CN100455610C - Interpolymer paste resin and its preparing method - Google Patents
Interpolymer paste resin and its preparing method Download PDFInfo
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- CN100455610C CN100455610C CNB021328625A CN02132862A CN100455610C CN 100455610 C CN100455610 C CN 100455610C CN B021328625 A CNB021328625 A CN B021328625A CN 02132862 A CN02132862 A CN 02132862A CN 100455610 C CN100455610 C CN 100455610C
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Abstract
The present invention relates to chloroethylene-vinyl acetate ester copolymer paste resin prepared by a micro suspension method or an emulsion copolymerization method and a preparation method thereof. The present invention has the essential technical scheme that a certain amount of monomer chloroethylene and a certain amount of monomer vinyl acetate ester are dispersed in water by a high-speed pump or slowly stirring under the protection of surface active agents so as to form fine liquid drops; copolymer latex of which the particle diameter is from 0.1 to 2 mu m is produced by polyreaction at 40 to 65 DEG C under the action of an oil-soluble trigger system or a water-solubility trigger system; the solid content of the latex is from 30 to 55%, and the latex forms the chloroethylene-vinyl acetate ester copolymer paste resin by spray drying. The present invention has the advantages that the chloroethylene and the vinyl acetate ester can carry out a reaction by the micro suspension method or the emulsion copolymerization method, and thus, the present invention not only has superior paste-forming performance which the chloroethylene-vinyl acetate ester copolymer resin obtained by the suspension method does not have, but also has the low-temperature plasticization performance of which the temperature is 30 to 40 DEG C lower than that of PVC paste resin.
Description
Technical field
The invention belongs to the macromolecule chemical industry technical field, specifically prepare vinyl chloride-vinyl acetate copolymer paste resin by little suspension or emulsion copolymerization method.
Background technology
At present domestic have polyvinyl chloride (PVC) to stick with paste rosin products production.The preparation main method has emulsion polymerization and microsuspension method, the product primary particle diameter is 0.1-2.0 μ m, is shaped as sphere, makes pasty state (plastipaste) form with softening agent and uses, plastipaste only needs heating plasticizing promptly to can be made into solid shape goods, and plasticization temperature is 140-230 ℃.Its main application fields is as follows:
(1) coated product: the interior finish of clothes and coat, gloves, raincoat, automotive interior trim, wallpaper, flooring laminate, duffel bag, train and passenger vehicle, tent, inflatable skeleton, inflatable lifesaving device, automobile headgear; Board, wallpaper, floor lining, paper coating, electrical instrumentation shell, refrigerator and washing machine and range fan shell.
(2) foamed molded product: the end, simulated leather, foaming flooring laminate, foaming wallpaper, shipping anti-collision device in sports pad, seat cushions, the footwear.
(3) sprayed product: the liner of electrical instrumentation shell, canned food coating, drum and groove.
(4) slush moulding product: seaboot, toy, headrest, balloon, rubber pipette bulb.
(5) dipping plastic product: window screening, handle for tool, gloves, seaboot, iron wire frame, fence, various auto parts.
(6) casting product (comprise dripping and mould): toy, bottle cap liner, outfall sewer liner, seal.
(7) rotation-formed product: toy, doll, artificial fruit, roadblock, Bicycle cushion, fascia.
(8) tackiness agent: the bonding of car bottom antirust and sealed binder, airduct and big pipe cap bonding, art metal furniture and apparatus.
Stick with paste the continuous development of resin treatment Application Areas in recent years along with PVC, some manufacture field requires lower (about 120 ℃) to plasticization temperature, and PVC sticks with paste resin and do not reach complete fusion plastification.For example, at present domestic existing tens PVC automobile plastisol factories, with the pvc plastisol condition of cure of PVC homopolymerization paste production of resins be 145 ℃ 30 minutes, and the drying room temperature of most of automobile factorys does not reach 140 ℃.And along with requirements of saving energy, automobile factory is further reducing plasticization temperature, requires solidifying below 120 ℃ even requiring to be solidified under 80～90 ℃ of temperature.The binding agent industry user of some PVC leatheroid, carpet uses the fabricbase material thermal resistance such as nylon, vinylon, terylene can be poor for another example, sticks with paste yielding contraction under the plasticization temperature condition of resin at PVC.Resin is stuck with paste in these fields all a kind of novel low-temperature plasticizing of demand.
The at present domestic vinyl chloride-vinyl acetate copolymer resins that has suspension polymerization to produce, the polyvinyl chloride resin identical with molecular weight is compared, have that processing temperature is lower, process velocity is fast, processing fluidity is good, snappiness is good, can fill more fillers, the advantage that solvability is good.Be mainly used in fields such as plastic floor brick, microgroove record, coating, fiber, tape tackiness agent, printing ink.Though the vinyl chloride-vinyl acetate copolymer resins of suspension polymerization production can reduce plasticization temperature, but product cut size is 50-250 μ m, and random, the porous of shape can only swelling in softening agent, can not become to stick with paste, thereby can not be applied to PVC paste resin treatment Application Areas.
