01 ~ 0.2 part, point
Granular media is 0.03 ~ 0.5 part, 100 parts of 0.001 ~ 0.03 part of pH adjusting agent and vinyl chloride, stirs 2 ~ 10 minutes, is warming up to 35 ~ 65
DEG C, polymerization starts timing；
2）By rare earth thermal stabilizer, 0.05 ~ 1 part is pumped into polymeric kettle with whole polymerization process constant speed；
3）When reaching polymerization terminal in polymeric kettle, adding 0.001 ~ 0.3 part of terminator stops reaction, continues 2 ~ 10 points of stirring
Slurry is drawn off after clock, will be pulp centrifuged, dry, produce polyvinyl chloride resin.
A kind of 2. preparation method of the excellent polyvinyl chloride resin of thermal stability according to claim 1, it is characterised in that：Step
Rapid 2）It is described with whole polymerization process constant speed be pumped into for：0.05 ~ 1 part of constant speed of rare earth thermal stabilizer is pumped into, being pumped into the time accounts for
It polymerize the 65 ~ 100% of total used time, it is step 1 to polymerize total used time）Polymerization starts timing to step 3）It polymerize the time used in terminal.
A kind of 3. preparation method of the excellent polyvinyl chloride resin of thermal stability according to claim 2, it is characterised in that：It is poly-
Total used time is closed as 3 ~ 10 hours.
A kind of 4. preparation method of the excellent polyvinyl chloride resin of thermal stability according to claim 1, it is characterised in that：Step
Rapid 2）Described rare earth thermal stabilizer starts to be pumped into the time as 5 ~ 10min after polymerization beginning timing.
A kind of 5. preparation method of the excellent polyvinyl chloride resin of thermal stability according to claim 1, it is characterised in that：Step
Rapid 2）Described rare earth thermal stabilizer Lanthanum Stearate.
A kind of 6. preparation method of the excellent polyvinyl chloride resin of thermal stability according to claim 1, it is characterised in that：Step
Rapid 3）Described polymerization terminal is step 3）Pressure drops to 0.08 ~ 0.12MPa of pressure difference in polymeric kettle.
A kind of 7. preparation method of the excellent polyvinyl chloride resin of thermal stability according to claim 1, it is characterised in that：Step
Rapid 1）The described vacuum vacuumized is -0.09 ~ -0.05 MPa.
A kind of 8. preparation method of the excellent polyvinyl chloride resin of thermal stability according to claim 1, it is characterised in that：Step
Rapid 2）Concrete operations be：By rare earth thermal stabilizer, 0.1 ~ 0.5 part is pumped into polymeric kettle with whole polymerization process constant speed.
A kind of 9. preparation method of the excellent polyvinyl chloride resin of thermal stability according to claim 1, it is characterised in that：Step
Rapid 1）Described initiation system is free radical type initiator, and dispersion is that polyvinyl alcohol dispersant disperses with cellulose ethers
The compound system of agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517292A (en) * | 2018-10-12 | 2019-03-26 | 安徽优丽普科技有限公司 | A kind of excellent anti-aging PVC board and preparation method thereof of thermal stability |
| CN109824806A (en) * | 2019-02-21 | 2019-05-31 | 内蒙古乌海化工有限公司 | A kind of production method and gained resin of polyvinyl chloride resin |
| CN110256780A (en) * | 2019-06-24 | 2019-09-20 | 中国石油化工股份有限公司 | Disposable transfusion device double-vane needle stand PVC PP Pipe Compound and the preparation method and application thereof |
| US11773194B2 (en) | 2018-10-29 | 2023-10-03 | Lg Chem, Ltd. | Vinyl chloride-based polymer and method for preparing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250335A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Production method of high-polymerization degree polyvinyl chloride resin |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104250335A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Production method of high-polymerization degree polyvinyl chloride resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517292A (en) * | 2018-10-12 | 2019-03-26 | 安徽优丽普科技有限公司 | A kind of excellent anti-aging PVC board and preparation method thereof of thermal stability |
| US11773194B2 (en) | 2018-10-29 | 2023-10-03 | Lg Chem, Ltd. | Vinyl chloride-based polymer and method for preparing same |
| CN109824806A (en) * | 2019-02-21 | 2019-05-31 | 内蒙古乌海化工有限公司 | A kind of production method and gained resin of polyvinyl chloride resin |
| CN110256780A (en) * | 2019-06-24 | 2019-09-20 | 中国石油化工股份有限公司 | Disposable transfusion device double-vane needle stand PVC PP Pipe Compound and the preparation method and application thereof |
| CN110256780B (en) * | 2019-06-24 | 2022-10-14 | 中国石油化工股份有限公司 | PVC (polyvinyl chloride) special material for double-wing needle base of disposable infusion apparatus as well as preparation method and application of PVC special material |
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