CN106554445A - 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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- CN106554445A CN106554445A CN201510625742.8A CN201510625742A CN106554445A CN 106554445 A CN106554445 A CN 106554445A CN 201510625742 A CN201510625742 A CN 201510625742A CN 106554445 A CN106554445 A CN 106554445A
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Abstract
A kind of preparation method of high concentration polyvinyl chloride solution, belongs to Polymer Synthesizing field.Characterized in that, preparation process is：The dioctyl phthalate of 100 weight portions is added first in pressure reaction still as solvent, add the peroxyesters initiator of 0.01 ~ 0.075 weight portion, pressure reaction still is evacuated to deoxidation 4 ~ 7 below -0.090MPa minute, again into kettle add 20 ~ 50 weight part of vinyl chloride monomers, being warming up to after being uniformly mixed under 40 DEG C ~ 70 DEG C of polymerization temperature carries out polyreaction, after the completion of polyreaction, exclude Vinyl Chloride Monomer in kettle, kettle temperature is down to into 15 DEG C ~ 35 DEG C again, discharging obtains final product polyvinyl chloride solution.The polyvinyl chloride resin solution for preparing of method that the present invention is provided has higher concentration and a good mobility, and solution is translucent state, without insoluble granule and impurity, with preferable degree of purity.
Description
Technical field
A kind of preparation method of high concentration polyvinyl chloride solution, belongs to Polymer Synthesizing field.
Background technology
Corvic（PVC）A kind of cheap, function admirable, using quite varied polymer, Corvic（PVC）Solution product has been applied to building and the packaging industries such as artificial leather, flooring laminate, glove material, wallpaper, leaching modeling, automobile decoration material at present.At present in polyvinyl chloride resin solution preparation process, the main product for adopting microsuspending method and emulsion polymerization technique to produce is stirred mixed method, i.e., common dissolving method with plasticizer equal solvent.
The polyvinyl chloride resin solution prepared using said method, its performance are subject to many restrictions.Wherein, maximum polyvinyl chloride resin properties of product, stirring and dissolving means and the Operating parameters for obtaining that are respectively polymerized of influence factor, properties of product affect the presence of uncontrollable factor, polyvinyl chloride resin solution product quality fluctuation is larger, and due to the paste PVC resin produced using microsuspending method or emulsion method, the impurity such as dispersant of the polymerization used in, emulsifying agent, electrolyte can be brought in solution into so that the quality stability of shaped article, heat stability and electric property etc. are affected obtained in Jing polyvinyl chloride resin solution.
The content of the invention
The technical problem to be solved in the present invention is：Overcome the deficiencies in the prior art, there is provided a kind of preparation method of the high concentration polyvinyl chloride solution of high cleanliness and good fluidity.
The technical solution adopted for the present invention to solve the technical problems is：The preparation method of the high concentration polyvinyl chloride solution, it is characterised in that preparation process is：The dioctyl phthalate of 100 weight portions is added first in pressure reaction still as solvent, add the peroxyesters initiator of 0.01 ~ 0.075 weight portion, pressure reaction still is evacuated to deoxidation 4 ~ 7 below -0.090MPa minute, again into kettle add 20 ~ 50 weight part of vinyl chloride monomers, being warming up to after being uniformly mixed under 40 DEG C ~ 70 DEG C of polymerization temperature carries out polyreaction, after the completion of polyreaction, exclude the Vinyl Chloride Monomer of residual in kettle, kettle temperature is down to into 15 DEG C ~ 35 DEG C again, discharging obtains final product polyvinyl chloride solution.