Summary of the invention
The purpose of this invention is to provide little suspension or emulsion copolymerization method vinylchlorid and-vinyl acetate are reacted, make vinyl chloride-vinyl acetate copolymer paste resin, the product primary particle diameter is 0.1-2.0 μ m.Promptly obtain the not available one-tenth of suspension method vinyl chloride-vinyl acetate copolymer resins and stuck with paste performance, had the low-temperature plasticizing performance of sticking with paste 30-40 ℃ of resin reduction than PVC again.
The object of the present invention is achieved like this: getting weight percent is the 70-97% first monomer vinylchlorid, weight percent is the 3-30% second monomer vinyl acetate, accounting under the tensio-active agent protection that weight percent monomer is 0.4-5%, use high-speed pump or slowly stir monomer is scattered in the water, form tiny drop; Accounting under the oil soluble or water soluble initiator effect that weight percent monomer is 0.01-0.50%, at 40-65 ℃ of polyreaction 4-40 hour, producing particle diameter was the copolymer emulsion of 0.1-2.0 μ m.The latex solid content is 30-55%, and latex forms vinyl chloride-vinyl acetate copolymer paste resin through spraying drying.
Emulsification system is to use the compound use of tensio-active agent.Its effect is the interfacial tension lowering that makes monomer and water before polymerization, is beneficial to form emulsion under the effect of machinery; In reaction, to protect the dispersive monomer droplet not assemble, keep the particle diameter of size droplet diameter and generation latex particle relatively stable; Reaction is final also must to play a part to protect latex stable.Tensio-active agent generally uses aniorfic surfactant and dispersion aids.Aniorfic surfactant for example, the sodium salt of longer chain fatty acid, sylvate, long chain alkyl sulfates, alkylaryl sulfonate.Preferred oleyl alcohol sodium sulfate, sodium laurylsulfate, hexadecanol sodium sulfate, succinate sodium sulfonate, Sodium dodecylbenzene sulfonate, tetradecyl benzene sulfonic acid sodium salt etc.Its consumption is accounting for the 0.2-3% of weight percent monomer, and consumption is 0.4-1.5% preferably.Dispersion aids is water-fast material, and usually with Fatty Alcohol(C12-C14 and C12-C18) or long chain alkane, both also can and use.As C
12-26Fatty Alcohol(C12-C14 and C12-C18) (hexadecanol, Stearyl alcohol, oleyl alcohol, n-Eicosanol, behenyl alcohol, tetracosanol and ceryl alcohol), TETRADECONIC ACID, stearic acid etc.The effect of dispersion aids is to make monomer droplet have ability at water and solubilising micella competition free radical, and reaction is mainly carried out in monomer droplet, and the latex particle size of generation is increased.The assistant for emulsifying agent consumption is accounting for the 0.2-2.0% of weight percent monomer, and consumption is 0.5-1.2% preferably.In addition, also can add nonionic surfactants.For example polyxyethylated ester, polyvalent alcohol alkyl ester, polyethylene oxide alkyl ethers, polyoxyethylene alkyl aryl ether and polyvalent alcohol cyclic ethers.Its consumption is the 0.05-1.5% that accounts for weight percent monomer
The organic property oil soluble composite initiator of the general use of little suspending copolymerization method initiator system mainly contains azo class and peroxide.The azo class is used Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) always, and consumption is accounting for the 0.005-0.10% of monomer weight, and consumption is 0.008-0.03% preferably.Peroxide is used lauroyl peroxide, benzoyl peroxide, peroxy dicarbonates, tert-butyl hydroperoxide pivalate, peroxidation two-3,5, the own ester of 5-trimethylammonium etc. always.Peroxy dicarbonates kind commonly used has: peroxy dicarbonate ethylhexyl, peroxy dicarbonate 2-ethoxy ethyl ester, peroxy dicarbonate hexadecyl ester, peroxy dicarbonate di-tert-butyl cyclohexyl, di-isopropyl peroxydicarbonate etc.Consumption is accounting for the 0.005-0.1% of weight percent monomer, and consumption is 0.01-0.03% preferably.Initiator system can be selected wherein two kinds of compound uses for use.
