CN102952224A - Low-polymerization-degree polyvinyl chloride pasty resin preparation method - Google Patents
Low-polymerization-degree polyvinyl chloride pasty resin preparation method Download PDFInfo
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- CN102952224A CN102952224A CN2011102491362A CN201110249136A CN102952224A CN 102952224 A CN102952224 A CN 102952224A CN 2011102491362 A CN2011102491362 A CN 2011102491362A CN 201110249136 A CN201110249136 A CN 201110249136A CN 102952224 A CN102952224 A CN 102952224A
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Abstract
The invention relates to the technical field of chloroethylene polymerization in the chemical industry for making chlorine and alkali, in particular to a low-polymerization-degree polyvinyl chloride pasty resin preparation method. The microsuspension polymerization process is adopted for chloroethylene polymerization, and chain transfer agent is added into a reaction system for one time before polymerization reaction or added into the reaction system in batches during polymerization at 52-56 DEG C to prepare polyvinyl chloride pasty resin with the polymerization degree of 500-900, wherein addition amount of the chain transfer agent is 0.02%-0.2% of weight of vinyl chloride monomer. The polymerization degree at the same temperature is lowered by adding the chain transfer agent during polymerization to enable the polymerization to be completed at low temperature. Therefore, polyvinyl chloride pasty resin prepared by the method has the advantages of low plasticizing temperature, excellent pasting performance, low paste adhesion, high foaming performance, high heat stability, high production stability and the like.
Description
Skill is stated the field
The present invention relates to chemical industry for making chlorine and alkali industry chloroethylene polymerization technical field, specifically a kind of polyvinyl-chloride of low-polymerization degree is stuck with paste the preparation method of resin.
Background technology
Polyvinyl chloride (Polyvinyl Chloride, the abbreviation polyvinyl chloride) resin is the thermal plasticity high polymer that is formed by polymerization of vinyl choride monomer, wherein pvc resin paste grade and softening agent and processing aid stir together and form stable plastipaste, and end article is produced in plasticizing through heating.Be mainly used in being processed into polyvinyl chloride wallpaper, leatheroid, foam floor, flame-retardant conveyor belt, battery separator, steel plate coating, toy for children, waterproof cloth, seal gasket for bottle cap, and various family adornments etc.Polymer poly is right, become to stick with paste property, stick with paste viscosity and thermostability is the main quality index of this series products.Usually pvc resin paste grade polymerization degree index is mainly by polymeric reaction temperature control, along with the rising product polymerization degree reduction of polymerization temperature.In order to make the polyvinyl-chloride of low-polymerization degree resin, polyreaction must be carried out under comparatively high temps, and higher polymerization temperature, not only the withstand voltage properties of polymeric kettle had high requirements, also can cause sticking still serious, and because PVC branchign of molecule degree increases the thermal stability variation that makes polyvinyl chloride (PVC) RESINS, just can be under relatively low polymerization temperature behind the interpolation chain-transfer agent, preparation polyvinyl-chloride of low-polymerization degree resin.The object of the invention: be exactly under relatively lower temp, reduce the method for the pvc resin paste grade product polymerization degree by adopting chain-transfer agent, realize the preparation of polyvinyl-chloride of low-polymerization degree paste resin.
Summary of the invention
The purpose of this invention is to provide a kind of polyvinyl-chloride of low-polymerization degree and stick with paste process for preparing resins.
For achieving the above object, the technical solution used in the present invention is:
A kind of polyvinyl-chloride of low-polymerization degree is stuck with paste the preparation method of resin: adopt microsuspension technique, under 52 ℃ of-56 ℃ of conditions, before polyreaction, add in the reaction system chain-transfer agent is disposable during polymerization, or add in the reaction system in the polymerization process in batches, the preparation polymerization degree is polyvinyl chloride (PVC) paste～resin of 500-900, and wherein the add-on of chain-transfer agent is the 0.02%-0.2% of vinyl chloride monomer quality.
Be the 50%-60% that adds required chain-transfer agent consumption before polyreaction described in batches the adding in the reaction system, when conversion rate of vinyl chloride reaches 75%-85%, more remaining chain-transfer agent is added in the reaction system.Described chain-transfer agent is unsaturated or saturated halogenated hydrocarbon or sulfocompound.Described chain-transfer agent is 2 one mercaptoethanols, trieline, 3-thiohydracrylic acid, isooctyl mercaptoacetate, the different monooctyl ester of thiohydracrylic acid.
