CN106554445B - A kind of preparation method of high concentration polyvinyl chloride solution - Google Patents
A kind of preparation method of high concentration polyvinyl chloride solution Download PDFInfo
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- CN106554445B CN106554445B CN201510625742.8A CN201510625742A CN106554445B CN 106554445 B CN106554445 B CN 106554445B CN 201510625742 A CN201510625742 A CN 201510625742A CN 106554445 B CN106554445 B CN 106554445B
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Abstract
A kind of preparation method of high concentration polyvinyl chloride solution, belongs to Polymer Synthesizing field.It is characterized in that, preparation step are as follows: the dioctyl phthalate of 100 parts by weight is added into pressure reaction still first as solvent, add the peroxyesters initiator of 0.01 ~ 0.075 parts by weight, pressure reaction still is evacuated to -0.090MPa or less deoxidation 4 ~ 7 minutes, 20 ~ 50 weight part of vinyl chloride monomers are added into kettle again, it is warming up to after being uniformly mixed under 40 DEG C ~ 70 DEG C of polymerization temperature and carries out polymerization reaction, after the completion of polymerization reaction, exclude vinyl chloride monomer in kettle, kettle temperature is down to 15 DEG C ~ 35 DEG C again, discharging is up to polyvinyl chloride solution.The polyvinyl chloride resin solution concentration with higher and good mobility that method provided by the invention is prepared, solution are translucent state, no insoluble granule and impurity, have preferable degree of purity.
Description
Technical field
A kind of preparation method of high concentration polyvinyl chloride solution, belongs to Polymer Synthesizing field.
Background technique
Corvic (PVC) is cheap one kind, function admirable, using very extensive polymer, polychlorostyrene second
Olefine resin (PVC) solution product has been applied to artificial leather, flooring laminate, glove material, wallpaper, leaching modeling, automobile decoration material etc. at present
Building and packaging industry.It is main that microsuspending method and emulsion polymerization technique is used to produce at present in polyvinyl chloride resin solution preparation process
Product and plasticizer equal solvent are stirred mixed method, i.e., common dissolving method.
The polyvinyl chloride resin solution prepared using the above method, performance is by various limitations.Wherein, influence factor is most
Big respectively polymerize obtained polyvinyl chloride resin properties of product, stirring and dissolving means and Operating parameters, and properties of product influence is deposited
In uncontrollable factor, polyvinyl chloride resin solution product quality fluctuation is larger, and due to being produced using microsuspending method or emulsion method
Paste PVC resin, the impurity such as polymerization dispersing agent, emulsifier, electrolyte used in can be brought in solution into, so that through PVC
Quality stability, thermal stability and electric property of shaped article made from resin solution etc. are affected.
Summary of the invention
The technical problem to be solved by the present invention is overcoming the deficiencies of the prior art and provide a kind of high cleanliness and good stream
The preparation method of the high concentration polyvinyl chloride solution of dynamic property.
The technical solution adopted by the present invention to solve the technical problems is: the preparation side of the high concentration polyvinyl chloride solution
Method, which is characterized in that preparation step are as follows: the dioctyl phthalate that 100 parts by weight are added into pressure reaction still first is made
For solvent, add the peroxyesters initiator of 0.01 ~ 0.075 parts by weight, pressure reaction still be evacuated to -0.090MPa with
Lower deoxidation 4 ~ 7 minutes, then 20 ~ 50 weight part of vinyl chloride monomers are added into kettle, 40 DEG C ~ 70 DEG C are warming up to after being uniformly mixed
Polymerization temperature under carry out polymerization reaction, after the completion of polymerization reaction, exclude remaining vinyl chloride monomer in kettle, then kettle temperature dropped
To 15 DEG C ~ 35 DEG C, discharging is up to polyvinyl chloride solution.