By the good emulsifying agent of prescription weighing, fully be dissolved in the quantitative pure water (DW) at dissolving vessel (equipment 3 among Fig. 1).Weighing initiator and (equipment 1,2 among Fig. 1) dissolving in its dissolving vessel.Polymeric kettle (equipment 6 among Fig. 1) is carried out vacuum deaeration, make the interior vacuum tightness of still reach 0.05-0.09MPa.Pure water, vinylchlorid (VC), vinyl acetate (VAC) and the emulsifying agent for preparing, the initiator that to stipulate flow then add in the dispersion tank (equipment 4 among Fig. 1) simultaneously, under disperseing pump (equipment 5 among Fig. 1) effect, material is disperseed to become stable dispersion liquid.Dispersion liquid is reinforced to polymeric kettle while circulating, and the dispersed feeding time is 10-80min.Behind reinforced the end, fill the nitrogen operation, still is pressed in the still increases 0.05-0.1MPa on the basis again.With hot water polymeric kettle is warming up to polymerization temperature.Polymerization temperature is controlled at 40-65 ℃.From reaction, the pressure in the polymeric kettle can slowly reduce.Keep temperature in the kettle to stablize 4～40hr, during to still internal pressure reduction by 0.1～0.4MPa, judge the polymerization terminal point according to the variation of jacket of polymerization temperature variation and pressure.After finishing polymerization, add the silicon-type defoamer to polymeric kettle.Begin then unreacted monomer slowly to be unloaded to gas holder be depressed into normal pressure from pushing back receipts.Simultaneously, polymeric kettle is heated up, make temperature in the kettle reach 70-85 ℃.When gauge pressure reaches 0.1MPa in the polymeric kettle, finish from pushing back receipts.Begin then to force to reclaim, start water ring vacuum pump, drive big vacuum tightness variable valve automatically gradually.When the polymeric kettle internal pressure reach-during 0.03-0.06MPa, finish to force to reclaim.Latex (LAT) in the polymeric kettle advances that to squeeze into blowing jar (equipment 7 among Fig. 1) through pump to be dried.Spray-dryer (equipment 8 among Fig. 1) is preheated to 50-100 ℃, carries out water transport and change, when treating that temperature in rises to 80-170 ℃, turn on pump adds latex, keeps temperature out at 40-70 ℃, and behind the discharge port resin process pulverizer (equipment 9 among Fig. 1), packing is finished product.Finished product grain size is at 0.1-10 μ m.
Vinyl chloride-vinyl acetate emulsion copolymerization reaction emulsification system is identical with little suspension copolymerization.
General water-soluble initiation peroxide, for example Potassium Persulphate, Sodium Persulfate, ammonium persulphate, tertbutyl peroxide, isopropyl benzene hydroperoxide, the hydrogen peroxide etc. of using of vinyl chloride-vinyl acetate emulsion copolymerization reaction initiator system.These initiators can use separately also can mix use.Its consumption accounts for the 0.01-1.0% of monomer weight percent.Sometimes also can add the compound (activator) that one or more have reductive action and can form redox-catalyst system, for example sulfoxylic acid aldehyde, hyposulfite, pyrosulfite, sulphite, thiosulphate etc.Iron protochloride commonly used, cupric chloride, copper sulfate, sodium bisulfite, sodium sulfoxylate formaldehyde, Sulfothiorine sinistrose or dextrose.Its consumption accounts for the 0.01-1.0% of monomer weight percent.Need add organic complexing agent in addition, improve polymerization rate, reduce the stability of level of residual monomers and enhancing emulsion.The for example an alkali metal salt of ethylenediamine tetraacetic acid (EDTA) or nitrilotriacetic acid(NTA) and ammonium salt, 1 of free form or salt form, 2-and 1,3-trimethylenedinitrilo-tertraacetic acid, diethylene triaminepentaacetic acid(DTPA) and derivative thereof (as the adjacent sodium ethylene diamine tetracetate of N-oxygen ethylethylenediamine tetraacethyl sodium, N-Virahol ethylenediamine triacetic acid sodium, N-oxygen ethyl diethylenetriamine tetraacethyl sodium or hexamethylene).But the emulsion copolymerization initiator system also can use the oil-soluble initiator in little suspending copolymerization.Oil-soluble initiator is compared with water soluble starter has the new particulate superiority of less generation in copolymerization.