The preparation method that polyvinyl-chloride of low-polymerization degree is stuck with paste resin is specially: with vinyl chloride monomer, deionized water, blending emulsifiers, oil-soluble initiator and chain-transfer agent, sending into dispersion tank disperses, join in the polymeric kettle of vacuum deaeration while disperseing, make it to form stable fine droplets, whole feed time was finished in 40-80 minute.And the supercharging of backward polymeric kettle inflated with nitrogen, make the still internal pressure increase 0.1MPa, polymeric kettle heats to 52 ℃-56 ℃, under this temperature, keep polyreaction, when the polymeric kettle internal pressure has descended 0.1-0.3Mpa, polyreaction finishes, and carries out vinyl chloride monomer and reclaims, and obtains the pvc resin paste grade that the polymerization degree is 500-900;
Wherein before polyreaction, add in the reaction system chain-transfer agent is disposable during the chain-transfer agent polymerization, or add in the reaction system in the polymerization process in batches.Be before polyreaction chain-transfer agent and vinyl chloride monomer, deionized water, blending emulsifiers, oil-soluble initiator add in the lump dispersion tank and disperse described in batches the adding in the reaction system, its chain-transfer agent add-on is the 50%-60% of the required chain-transfer agent consumption of whole polyreaction, in polymeric kettle, added the residue chain-transfer agent again in polyreaction 8-10 hour, continue to keep polyreaction, when the polymeric kettle internal pressure has descended 0.2Mpa, polyreaction finishes, and carries out vinyl chloride monomer and reclaims.Latex is spray-dried, gets the pvc resin paste grade that the polymerization degree is 500-900.Take other group components of vinylchlorid 100 weight parts as, deionized water 70-120 weight part, blending emulsifiers 0.5-5 weight part, oil soluble composite initiator 0.0005-0.002 weight part, chain-transfer agent 0.02-0.2 weight part.
Blending emulsifiers is comprised of anion surfactant, the pure and mild nonionogenic tenside of long-chain fat, take other group components of blending emulsifiers 100 weight parts as, anion surfactant 40-50 weight part, long chain aliphatic alcohol 50-60 weight part, nonionogenic tenside 3-5 weight part.Described anion surfactant is sodium lauryl sulphate, sodium laurylsulfate, hexadecanol sodium sulfate.Described long chain aliphatic alcohol is lauryl alcohol, C
12-20Alcohol mixture.Described polyoxyethylene alkyl ester, Voranol EP 2001.Described oil soluble composite initiator is azo compound and organo-peroxide.Described oil soluble composite initiator, in oil soluble composite initiator 100 weight parts, wherein group component is, azo compound 70-80 weight part, organo-peroxide 20-30 weight part.Described azo compound is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Organo-peroxide is dilauroyl peroxide or peroxy dicarbonate ethylhexyl.
Reaction principle, the present invention prepares low-molecular-weight pvc resin paste grade, and for avoiding adopting higher polymerization temperature, we adopt in microsuspension and add chain-transfer agent, and it is right to reduce polymer poly.Chain-transfer agent is a kind of very active material in polymerization reaction system, it is easy to react with the macromolecular radical that is increasing, living chain is stopped, chain-transfer agent itself generates again new free radical simultaneously, the activity of this free radical is active identical or close with macromolecular radical, thereby can continue initiated polymerization.Can reduce the polymerization degree of polymkeric substance after the adding chain-transfer agent, polyreaction is not then had too much influence.
The advantage that the present invention has: the present invention adopts and adds chain-transfer agent in the polymerization process, realizes reducing the right purpose of polymer poly under the uniform temp.Make to be aggregated under the relatively lower temp and carry out, so the pvc resin paste grade prepared of preparation method of the present invention, have plasticization temperature low, become to stick with paste excellent property, stick with paste that viscosity is low, foam performance good, Heat stability is good, production stability high.
Embodiment
The below will be described in further detail invention by example, and technical scheme embodiment of the present invention comprises two kinds, and the key distinction once adds before polymerization and chain-transfer agent in batches adding in polymerization process in chain-transfer agent.The vinyl chloride monomer that is adopted among the embodiment in addition can adopt carbide acetylene method and process for oxychlorination of ethylene preparation, and vinyl chloride monomer purity is more than 99%.