Plasticizer type solvent used in polyvinyl chloride resin solution is prepared using common dissolution process under usual conditions, is ok
Solvent as polymerization of vinyl choride monomer, solvent need to have with polyvinyl chloride resin that excellent compatibility, thermal stability be good, volatility
It is low, cheap.The plasticizer type solvent used as chloroethylene polymerization can there are many, it is common as dibutyl sebacate,
Diethyl phthalate, dibutyl phthalate, epoxidised fatty dibutyl phthalate, dioctyl sebacate, dioctyl adipate,
Dioctyl terephthalate etc., but it is of the invention studies have shown that the increasing that dioctyl phthalate polymerize as vinyl chloride solution
Dosage form solvent good advantage is moulded, main cause is it and polyvinyl chloride resin has dissolved efficiency appropriate, therefore in the course of the polymerization process may be used
To obtain the high concentration polyvinyl chloride resin solution of good fluidity.In preparing vinyl chloride-base polymer solution of the invention, if with 100
Part dioctyl phthalate is solvent, and 20 ~ 50 parts of vinyl chloride monomer should be added for carried out converging operation.Due to chlorine
Ethylene has excellent solubility property in dioctyl phthalate, if polymerizeing added monomer is lower than 20 parts, vinyl chloride monomer
Partial pressure in polymerization system gas phase is relatively low, can not be determined polymerization reaction process using pressure reduction method and be controlled polymerization conversion
Rate.And if be higher than 50 parts, but the vinyl chloride monomer of polymerization conversion is limited, and it is excessive to will cause unreacted monomer, so that MONOMER RECOVERY
Overlong time influences the economy of production process.
The mass content of polyvinyl chloride resin is 9% ~ 10% in the polyvinyl chloride solution.The present invention utilizes phthalic acid two
Monooctyl ester has higher concentration as polyvinyl chloride solution prepared by solvent, the mass content of polyvinyl chloride resin in polyvinyl chloride solution
It can achieve 10%, the significantly larger than content of the polyvinyl chloride resin of the prior art.
The peroxyesters initiator is dicetyl peroxydicarbonate two (2- ethylhexyl) ester, the tertiary fourth of peroxidating neodecanoic acid
One of ester, peroxidating pivalic acid tert-pentyl ester or cumyl peroxyneodecanoate, two or more arbitrary proportion
Compound.To carry out chloroethylene polymerization reaction of the invention, needing to be added in dioctyl phthalate, there is heat to cause function
The initiator of effect.As thermal initiator, the preferred peroxyesters initiator of oil-soluble good heat stability of the present invention, packet
Dicetyl peroxydicarbonate two (2- ethylhexyl) ester is included, new peroxide tert-butyl caprate, peroxidating pivalic acid tert-pentyl ester, peroxidating are new
Capric acid isopropyl phenyl ester etc..These initiators can be used alone, can also be by two of them or two or more compound uses, this takes
The certainly matching requirement of the half-life period of the temperature used by polymerizeing and decomposition of initiator.
Preferably, the polymerization temperature is 55 ~ 65 DEG C.Polymerization temperature is the key that rate of polymerization governing factor, at this
Reaction process enough can be readily controlled under the conditions of invention solvent reaction.When polymerization temperature is 55 ~ 65 DEG C, it is poly- that this can be controlled
It closes reaction and reaches highest polyvinyl chloride resin content, while guaranteeing the efficiency of polymerization reaction.
The condition that the polymerization reaction is completed is that the pressure in pressure reaction still is down to the MPa of 0.82 MPa ~ 0.69.It is poly-
The performance level for closing reaction can judge that the Rule of judgment that polymerization reaction of the present invention is completed is to pass through by pressure drop
Vinyl chloride reaction pressure changes to carry out.Vinyl chloride is in polymerization process, with the generation of vinyl chloride-base polymer, gas
Vinyl chloride monomer partial pressure (ratio) reduces in phase, therefore the performance level of polymerization reaction can be judged by pressure drop.Due to
The variation of the conditions such as monomer ratio in different polymerization temperature, charging coefficient and material, influences polymerization in the present invention and judges
Pressure range it is also different.Under the conditions of the present invention, it can sentence when pressure is down to 0.82 MPa ~ 0.69 MPa
Disconnected polymerization reaction reaches optimal reaction completion condition, continues having little significance for reflection.