Vinylchlorid and the earlier synthetic seed emulsion of-vinyl acetate emulsion copolymerization technology, particle diameter is 0.1-0.5 μ m.Seed emulsion further generates finished product latex with the monomer that adds continuously in proportion, emulsifying agent, initiator for reaction again, and particle diameter is 0.3-2.0 μ m.Seed emulsion is synthetic, at first is emulsifying agent, initiator solvent soln (process for preparation is with little suspending copolymerization technology), and initiator solution adds in the seeding polymerization still.Vinylchlorid, Vinyl Acetate Monomer, emulsifier solution are squeezed in the still in proportion with volume pump, carry out polyreaction.Come the controlled polymerization temperature by control monomer, emulsifying agent feed rate.After seed emulsion is synthetic, following step polyreaction.Prepare emulsifying agent, initiator, alkaline solution (process for preparation is with little suspending copolymerization technology) earlier.In polymeric kettle, add quantitative pure water, emulsifying agent, alkali lye, initiator, complexing agent, seed emulsion, start and stir.With nitrogen and vacuum deaeration.Initial monomers vinylchlorid, vinyl acetate are added in the polymeric kettle, be warming up to polymerization temperature (40-65 ℃) polymerization after 1 hour, the still internal pressure descends, use volume pump equilibrium in still interpolation monomer vinylchlorid and vinyl acetate, emulsifying agent, activator by filling a prescription, behind reinforced the end, reacted 4-40 hour.When the still internal pressure drops to 0.4MPa, finish copolymerization.Process is with little suspending copolymerization technology later on.
In the vinyl chloride-vinyl acetate emulsion copolymerization vinyl acetate add also can be only in seed emulsion synthetic or only under go on foot in the polyreaction.
The vinyl chloride-vinyl acetate emulsion copolymerization also can synthesize seed emulsion, only adopts one step of back emulsion copolymerization.
The ratio of little suspension of vinyl chloride-vinyl acetate or emulsion copolymerization vinylchlorid and Vinyl Acetate Monomer and water is at 0.5-3: 1, and in order to obtain the latex of solid content high as far as possible (35-53%), the proportional range of monomer and water is preferably in 0.6-1.2: 1.
Little suspension of vinyl chloride-vinyl acetate or emulsion copolymerization reaction: conversion rate of vinyl chloride is 70-95%, and the vinyl acetate between to for plastic ester conversion rate is 50-70%.
Vinylchlorid is with to carry out the vinyl acetate copolymerized reaction mechanism of closing as follows:
Vinylchlorid is stuck with paste resin with-vinyl acetate copolymerized paste resin with PVC and is compared, owing to embedded the vinyl acetate between to for plastic ester molecule in the PVC molecule, molecule segment is by homogeneous
Become
The closelypacked vinylchlorid segment rigid structure that is present in the homopolymer has suffered destruction, has weakened intermolecular polarity, has reduced intermolecular gravitation, and has made its performance that variation take place.Being mainly reflected in vinylchlorid and-vinyl acetate copolymerized paste resin sticks with paste resin than the PVC of similar molecular weight and has than low gel temperature and melt temperature (reducing 30-40 ℃).On the other hand, the introducing of ester group in the vinyl acetate between to for plastic ester molecule can improve softening agent to dissolving resin speed, increases the bounding force of resin and various adhesive substrate.
Vinyl chloride-vinyl acetate copolymer paste resin as reduce processing temperature, improve plasticizing rate, the important means of improving product properties is widely used in industries such as PVC automobile plastisol (comprising chassis preventing stone coating, vehicle body weld seam seal gum spot welding glue, filter core glue, buffering adhesive etc.), PVC square carpet backing binding agent, printing inks, heat-sensitive fabric coating, slush moulding heel, paulin and chemical foaming goods.Vinyl chloride-vinyl acetate copolymer paste resin can be used separately, also can stick with paste resin with PVC and be used.Vinyl chloride-vinyl acetate copolymer paste resin can be applied to the Application Areas that PVC sticks with paste resin fully, makes the user reduce processing temperature, improves process velocity and quality product.
The performance of vinyl chloride-vinyl acetate copolymer paste resin depends mainly on the mean polymerisation degree of multipolymer and the composition of multipolymer.The influence that mean polymerisation degree is formed by polymerization temperature and multipolymer mainly; The composition of multipolymer then depends on feeding quantity, water and the factors such as monomeric proportioning and transformation efficiency of vinyl acetate.The most important thing is to determine the polymerization technology condition of desired mean polymerisation degree for the preparation of the interpolymer paste resin of a certain composition.In addition, the multipolymer of preparation chemical constitution homogeneous is an important problems.Because the reactivity ratio of vinylchlorid is bigger than the reactivity ratio of vinyl acetate, i.e. vinylchlorid than the vinyl acetate reaction hurry up during copolymerization.In order to prepare the multipolymer of chemical constitution homogeneous, on polymerization technique, can divide vinyl acetate several steps to add.But in order to simplify the operation, adopt two kinds of monomers once to feed intake simultaneously among the present invention, gained copolymerized product performance also can satisfy service requirements, and the per-cent of vinyl acetate should be bigger than vinyl acetate content per-cent in the expection multipolymer when feeding intake.