Plasticizer type solvent used by polyvinyl chloride resin solution is prepared using common dissolution process under usual conditions, the solvent of polymerization of vinyl choride monomer is can be used as, solvent needs to have that excellent compatibility, heat stability are good, volatility is low, cheap with polyvinyl chloride resin.Can have various as the plasticizer type solvent that chloroethylene polymerization is used, conventional such as dibutyl sebacate, diethyl phthalate, dibutyl phthalate, epoxidised fatty dibutyl phthalate, di-n-octyl sebacate, dioctyl adipate, DOTP etc., but the research of the present invention shows, the plasticizer type solvent good advantage that dioctyl phthalate is polymerized as vinyl chloride solution, main cause is which has appropriate dissolved efficiency with polyvinyl chloride resin, therefore can obtain the high concentration polyvinyl chloride resin solution of good fluidity in the course of the polymerization process.In the vinyl chloride-base polymer solution for preparing the present invention, if with 100 parts of dioctyl phthalates as solvent, 20 ~ 50 parts of Vinyl Chloride Monomer should be added for carried out converging operationJu Hecaozuo.As vinyl chloride has excellent solubility property in dioctyl phthalate, if monomer is less than 20 parts added by polymerization, partial pressure of the Vinyl Chloride Monomer in polymerization system gas phase is low, it is impossible to determines polyreaction process using reduced pressure method and controls polymerisation conversion.And if be higher than 50 parts, but the Vinyl Chloride Monomer of polymerization conversion is limited, and unreacted monomer can be caused excessive so that MONOMER RECOVERY overlong time, has influence on the economy of production process.
In described polyvinyl chloride solution, the mass content of polyvinyl chloride resin is 9% ~ 10%.With higher concentration, in polyvinyl chloride solution, the mass content of polyvinyl chloride resin can reach 10% to the polyvinyl chloride solution that the present invention is prepared as solvent using dioctyl phthalate, significantly larger than the content of the polyvinyl chloride resin of prior art.
Described peroxyesters initiator is peroxy dicarbonate two（2- ethylhexyls）One kind, two or more arbitrary proportion complex in ester, new peroxide tert-butyl caprate, peroxidating pivalic acid tert-pentyl ester or cumyl peroxyneodecanoate.To carry out the chloroethylene polymerization reaction of the present invention, need the initiator with thermal initiation effect is added in dioctyl phthalate.As thermal initiator, the preferred peroxyesters initiator of oil-soluble good heat stability of the present invention, including peroxy dicarbonate two（2- ethylhexyls）Ester, new peroxide tert-butyl caprate, peroxidating pivalic acid tert-pentyl ester, cumyl peroxyneodecanoate etc..These initiators can be used alone, it is also possible to by two of which or two or more compound uses, and what this depended on the adopted temperature of polymerization and the half-life of decomposition of initiator matches requirement.
Preferably, described polymerization temperature is 55 ~ 65 DEG C.Polymerization temperature is the crucial governing factor of rate of polymerization, under the conditions of solvent reaction of the present invention enough can readily control reaction process.When polymerization temperature is 55 ~ 65 DEG C, this polyreaction can be controlled and reach highest polyvinyl chloride resin content, while ensureing the efficiency of polyreaction.
The condition that described polyreaction is completed is that the pressure in pressure reaction still is down to 0.82 MPa
~0.69 MPa.The performance level of polyreaction can be judged by pressure drop, and the Rule of judgment that polyreaction of the present invention is completed is carrying out by the change of vinyl chloride reaction pressure.Vinyl chloride in polymerization process, with the generation of vinyl chloride-base polymer, Vinyl Chloride Monomer partial pressure in gas phase（Ratio）Reduce, therefore the performance level of polyreaction can be judged by pressure drop.Due to the change of the condition such as monomer ratio in different polymerization temperatures, charging coefficient and material, affect the pressure range of polymerization judgement in the present invention also different.Under the conditions of the present invention, when pressure is down to 0.82 MPa
May determine that during ~ 0.69 MPa that polyreaction reaches optimal reaction and completes condition, continue having little significance for reflection.