Polymerization reaction needs of the invention carry out under conditions of anoxybiotic.Preferably, it is taken out in the pressure reaction still true
The vacuum degree of empty deoxidation is -0.150MPa ~ -0.100MPa.Polymerization reaction needs of the invention carry out under conditions of anoxybiotic,
It is that -0.150MPa ~ -0.100MPa can fully ensure that of the invention exhausted that the vacuum degree that vacuumizes is controlled when initial evacuation deoxidation
Oxygen condition.
Preferably, the additional amount of the peroxyesters initiator is 0.035 ~ 0.060 parts by weight.Cause in the present invention
Agent dosage, using relative to the vinyl chloride monomer gross mass being added as standard, wherein initiator dosage number, it is main consider it is poly-
Close the control in reaction time and the cooling ability of reactive polymeric.When initiator amount is lower than 0.035 part, polymerization reaction time meeting
Extend, economy is poorer than me.And when being higher than 0.060 part, polymerization reaction is very fast, and reaction process controls difficulty and increases, and is unfavorable for gathering
The stability and safety of closing operation.But it can be by adjusting polymerization temperature under above-mentioned 0.01 ~ 0.075 part of the dosage of the present invention
Guarantee being normally carried out for polymerization reaction of the present invention with monomer concentration.
The pressure reaction still is evacuated to -0.090MPa or less deoxidation 5 minutes.Reach best deoxidation effect.
The additional amount of the vinyl chloride monomer is 37 ~ 42 parts by weight.
Compared with prior art, beneficial to effect possessed by a kind of preparation method of high concentration polyvinyl chloride solution of the invention
Fruit is: method of the invention can be prepared using dioctyl phthalate as solvent polyvinyl chloride solution, which has
Not only high concentration but also the characteristics of good fluidity.Compared to the resin produced using emulsion polymerization technique and process for suspension polymerization, adopt
The polyvinyl chloride resin solution being prepared with method provided by the invention has without containing impurity such as emulsifier, dispersing agent, inorganic salts
Preferable solution purity degree, solution are translucent state, no insoluble granule and impurity.
Specific embodiment
The present invention is further illustrated below by specific embodiment, wherein embodiment 1 is most preferred embodiment.Each reality
Apply polyvinyl chloride resin polymer content mensuration mode in solution are as follows: be measured using weight method, polyvinyl chloride resin content is pressed in solution
Following formula calculates,
In formula, s: polyvinyl chloride resin content (%) in solution；me: final polyvinyl chloride resin solution product gross mass (g)；m0: polymerization
The plasticizer quality (g) of addition；The mobile performance and apparent condition of chloroethylene polymerization resin solution are intuitively observed using naked eyes
Mode.
Embodiment 1
2.80kg dioctyl phthalate, peroxide are sequentially added into the 5L stainless steel pressure reaction kettle equipped with blender
Change neodecanoic acid isopropyl phenyl ester 0.40g, dicetyl peroxydicarbonate two (2- ethylhexyl) ester 0.60g, capping kettle opens stirring,
Vacuum is extracted, deoxidation 5 minutes under the conditions of pressure is lower than -0.090MPa, then vinyl chloride monomer 1.0kg, room temperature are added into kettle
It is stirred 10 minutes, kettle temperature is risen to 60 DEG C and starts to react.After polymerization pressure depreciation reaches 0.069MPa, kettle is excluded
Interior vinyl chloride monomer, then kettle temperature is brought down below 35 DEG C, discharging.By observation, it can be seen that, polymer solution is in slightly partially yellow
Translucent flow regime, no insoluble particulates.PVC polymer solution gross weight 3090g is calculated and is known polyvinyl chloride resin in solution
Content 10.4%, solution are in the yellowish translucent of good fluidity.