Advantage of the present invention is with little suspension or emulsion copolymerization method vinylchlorid and-vinyl acetate to be reacted, promptly obtain the not available good one-tenth of suspension method vinyl chloride-vinyl acetate copolymer resins and stuck with paste performance, had the low-temperature plasticizing performance of sticking with paste 30-40 ℃ of resin reduction than PVC again.
Description of drawings
Below in conjunction with accompanying drawing the present invention is described in further detail
Fig. 1 is little suspending copolymerization process flow diagram of the present invention
Fig. 2 is little suspending copolymerization process principle figure of the present invention
Embodiment
Below will the present invention will be further described by embodiment, but following example only is the present invention's example wherein, the interest field of not representing the present invention and being limited.
Embodiment 1:
Prescription feeds intake: vinylchlorid 95 (weight percent, down together), vinyl acetate 5, pure water 120, sodium laurylsulfate 1.2, C
12-26Fatty Alcohol(C12-C14 and C12-C18) 1.5,2,2'-Azobis(2,4-dimethylvaleronitrile) 0.02, toluene 0.1, peroxy dicarbonate ethylhexyl 0.01.
With sodium laurylsulfate, C
12-26Fatty Alcohol(C12-C14 and C12-C18), 10 parts of pure water (DW) join in the emulsifiers dissolve jar (equipment 3 among Fig. 1) and stir.2,2'-Azobis(2,4-dimethylvaleronitrile), toluene, 5 parts of pure water are joined in the initiator dissolving vessel 1 (equipment 1 among Fig. 1) and stir.Peroxy dicarbonate ethylhexyl, 5 parts of pure water are joined in the initiator dissolving vessel 2 (equipment 2 among Fig. 1) and stir.Simultaneously the emulsifying agent after vinylchlorid (VC), vinyl acetate (VAC), pure water (100 parts), the dissolving, initiator are added dispersion tank (equipment 4 among Fig. 1), open and disperse pump (equipment 5 among Fig. 1), reinforced while disperseing toward polymeric kettle (equipment 6 among Fig. 1), the dispersed feeding time is 45min, and the polymeric kettle internal pressure is 0.35MPa.It is 0.45MPa that polymeric kettle is carried out inflated with nitrogen to still internal pressure.With hot water polymeric kettle is warming up to 45 ℃.Keep temperature in the kettle stable, during to still internal pressure reduction 0.20MPa, finish polymerization.In still, add defoamer.Through after pushing back receipts, forcing to reclaim, the latex (LAT) in the polymeric kettle is squeezed into blowing jar (equipment 7 among Fig. 1).Spray-dryer (equipment 8 among Fig. 1) is preheated to 80-100 ℃, carries out water transport and change, when treating that temperature in rises to 100-120 ℃, turn on pump adds latex, keep temperature out at 45～65 ℃, behind the discharge port resin process pulverizer (equipment 9 among Fig. 1), packing is finished product.
Conversion rate of vinyl chloride is 90.6%, and the vinyl acetate between to for plastic ester conversion rate is 60.6%.
The check analysis result is as follows: (pressing the Q/SHG.J02.146-1999 standard testing)
Product quality indicator
Embodiment 2
Step by embodiment 1 is carried out.
Prescription feeds intake: vinylchlorid 93 (weight percent, down together), vinyl acetate 7, pure water 110, Sodium dodecylbenzene sulfonate 1.2, C
12-26Fatty Alcohol(C12-C14 and C12-C18) 0.9, lipid acid 0.3, Diisopropyl azodicarboxylate 0.023, peroxy dicarbonate di-tert-butyl cyclohexyl 0.018.
The dispersed feeding time is 70min
55 ℃ of polymerization temperatures
Conversion rate of vinyl chloride is 86.5%, and the vinyl acetate between to for plastic ester conversion rate is 50.4%.
The check analysis result is as follows:
Product quality indicator
Embodiment 3
Step by embodiment 1 is carried out.
Prescription feeds intake: vinylchlorid 86, vinyl acetate 14, pure water 100, tetradecyl benzene sulfonic acid sodium salt 0.9, C
14,2-26Fatty Alcohol(C12-C14 and C12-C18) 1.0, benzoyl peroxide 0.027, di-isopropyl peroxydicarbonate 0.016.
The dispersed feeding time is 65min
53 ℃ of polymerization temperatures
Conversion rate of vinyl chloride is 92.8%, and the vinyl acetate between to for plastic ester conversion rate is 67%.
The check analysis result is as follows:
Product quality indicator
Embodiment 4
Step by embodiment 1 is carried out.
Prescription feeds intake: vinylchlorid 80 (weight percent, down together), vinyl acetate 20, pure water 95, succinate sodium sulfonate 1.1, C
12-26Fatty Alcohol(C12-C14 and C12-C18) 0.7, lipid acid 0.15, lauroyl peroxide 0.03, peroxy dicarbonate 2-ethoxyethyl ester 0.02.