The polyreaction of the present invention needs to carry out under conditions of anoxybiotic.Preferably, in described pressure reaction still, the vacuum of evacuation deoxidation is -0.150MPa ~ -0.100MPa.The polyreaction of the present invention needs to carry out under conditions of anoxybiotic, and the vacuum that evacuation is controlled in initial evacuation deoxidation is the anoxic condition that -0.150MPa ~ -0.100MPa can fully ensure that the present invention.
Preferably, the addition of described peroxyesters initiator is 0.035 ~ 0.060 weight portion.Initiator amount in the present invention, with relative to the Vinyl Chloride Monomer gross mass for being added as standard, wherein initiator dosage number, the main control for considering polymerization reaction time and reactive polymeric remove heat energy power.When initiator amount is less than 0.035 part, polymerization reaction time can extend, and economy is poorer than me.And when being higher than 0.060 part, polyreaction is very fast, reaction process control difficulty increases, and is unfavorable for stability and the safety of converging operationJu Hecaozuo.But can pass through to adjust polymerization temperature under consumption of the invention above-mentioned 0.01 ~ 0.075 part and monomer concentration ensures being normally carried out for polyreaction of the present invention.
Described pressure reaction still is evacuated to deoxidation 5 below -0.090MPa minute.Reach optimal deoxidation effect.
The addition of described Vinyl Chloride Monomer is 37 ~ 42 weight portions.
Compared with prior art, a kind of preparation method of high concentration polyvinyl chloride solution of the invention is had an advantageous effect in that：The method of the present invention can be prepared with dioctyl phthalate as solvent polyvinyl chloride solution, and the solution 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, the polyvinyl chloride resin solution that the method provided using the present invention is prepared does not contain the impurity such as emulsifying agent, dispersant, inorganic salt, with preferable solution purity degree, solution is translucent state, without insoluble granule and impurity.
Specific embodiment
The present invention is further illustrated below by specific embodiment, wherein embodiment 1 is most preferred embodiment.In each embodiment solution, polyvinyl chloride resin polymer content mensuration mode is：It is measured using weight method, in solution, polyvinyl chloride resin content is calculated as follows,
In formula, s：Polyvinyl chloride resin content in solution（%）；me：Final polyvinyl chloride resin solution product gross mass（g）；m0：The plasticizer quality of polymerization addition（g）；The mobile performance and apparent condition of chloroethylene polymerization resin solution is by the way of naked eyes observation directly perceived.
Embodiment 1
2.80kg dioctyl phthalates, cumyl peroxyneodecanoate 0.40g, peroxy dicarbonate two are sequentially added in the 5L stainless steel pressure reactors for being furnished with agitator（2- ethylhexyls）Ester 0.60g, capping kettle open stirring, extracting vacuum, the deoxidation 5 minutes under the conditions of pressure is less than -0.090MPa, then into kettle, add Vinyl Chloride Monomer 1.0kg, stirring at normal temperature to mix 10 minutes, kettle temperature risen to 60 DEG C and starts reaction.After polymerization pressure depreciation reaches 0.069MPa, Vinyl Chloride Monomer in kettle is excluded, then kettle temperature is brought down below into 35 DEG C, discharging.Can be seen by observation, polymer solution is in slightly partially yellow translucent flow regime, without insoluble particulates.PVC polymer solution gross weight 3090g, calculates and understands polyvinyl chloride resin content 10.4% in solution, slightly yellow translucent of the solution in good fluidity.
Embodiment 2
Converging operationJu Hecaozuo method is same as Example 1, except that in pressure less than deoxidation under the conditions of -0.100MPa 4 minutes, then the Vinyl Chloride Monomer of 0.6kg is added into kettle, and polymerization pressure is reduced to 0.072MPa.It is 3104g finally to weigh PVC polymer solution, calculates and understands polyvinyl chloride resin content 9. 8% in solution, slightly yellow translucent of the solution in good fluidity.