Embodiment 2
Converging operation method is same as Example 1, except that deoxidation 4 divides under the conditions of pressure is lower than -0.100MPa
Clock, then the vinyl chloride monomer of 0.6kg is added into kettle, polymerization pressure is reduced to 0.072MPa.It is molten finally to weigh PVC polymer
Liquid is 3104g, calculates and knows polyvinyl chloride resin content 9. 8% in solution, and solution is in the yellowish translucent of good fluidity.
Embodiment 3
Converging operation method is same as Example 1, the difference is that using new peroxide tert-butyl caprate 0.65g and peroxidating
Pivalic acid tert-pentyl ester 0.33g makees initiator, and causes polymerization under the conditions of 65 DEG C.Polymerization pressure is reduced to 0.082MPa.Most
PVC polymer solution gross weight 3104g is obtained eventually, is calculated and is known polyvinyl chloride resin content 9.7% in solution, solution is in good fluidity
Yellowish translucent.
Embodiment 4
Converging operation method is same as Example 1, the difference is that deoxidation 4 minutes under the conditions of pressure is lower than -0.150MPa,
Vinyl chloride monomer 1.4kg is added into kettle again, and peroxidating pivalic acid tert-pentyl ester 1.68g is added and makees initiator, and in 65 DEG C of items
Cause polymerization under part.Polymerization pressure is reduced to 0.080MPa.PVC polymer solution gross weight 3077g is finally obtained, calculates and knows
Polyvinyl chloride resin content 9.0% in solution, solution are in the yellowish translucent of good fluidity.
Embodiment 5
Converging operation method is same as Example 1, the difference is that deoxidation 7 minutes under the conditions of pressure is lower than -0.090MPa,
Vinyl chloride monomer 1.2kg is added into kettle again, and makees initiator using peroxidating pivalic acid tert-pentyl ester 2.1g, under the conditions of 40 DEG C
Cause polymerization.Polymerization pressure is reduced to 0.075MPa.PVC polymer solution gross weight 3101g is finally obtained, calculates and knows solution
Middle polyvinyl chloride resin content 9.7%, solution are in the yellowish translucent of good fluidity.
Embodiment 6
Converging operation method is same as Example 1, the difference is that vinyl chloride monomer dosage is 0.56kg, and is added and used
It aoxidizes two carbonic acid two (2- ethylhexyl) ester 0.28g and makees initiator, cause polymerization under the conditions of 70 DEG C.Polymerization pressure is reduced to
0.079MPa finally obtains PVC polymer solution gross weight 3122g, and polyvinyl chloride resin content 9.1% in solution, solution is in a flowable
Yellowish translucent.
Comparative example 1
Clean 500mL glass beaker is taken, 184.0g dioctyl phthalate liquid is weighed in beaker, in stirring
Under, the 16.0g trade mark is added and is the paste PVC resin of PSH-30, then is heated uniformly to 60 ~ 70 DEG C of areas with 1000W closed electric furnace
Between, stirring and dissolving 240 minutes.Observation mixes liquid status after stopping heating and stirring, it can be seen that suitably causes in no addition
Still there is white opacity particulate matter insoluble in dioctyl phthalate solution when agent in solution.
Comparative example 2
Operating method and formula are same as Example 1, except that when the control of polymerization pressure depreciation is
When 0.090MPa, polymerization reaction kettle agitating shaft vibrates, and stops stirring, starts to exclude vinyl chloride monomer in kettle, and by kettle temperature
It can see after 30 DEG C are brought down below hereinafter, opening polymeric kettle by observation, polymer solution is in the jelly state of difficult flowing.It receives
Collect PVC polymer solution gross weight 3156g, calculates and know polyvinyl chloride resin content 11.3% in solution.When not in pressure drop appropriate
When reaction was completed, the mobility of polymer solution will affect.But polyvinyl chloride resin content is still able to maintain higher.