The dispersed feeding time is 50min
48 ℃ of polymerization temperatures
Conversion rate of vinyl chloride is 93.4%, and the vinyl acetate between to for plastic ester conversion rate is 67.6%.
The check analysis result is as follows:
Product quality indicator
Embodiment 5
Step by embodiment 1 is carried out.
Prescription feeds intake: vinylchlorid 94 (weight percent, down together), vinyl acetate 6, pure water 90, hexadecanol sodium sulfate 0.88, C
12-26Fatty Alcohol(C12-C14 and C12-C18) 0.92,2,2'-Azobis(2,4-dimethylvaleronitrile) 0.025, peroxidation two-3,5, the own ester 0.015 of 5-trimethylammonium.
The dispersed feeding time is 60min
51 ℃ of polymerization temperatures
Conversion rate of vinyl chloride is 93%, and the vinyl acetate between to for plastic ester conversion rate is 65%.
The check analysis result is as follows:
Product quality indicator
Embodiment 6
Step by emulsion copolymerization technology is carried out.
The seed prescription that feeds intake: vinylchlorid 100 (weight percent, down with), pure water 150, sodium lauryl sulphate 0.6, C
12-26Fatty Alcohol(C12-C14 and C12-C18) 0.2, Potassium Persulphate 0.02, Sulfothiorine 0.12, cupric chloride 0.01.
The polymerization prescription that feeds intake: vinylchlorid 93 (weight percent, down with), vinyl acetate 7, pure water 100, sodium lauryl sulphate 0.7, Potassium Persulphate 0.01, Sulfothiorine 0.10, cupric chloride 0.003.
At first be by formula ratio dissolved emulsifier, initiator (process for preparation is with little suspending copolymerization technology), initiator solution adds in the seeding polymerization still.Vinylchlorid, Vinyl Acetate Monomer, emulsifier solution are squeezed in the still in proportion with volume pump, carry out under 40-65 ℃ polyreaction 4-40 hour.After seed emulsion is synthetic, prepare emulsifying agent, initiator, alkaline solution (process for preparation is with little suspending copolymerization technology) again.In polymeric kettle, add quantitative pure water, emulsifying agent, alkali lye, initiator, seed emulsion, start and stir.With nitrogen and vacuum deaeration.Initial monomers vinylchlorid, vinyl acetate are added in the polymeric kettle, be warming up to polymerization temperature (40-65 ℃) polymerization after 1 hour, use volume pump equilibrium in still interpolation monomer vinylchlorid and vinyl acetate, emulsifying agent, activator by filling a prescription, after the reinforced end, reacted 4-40 hour.When the still internal pressure drops to 0.4MPa, finish copolymerization.Process is with little suspending copolymerization technology later on.
53 ℃ of polymerization temperatures
Conversion rate of vinyl chloride is 91%, and the vinyl acetate between to for plastic ester conversion rate is 61%.
The check analysis result is as follows:
Product quality indicator
Embodiment 7
Step by emulsion copolymerization technology is carried out.
The polymerization prescription that feeds intake: vinylchlorid 95 (weight percent, down with), vinyl acetate 5, pure water 150, sodium lauryl sulphate 3.0, C
12-26Fatty Alcohol(C12-C14 and C12-C18) 1.5, TETRADECONIC ACID 0.2, hydrogen peroxidase 10 .2,, iron protochloride 0.005, disodium EDTA 0.10.
Preparation emulsifying agent, initiator, alkaline solution (process for preparation is with little suspending copolymerization technology).In polymeric kettle, add quantitative pure water, emulsifying agent, alkali lye, initiator, complexing agent, start and stir.With nitrogen and vacuum deaeration.Initial monomers vinylchlorid, vinyl acetate are added in the polymeric kettle, be warming up to polymerization temperature (40-65 ℃) polymerization after 1 hour, use volume pump equilibrium in still interpolation monomer vinylchlorid and vinyl acetate, emulsifying agent, activator by filling a prescription, after the reinforced end, reacted 4-40 hour.When the still internal pressure drops to 0.4MPa, finish copolymerization.Process is with little suspending copolymerization technology later on.
45 ℃ of polymerization temperatures
Conversion rate of vinyl chloride is 87.8%, and the vinyl acetate between to for plastic ester conversion rate is 59.6%.