Embodiment 1
Vinylchlorid 21000kg, pure water 18500kg, 2,2'-Azobis(2,4-dimethylvaleronitrile) 2.56kg, peroxy dicarbonate ethylhexyl 0.5kg, sodium lauryl sulphate 200kg, C
12-20Fatty Alcohol(C12-C14 and C12-C18) 150kg, trieline 117kg, above-mentioned each material is sent into dispersion tank to be disperseed, to join the polymeric kettle of vacuum deaeration while disperseing, make it to form stable fine droplets, whole feed time was finished in 50 minutes, then to the supercharging of polymeric kettle inflated with nitrogen, make the still internal pressure increase 0.1MPa, polymeric kettle is heated to 56 ℃, keeps polyreaction under this temperature, when the still internal pressure has descended 0.2Mpa, polyreaction finishes, whole polymerization reaction time 15 hours, polymerization latex solid content 48.9%.Add the 10kg Voranol EP 2001, stirred 30 minutes, spray-dried under 160 ℃, pulverizing obtains the pvc resin paste grade finished product, and mean polymerisation degree 860 is stuck with paste viscosity 3200mPa.s.
Embodiment 2
Vinylchlorid 19000kg, pure water 18800kg, 2,2'-Azobis(2,4-dimethylvaleronitrile) 3.25kg, peroxy dicarbonate ethylhexyl 0.35kg, sodium lauryl sulphate 190kg, C
12-20Fatty Alcohol(C12-C14 and C12-C18) 140kg, isooctyl mercaptoacetate 38kg, above-mentioned each material is sent into dispersion tank to be disperseed, to join the polymeric kettle of vacuum deaeration while disperseing, make it to form stable fine droplets, whole feed time was finished in 50 minutes, and the supercharging of backward polymeric kettle inflated with nitrogen, make the still internal pressure increase 0.1MPa, polymeric kettle is heated to 54 ℃, keeps polyreaction under this temperature, when still internal pressure decline 0.2Mpa, polyreaction finishes, whole polymerization reaction time 18 hours, polymerization latex solid content 46.8%.Add the 9kg Voranol EP 2001, stirred 30 minutes, spray-dried under 160 ℃, pulverizing obtains the pvc resin paste grade finished product, and mean polymerisation degree 680 is stuck with paste viscosity 3350mPa.s.
Embodiment 3
Vinylchlorid 19000kg, pure water 18800kg, 2,2'-Azobis(2,4-dimethylvaleronitrile) 2.9kg, peroxy dicarbonate ethylhexyl 0.3kg, sodium lauryl sulphate 190kg, C
12-20Fatty Alcohol(C12-C14 and C12-C18) 140kg, isooctyl mercaptoacetate 18kg, above-mentioned each material is sent into dispersion tank to be disperseed, to join the polymeric kettle of vacuum deaeration while disperseing, make it to form stable fine droplets, whole feed time was finished in 50 minutes, and the supercharging of backward polymeric kettle inflated with nitrogen, make the still internal pressure increase 0.1MPa, polymeric kettle is heated to 54 ℃, keeps polyreaction under this temperature, polyreaction added isooctyl mercaptoacetate 16kg in 10 hours again, when still internal pressure decline 0.2Mpa, whole polymerization reaction time 16 hours, polymerization latex solid content 46.8%.After polymerization finishes, add 9kg polyoxyethylene alkyl ester, stirred 30 minutes, spray-dried under 160 ℃, pulverizing obtains the pvc resin paste grade finished product, and mean polymerisation degree 650 is stuck with paste viscosity 3020mPa.s.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a polyvinyl-chloride of low-polymerization degree is stuck with paste the preparation method of resin, it is characterized in that: adopt microsuspension technique, under 52 ℃ of-56 ℃ of conditions, before polyreaction, add in the reaction system chain-transfer agent is disposable during polymerization, or add in the reaction system in the polymerization process in batches, the preparation polymerization degree is polyvinyl chloride (PVC) paste～resin of 500-900, and wherein the add-on of chain-transfer agent is the 0.02%-0.2% of vinyl chloride monomer quality.
2. stick with paste the preparation method of resin by polyvinyl-chloride of low-polymerization degree claimed in claim 1, it is characterized in that: be the 50%-60% that adds required chain-transfer agent consumption before polyreaction described in batches the adding in the reaction system, when conversion rate of vinyl chloride reaches 75%-85%, more remaining chain-transfer agent is added in the reaction system.
3. the preparation method who sticks with paste resin by claim 1 or 2 described polyvinyl-chloride of low-polymerization degree, it is characterized in that: described chain-transfer agent is unsaturated or saturated halogenated hydrocarbon or sulfocompound.
4. stick with paste the preparation method of resin by polyvinyl-chloride of low-polymerization degree claimed in claim 3, it is characterized in that: described chain-transfer agent is 2 one mercaptoethanols, trieline, 3-thiohydracrylic acid, isooctyl mercaptoacetate, the different monooctyl ester of thiohydracrylic acid.