Comparative example 3
Main formula and operating method are same as Example 5, the difference is that replacing with dioctyl phthalate to benzene
Diformazan dioctyl phthalate.When polymerization pressure drop reaches 0.080MPa, polymeric kettle stirring is vibrated, and stops stirring.It is residual to exclude vinyl chloride
After remaining monomer and cooling, it is found that material is in immobilising gelatin in kettle.Gross mass known to collecting solution weighing is 3010g, meter
Calculating polyvinyl chloride resin content is 7.0%.It can be seen that when replacing dioctyl phthalate using the dioctyl terephthalate of different key mappings
When, it still cannot obtain the polyvinyl chloride solution of polyvinyl chloride resin content height and good fluidity.
Comparative example 4
Polymerization formula and operating procedure are same as Example 3, the difference is that dioctyl phthalate is replaced with adjacent benzene
Dicarboxylate.Polymeric kettle stirring is vibrated when polymerization pressure is reduced to 0.087MPa, stops stirring.Object in final kettle
Expect to be in gelatin, collects solution and be weighed as 3024g, polyvinyl chloride resin content 7.4%.When using phthalic acid diethyl similar in property
When ester replaces dioctyl phthalate, the polyvinyl chloride solution of polyvinyl chloride resin content height and good fluidity still cannot be obtained.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Claims (8)
1. a kind of preparation method of high concentration polyvinyl chloride solution, which is characterized in that preparation step are as follows: first to pressure reaction still
The middle dioctyl phthalate that 100 parts by weight are added adds the peroxyesters of 0.01 ~ 0.075 parts by weight as solvent
Initiator, pressure reaction still are evacuated to -0.090MPa or less deoxidation 4 ~ 7 minutes, then 20 ~ 50 parts by weight chloroethenes are added into kettle
Alkene monomer is warming up under 40 DEG C ~ 70 DEG C of polymerization temperature after being uniformly mixed and carries out polymerization reaction, when polymerization reaction is completed
Afterwards, remaining vinyl chloride monomer in kettle is excluded, then kettle temperature is down to 15 DEG C ~ 35 DEG C, discharging is up to polyvinyl chloride solution；
The condition that the polymerization reaction is completed is that the pressure in pressure reaction still is down to the MPa of 0.082 MPa ~ 0.069.
2. a kind of preparation method of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that: described is poly-
The mass content of polyvinyl chloride resin is 9% ~ 10% in vinyl chloride solution.
3. a kind of preparation method of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that: the mistake
Oxidation esters initiator is dicetyl peroxydicarbonate two (2- ethylhexyl) ester, new peroxide tert-butyl caprate, peroxidating pivalic acid
One of tert-pentyl ester or cumyl peroxyneodecanoate, two or more arbitrary proportion compound.
4. a kind of preparation method of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that: described is poly-
Closing temperature is 55 ~ 65 DEG C.
5. a kind of preparation method of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that: the pressure
The vacuum degree that deoxidation is vacuumized in power reaction kettle is -0.150MPa ~ -0.100MPa.
6. a kind of preparation method of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that: the mistake
The additional amount for aoxidizing esters initiator is 0.035 ~ 0.060 parts by weight.
7. a kind of preparation method of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that: the pressure
Power reaction kettle is evacuated to -0.090MPa or less deoxidation 5 minutes.
8. a kind of preparation method of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that: the chlorine
The additional amount of vinyl monomer is 37 ~ 42 parts by weight.
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| CN102952225A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Suspension polymerization method for reducing polyvinyl chloride resin fisheyes |
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| CN102952225A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Suspension polymerization method for reducing polyvinyl chloride resin fisheyes |
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