The check analysis result is as follows:
Product quality indicator
Claims (14)
1, a kind of preparation method who prepares vinyl chloride-vinyl acetate copolymer paste resin by little suspending copolymerization method, getting weight percent earlier is the 70-97% first monomer vinylchlorid, weight percent is the 3-30% second monomer vinyl acetate, accounting under the emulsification system protection that weight percent monomer is 0.2-5% then, using 4000-10000 rev/min high-speed pump monomer to be separated into the drop of 0.8-1.5 μ m; Select for use to account for the oil soluble initiator system that weight percent monomer is 0.01-0.5%, initiated polymerization in monomer droplet, producing particle diameter is the copolymer emulsion of 0.8-1.5 μ m; The latex solid content is 30-55%, and latex forms vinyl chloride-vinyl acetate copolymer paste resin through spraying drying; Above-mentioned each components contents sum equals 100%;
Emulsification system is the combination of one or more anion surfactant and one or more dispersion aids; Anion surfactant is sodium salt, sylvate, long chain alkyl sulfates or the alkylaryl sulfonate of longer chain fatty acid, wherein the sodium salt of longer chain fatty acid is: oleyl alcohol sodium sulfate, sodium laurylsulfate or hexadecanol sodium sulfate, and alkylaryl sulfonate is: succinate sodium sulfonate, Sodium dodecylbenzene sulfonate, tetradecyl benzene sulfonic acid sodium salt; Dispersion aids is C
12-26Fatty Alcohol(C12-C14 and C12-C18), TETRADECONIC ACID, stearic acid, wherein C
12-26Fatty Alcohol(C12-C14 and C12-C18) is hexadecanol, Stearyl alcohol, oleyl alcohol, n-Eicosanol, behenyl alcohol, tetracosanol or ceryl alcohol;
The oil soluble initiator system is the combination of one or both azo classes and one or more superoxide; Wherein the azo class is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Superoxide is lauroyl peroxide, benzoyl peroxide, peroxy dicarbonates, tert-butyl hydroperoxide pivalate, peroxidation two-3,5, the own ester of 5-trimethylammonium.
2, the preparation method of interpolymer paste resin according to claim 1, it is characterized in that peroxy dicarbonate is: the peroxy dicarbonate ethylhexyl, peroxy dicarbonate 2-ethoxy ethyl ester, the peroxy dicarbonate hexadecyl ester, peroxy dicarbonate di-tert-butyl cyclohexyl or di-isopropyl peroxydicarbonate.
3, the preparation method of interpolymer paste resin according to claim 1 is characterized in that wherein anion surfactant accounts for the 0.2-3.0% of total monomer weight, and dispersion aids accounts for the 0.2-2.0% of total monomer weight.
4, the preparation method of interpolymer paste resin according to claim 1 is characterized in that wherein anion surfactant accounts for the 0.4-1.5% of total monomer weight, and dispersion aids accounts for the 0.5-1.2% of total monomer weight.
5, the preparation method of interpolymer paste resin according to claim 1 is characterized in that wherein azo class accounts for the 0.005-0.1% of total monomer weight, and the superoxide in the oil-soluble initiator accounts for the 0.005-0.1% of total monomer weight.
6, the vinyl chloride-vinyl acetate copolymer paste resin for preparing according to any one described method among the claim 1-5.
7, a kind of preparation method who prepares vinyl chloride-vinyl acetate copolymer paste resin by the emulsion copolymerization method, getting weight percent earlier is the 70-97% first monomer vinylchlorid, weight percent is the 3-30% second monomer vinyl acetate, accounting under the emulsification system protection that weight percent monomer is 0.4-4%, under agitation monomer is scattered in the water, forms drop; Accounting under the oil soluble or water soluble initiator effect that weight percent monomer is 0.01-0.50%, at 40-65 ℃ of polyreaction 4-40 hour, producing particle diameter was the copolymer emulsion of 0.1-2.0 μ m then; The latex solid content is 30-55%, and latex forms vinyl chloride-vinyl acetate copolymer paste resin through spraying drying; Above-mentioned each components contents sum equals 100%;
Emulsification system is the combination of one or more anion surfactant and one or more dispersion aids; Anion surfactant is sodium salt, sylvate, long chain alkyl sulfates or the alkylaryl sulfonate of longer chain fatty acid, wherein the sodium salt of longer chain fatty acid is: oleyl alcohol sodium sulfate, sodium laurylsulfate or hexadecanol sodium sulfate, and alkylaryl sulfonate is: succinate sodium sulfonate, Sodium dodecylbenzene sulfonate or tetradecyl benzene sulfonic acid sodium salt; Dispersion aids is C
12-26Fatty Alcohol(C12-C14 and C12-C18), TETRADECONIC ACID, stearic acid, wherein C
12-26Fatty Alcohol(C12-C14 and C12-C18) is hexadecanol, Stearyl alcohol, oleyl alcohol, n-Eicosanol, behenyl alcohol, tetracosanol or ceryl alcohol;
The oil soluble initiator system is the combination of one or both azo classes and one or more superoxide; Wherein the azo class is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Superoxide is lauroyl peroxide, benzoyl peroxide, peroxy dicarbonates, tert-butyl hydroperoxide pivalate, peroxidation two-3,5 or the own ester of 5-trimethylammonium;
Water soluble initiator is that one or more peroxides are or/and the combination of one or more reductive agents; Peroxide wherein is Potassium Persulphate, Sodium Persulfate, ammonium persulphate, tertbutyl peroxide, isopropyl benzene hydroperoxide or hydrogen peroxide; Reductive agent wherein is sulfoxylic acid aldehyde, hyposulfite, pyrosulfite, sulphite or thiosulphate.