5. stick with paste the preparation method of resin by polyvinyl-chloride of low-polymerization degree claimed in claim 1, it is characterized in that: with vinyl chloride monomer, deionized water, blending emulsifiers, oil-soluble initiator and chain-transfer agent, sending into dispersion tank disperses, join in the polymeric kettle of vacuum deaeration while disperseing, make it to form stable fine droplets, whole feed time was finished in 40-80 minute.And the supercharging of backward polymeric kettle inflated with nitrogen, make the still internal pressure increase 0.1MPa, polymeric kettle heats to 52 ℃-56 ℃, under this temperature, keep polyreaction, when the polymeric kettle internal pressure has descended 0.1-0.3Mpa, polyreaction finishes, and carries out vinyl chloride monomer and reclaims, and obtains the pvc resin paste grade that the polymerization degree is 500-900;
Wherein before polyreaction, add in the reaction system chain-transfer agent is disposable during the chain-transfer agent polymerization, or add in the reaction system in the polymerization process in batches.
6. stick with paste the preparation method of resin by polyvinyl-chloride of low-polymerization degree claimed in claim 5, it is characterized in that: be chain-transfer agent and vinyl chloride monomer before polyreaction described in batches the adding in the reaction system, deionized water, blending emulsifiers, oil-soluble initiator adds in the lump dispersion tank and disperses, its chain-transfer agent add-on is the 50%-60% of the required chain-transfer agent consumption of whole polyreaction, in polymeric kettle, added the residue chain-transfer agent again in polyreaction 8-10 hour, continue to keep polyreaction, when the polymeric kettle internal pressure has descended 0.2Mpa, polyreaction finishes, and carries out vinyl chloride monomer and reclaims.Latex is spray-dried, gets the pvc resin paste grade that the polymerization degree is 500-900.
7. stick with paste the preparation method of resin by polyvinyl-chloride of low-polymerization degree claimed in claim 5, it is characterized in that: take other group components of vinylchlorid 100 weight parts as, deionized water 70-120 weight part, blending emulsifiers 0.5-5 weight part, oil soluble composite initiator 0.0005-0.002 weight part, chain-transfer agent 0.02-0.2 weight part.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104856799A (en) * | 2015-06-16 | 2015-08-26 | 连云港市一明医疗科技有限公司 | Ophthalmic therapy device |
| CN105843187A (en) * | 2016-03-31 | 2016-08-10 | 唐山三友氯碱有限责任公司 | DCS charging control method of producing PVC paste resin by polymerizer |
| CN107141386A (en) * | 2017-06-16 | 2017-09-08 | 唐山三友氯碱有限责任公司 | A kind of method for producing PVC paste resin and reaction retracting device |
| CN107501449A (en) * | 2017-08-23 | 2017-12-22 | 天津渤天化工有限责任公司 | Pvc paste resin and preparation method thereof |
| CN107602745A (en) * | 2017-09-30 | 2018-01-19 | 北京化工大学 | Ultra low polymerization degree polyvinyl chloride nano particle and preparation method thereof |
| CN108822443A (en) * | 2018-07-21 | 2018-11-16 | 安徽启慧信息科技有限公司 | A kind of floor and preparation method thereof with PVC construction material |
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| JP2009068024A (en) * | 2009-01-08 | 2009-04-02 | Tosoh Corp | Process for production of vinyl chloride resin for paste |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104856799A (en) * | 2015-06-16 | 2015-08-26 | 连云港市一明医疗科技有限公司 | Ophthalmic therapy device |
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| CN105843187A (en) * | 2016-03-31 | 2016-08-10 | 唐山三友氯碱有限责任公司 | DCS charging control method of producing PVC paste resin by polymerizer |
| CN105843187B (en) * | 2016-03-31 | 2018-03-27 | 唐山三友氯碱有限责任公司 | A kind of polymeric kettle produces PVC paste resin DCS charging control methods |
| CN107141386A (en) * | 2017-06-16 | 2017-09-08 | 唐山三友氯碱有限责任公司 | A kind of method for producing PVC paste resin and reaction retracting device |
| CN107501449A (en) * | 2017-08-23 | 2017-12-22 | 天津渤天化工有限责任公司 | Pvc paste resin and preparation method thereof |
| CN107602745A (en) * | 2017-09-30 | 2018-01-19 | 北京化工大学 | Ultra low polymerization degree polyvinyl chloride nano particle and preparation method thereof |
| CN107602745B (en) * | 2017-09-30 | 2019-12-24 | 北京化工大学 | Polyvinyl chloride nano particle with ultralow polymerization degree and preparation method thereof |
| CN108822443A (en) * | 2018-07-21 | 2018-11-16 | 安徽启慧信息科技有限公司 | A kind of floor and preparation method thereof with PVC construction material |
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Application publication date: 20130306 |