Embodiment 3
Converging operationJu Hecaozuo method is same as Example 1, except for the difference that makees initiator using new peroxide tert-butyl caprate 0.65g and peroxidating pivalic acid tert-pentyl ester 0.33g, and causes polymerization under the conditions of 65 DEG C.Polymerization pressure is reduced to 0.082MPa.PVC polymer solution gross weight 3104g is finally given, is calculated and is understood polyvinyl chloride resin content 9.7% in solution, slightly yellow translucent of the solution in good fluidity.
Embodiment 4
Converging operationJu Hecaozuo method is same as Example 1, except for the difference that deoxidation 4 minutes under the conditions of pressure is less than -0.150MPa, then Vinyl Chloride Monomer 1.4kg is added into kettle, and adds peroxidating pivalic acid tert-pentyl ester 1.68g to make initiator, and causes polymerization under the conditions of 65 DEG C.Polymerization pressure is reduced to 0.080MPa.PVC polymer solution gross weight 3077g is finally given, is calculated and is understood polyvinyl chloride resin content 9.0% in solution, slightly yellow translucent of the solution in good fluidity.
Embodiment 5
Converging operationJu Hecaozuo method is same as Example 1, except for the difference that deoxidation 7 minutes under the conditions of pressure is less than -0.090MPa, then Vinyl Chloride Monomer 1.2kg is added into kettle, and makees initiator using peroxidating pivalic acid tert-pentyl ester 2.1g, causes polymerization under the conditions of 40 DEG C.Polymerization pressure is reduced to 0.075MPa.PVC polymer solution gross weight 3101g is finally given, is calculated and is understood polyvinyl chloride resin content 9.7% in solution, slightly yellow translucent of the solution in good fluidity.
Embodiment 6
Converging operationJu Hecaozuo method is same as Example 1, and except for the difference that Vinyl Chloride Monomer dosage is 0.56kg, and is added using peroxy dicarbonate two（2- ethylhexyls）Ester 0.28g makees initiator, causes polymerization under the conditions of 70 DEG C.Polymerization pressure is reduced to 0.079MPa, finally gives PVC polymer solution gross weight 3122g, polyvinyl chloride resin content 9.1% in solution, solution slightly yellow translucent in a flowable.
Comparative example 1
Take clean 500mL glass beakers, 184.0g dioctyl phthalate liquid is weighed in beaker, under stirring, the 16.0g trades mark is added for the paste PVC resin of PSH-30,60 ~ 70 DEG C of interval, stirring and dissolving 240 minutes are heated uniformly to 1000W closed electric furnaces again.Observation mixing liquid status after stopping heating and stirring, it can be seen that still have white opacity particulate matter when appropriate initiator is not added in solution insoluble in dioctyl phthalate solution.
Comparative example 2
Operational approach and formula are same as Example 1, except that when polymerization pressure depreciation is controlled to 0.090MPa, there is vibration in polymerization reaction kettle shaft, stop stirring, start to exclude Vinyl Chloride Monomer in kettle, and kettle temperature is brought down below into less than 30 DEG C, can be seen by observation after opening polymeric kettle, jelly state of the polymer solution in difficult flowing.PVC polymer solution gross weight 3156g is collected, is calculated and is understood polyvinyl chloride resin content 11.3% in solution.When without reaction is terminated in appropriate pressure drop, the mobility of polymer solution can be affected.But polyvinyl chloride resin content remains to keep higher.
Comparative example 3
Main formula and operational approach are same as Example 5, and dioctyl phthalate is replaced with DOTP except for the difference that.When polymerization pressure drop is up to 0.080MPa, there is vibration in polymeric kettle stirring, stops stirring.After excluding vinyl chloride residual monomer cooling, it is found that material is in immobilising gelatin in kettle.Collect solution weighing and understand that gross mass is 3010g, it is 7.0% to calculate polyvinyl chloride resin content.It can be seen that the polyvinyl chloride solution of polyvinyl chloride resin content height and good fluidity when dioctyl phthalate is replaced using the DOTP of different key mappings, still can not be obtained.