8, the preparation method of interpolymer paste resin according to claim 7, it is characterized in that peroxy dicarbonate is: the peroxy dicarbonate ethylhexyl, peroxy dicarbonate 2-ethoxy ethyl ester, the peroxy dicarbonate hexadecyl ester, peroxy dicarbonate di-tert-butyl cyclohexyl or di-isopropyl peroxydicarbonate.
9, the preparation method of interpolymer paste resin according to claim 7 is characterized in that wherein anion surfactant accounts for the 0.2-3.0% of total monomer weight, and dispersion aids accounts for the 0.2-2.0% of total monomer weight.
10, the preparation method of interpolymer paste resin according to claim 7 is characterized in that wherein anion surfactant accounts for the 0.4-1.5% of total monomer weight, and dispersion aids accounts for the 0.5-1.2% of total monomer weight.
11, the preparation method of interpolymer paste resin according to claim 7 is characterized in that wherein azo class accounts for the 0.005-0.1% of total monomer weight, and the superoxide in the oil-soluble initiator accounts for the 0.005-0.1% of total monomer weight.
12, the preparation method of interpolymer paste resin according to claim 7 is characterized in that the peroxide of water soluble initiator wherein accounts for the 0.005-0.1% of total monomer weight, and reductive agent accounts for the 0.005-0.1% of total monomer weight.
13, the preparation method of interpolymer paste resin according to claim 7, it is characterized in that in water soluble initiator, also adding the organic complexing agent of trace, this organic complexing agent is the alkali metal salts or ammonium salt of ethylenediamine tetraacetic acid (EDTA) or nitrilotriacetic acid(NTA), 1 of free form or salt form, ethylenediamine tetraacetic acid (EDTA) or diethylene triaminepentaacetic acid(DTPA) in the 2-or 1,3-.
14, the vinyl chloride-vinyl acetate copolymer paste resin for preparing according to any one described method among the claim 7-13.
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| CN100509882C (en) * | 2005-12-13 | 2009-07-08 | 沈阳化工股份有限公司 | Dextrin for producing PVC gloves and production thereof |
| CN102417556B (en) * | 2011-11-22 | 2014-04-16 | 上海氯碱化工股份有限公司 | Method for preparing vinyl chloride-vinyl acetate copolymer paste resin |
| CN102766231B (en) * | 2012-08-08 | 2015-03-25 | 上海氯碱化工股份有限公司 | Synthesis method of hydroxylated polyvinyl chloride copolymer resin |
| CN102807644A (en) * | 2012-08-29 | 2012-12-05 | 沈阳化工股份有限公司 | High-performance copolymerized paste resin and preparation method thereof |
| CN103526589A (en) * | 2013-10-23 | 2014-01-22 | 合肥聚合辐化技术有限公司 | Aromatic polyurethane pigment printing binding agent and preparation method thereof |
| CN105985479A (en) * | 2015-02-02 | 2016-10-05 | 北京化工大学 | Preparation of acrylate modified vinyl chloride-vinyl acetate copolymerized resin through microsuspension polymerization |
| JP6828462B2 (en) * | 2016-02-09 | 2021-02-10 | 東ソー株式会社 | Vinyl chloride-vinyl acetate copolymer particles and automobile underbody coating agent |
| CN108424485A (en) * | 2018-03-23 | 2018-08-21 | 安徽天辰化工股份有限公司 | A kind of production method of vinyl chloride-vinyl acetate interpolymer paste resin |
| CN109173965A (en) * | 2018-10-09 | 2019-01-11 | 天津渤化工程有限公司 | Emulsion method pastes the closed continuous producing apparatus of resin device and method |
| CN109467633B (en) * | 2018-10-10 | 2022-04-08 | 中国石油化工股份有限公司 | Preparation method of vinyl chloride-acrylate copolymer |
| CN110919949B (en) * | 2019-11-22 | 2022-02-18 | 安徽喜宝高分子材料有限公司 | Preparation method of corrosion-resistant waterproof flame-retardant elastic coiled material |
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