Comparative example 4
Polymerization formula and operating procedure are same as Example 3, and dioctyl phthalate is replaced with diethyl phthalate except for the difference that.There is vibration in polymeric kettle stirring when polymerization pressure is reduced to 0.087MPa, stops stirring.In final kettle, material is collected solution and is weighed as 3024g, polyvinyl chloride resin content 7.4% in gelatin.When dioctyl phthalate is replaced using the close diethyl phthalate of property, the polyvinyl chloride solution of polyvinyl chloride resin content height and good fluidity still can not be obtained.
The above, is only presently preferred embodiments of the present invention, is not the restriction for making other forms to the present invention, and any those skilled in the art are changed or be modified as the Equivalent embodiments of equivalent variations possibly also with the technology contents of the disclosure above.But it is every without departing from technical solution of the present invention content, according to any simple modification, equivalent variations and remodeling that the technical spirit of the present invention is made to above example, still fall within the protection domain of technical solution of the present invention.
Claims (9)
1. a kind of preparation method of high concentration polyvinyl chloride solution, it is characterised in that preparation process is：The dioctyl phthalate of 100 weight portions is added first in pressure reaction still as solvent, add the peroxyesters initiator of 0.01 ~ 0.075 weight portion, pressure reaction still is evacuated to deoxidation 4 ~ 7 below -0.090MPa minute, again into kettle add 20 ~ 50 weight part of vinyl chloride monomers, being warming up to after being uniformly mixed under 40 DEG C ~ 70 DEG C of polymerization temperature carries out polyreaction, after the completion of polyreaction, exclude the Vinyl Chloride Monomer of residual in kettle, kettle temperature is down to into 15 DEG C ~ 35 DEG C again, discharging obtains final product polyvinyl chloride solution.
2. the preparation method of a kind of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that：In described polyvinyl chloride solution, the mass content of polyvinyl chloride resin is 9% ~ 10%.
3. the preparation method of a kind of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that：Described peroxyesters initiator is peroxy dicarbonate two（2- ethylhexyls）One kind, two or more arbitrary proportion complex in ester, new peroxide tert-butyl caprate, peroxidating pivalic acid tert-pentyl ester or cumyl peroxyneodecanoate.
4. the preparation method of a kind of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that：Described polymerization temperature is 55 ~ 65 DEG C.
5. the preparation method of a kind of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that：The condition that described polyreaction is completed is that the pressure in pressure reaction still is down to 0.082 MPa ~ 0.069 MPa.
6. the preparation method of a kind of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that：In described pressure reaction still, the vacuum of evacuation deoxidation is -0.150MPa ~ -0.100MPa.
7. the preparation method of a kind of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that：The addition of described peroxyesters initiator is 0.035 ~ 0.060 weight portion.
8. the preparation method of a kind of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that：Described pressure reaction still is evacuated to deoxidation 5 below -0.090MPa minute.
9. the preparation method of a kind of high concentration polyvinyl chloride solution according to claim 1, it is characterised in that：The addition of described Vinyl Chloride Monomer is 37 ~ 42 weight portions.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484572A (en) * | 2020-05-12 | 2020-08-04 | 上海宝钱化工有限公司 | Preparation method of water-phase method coating-grade perchloroethylene resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5298791A (en) * | 1976-02-17 | 1977-08-18 | Stauffer Chemical Co | Preparation of polyvinyl chloride having little unreacted vinyl chloride content |
| 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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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5298791A (en) * | 1976-02-17 | 1977-08-18 | Stauffer Chemical Co | Preparation of polyvinyl chloride having little unreacted vinyl chloride content |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484572A (en) * | 2020-05-12 | 2020-08-04 | 上海宝钱化工有限公司 | Preparation method of water-phase method coating-grade perchloroethylene resin |
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