CN105153335A - Polyvinyl alcohol, and preparation method and application thereof - Google Patents
Polyvinyl alcohol, and preparation method and application thereof Download PDFInfo
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- CN105153335A CN105153335A CN201410228407.XA CN201410228407A CN105153335A CN 105153335 A CN105153335 A CN 105153335A CN 201410228407 A CN201410228407 A CN 201410228407A CN 105153335 A CN105153335 A CN 105153335A
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Abstract
The invention provides polyvinyl alcohol, which is characterized by having the average degree of polymerization in a range of 50-500, the alcoholysis degree in a range of 30-65 mol%, and the viscosity no more than 1500 mPa*s. Polyvinyl alcohol is prepared into an aqueous solution, which is taken as an auxiliary dispersant for suspension polymerization of vinyl polymers. The cloud point of an aqueous solution, the concentration of which is 5 wt%, (that is, a polyvinyl alcohol aqueous solution of 5 wt%), is no less than 1 DEG C and less than 15 DEG C. The viscosity measured at 25 DEG C of an aqueous solution, the concentration of which is 40 wt%, is no more than 1500 mpa*s. Gel and layering don't appear in an aqueous solution, the concentration of which is in a range of 30wt%-50wt%, in at least one year, so that the aqueous solution is extremely excellent in stability.
Description
Technical field
The invention belongs to field of organic polymer compound, be specifically related to polyvinyl alcohol and preparation method thereof, especially can be used as vinylic polymers suspension polymerization auxiliary dispersants.
Background technology
Usually, the polymerization degree is not higher than 500, and alcoholysis degree is not widely used as the auxiliary dispersants of vinylic chemical compound (especially vinylchlorid) suspension polymerization higher than the polyvinyl alcohol of 60mol%.But alcoholysis degree not higher than the polyvinyl alcohol of 60mol% due to water-soluble poor; so this series products can only with solid particulate or it being dissolved as water/alcoholic solution be supplied to user's use; when suspension polymerization of VC; use solid particle material that operability can be made severe; and can not give full play to as the effect of auxiliary dispersants; and when using the solution product of water/alcoholic solvent, the pollution problem of alcoholic solvent to environment can be produced, affect the COD value of PVC factory waste discharge.In order to solve problems, just occur on side chain, bring the research of the modified PVA aqueous solution such as amido, carboxyl, sulfonic group as auxiliary dispersants into, but the pH value of suspension polymerization of VC system during the use of ionic modified PVA, can be changed, affect the stability of system, the characteristic of dispersion agent can not effectively be played, make that the vinylic polymers porosity that obtains is not high, void distribution heterogeneity, its demonomerization and add softening agent and add man-hour plasticizer absorption ability and can not reach desirable.In addition, also the polyvinyl alcohol adopting vinyl acetate between to for plastic and other vinyl ethers to carry out modification by copolymerization is had, although this polyvinyl alcohol water dissolution is good, when making the dispersion agent product of aqueous solution, viscosity stability is excellent, but production cost obviously increases, and production process is complicated, when gained modified polyvinyl alcohol is mixed with the aqueous products of high density, viscosity is still very high, and when it is applied, operability is severe.
Summary of the invention
The object of the present invention is to provide a kind of polyvinyl alcohol, the aqueous solution that can be mixed with high density is used as the auxiliary dispersants of vinylic polymers suspension polymerization, and this auxiliary dispersants makes the good stability of vinylic polymers suspension polymerization system, obtained vinylic polymers resin property good.
The object of the invention is to be realized by following measures:
A kind of polyvinyl alcohol, it is characterized in that: mean polymerisation degree is 50 ~ 500, alcoholysis degree is 30mol% ~ 65mol%, viscosity≤1500mPa.s.Preferably, mean polymerisation degree is 50 ~ 300, and alcoholysis degree is 35mol% ~ 60mol%, viscosity≤1200mPa.s.Polyvinyl alcohol of the present invention has good water-soluble, adopt vinylic polymers auxiliary dispersants prepared by this polyvinyl alcohol, its viscosity is low and stable, using method is simple, easy operation, have excellent dispersive ability, plasticizer absorptiveness and demonomerization, the polyvinyl chloride resin using this auxiliary dispersants to obtain has excellent processibility.
Above-mentioned polyvinyl alcohol, is characterized in that: to be made into concentration be 5wt% aqueous solution cloud point is 1 DEG C≤cloud point <15 DEG C (5wt% polyvinyl alcohol water solution).Cloud point is the distinctive character of polyvinyl alcohol dispersion agent, directly determine the result of use of dispersion agent, if cloud point temperature is too low, such as lower than 1 DEG C, during use, dispersate is separated with water, and the dispersion effect of dispersion agent can not be not fully exerted, if higher than 15 DEG C, then dispersed dispersive ability obviously weakens, and the plasticizer absorptiveness of synthetic resins obviously reduces, thus affects processibility thereafter.
Another object of the present invention is to the preparation method providing above-mentioned polyvinyl alcohol, the method is simple.The object of the invention is to be realized by following measures:
The preparation method of above-mentioned polyvinyl alcohol, comprises polymerization, Alcoholysis Step, it is characterized in that: described polymerization adopts solvent pairs, and with chain transfer constant C
s: 1.0 × 10
4~ 80.0 × 10
4the solvent of (60 DEG C) is as the second solvent.First solvent adopts typical polymerization solvent, as methyl alcohol, ethanol, acetone, benzene, toluene, ritalin, vinyl acetic monomer or the trimethyl carbinol, Virahol etc., and particular methanol in actual production.The present invention is by the solution polymerization of research VAC, the second solvent is introduced in polymerization, prepare the polyvinyl acetate resin (PVAc) of ultra low polymerization degree, PVAc is through catalytic alcoholysis such as acid or alkali, obtain the low viscous PVA of low polymerization degree low alcoholysis level of the present invention, can be used for preparation suspension polymerization auxiliary dispersants.The present invention, by introducing second solvent, shortens molecular chain, thus indirectly controls in polyvinyl alcohol molecule and intermolecular hydrogen bonding, thus realizes the viscosity stability of polyvinyl alcohol water solution.
Preferably, above-mentioned second solvent is one or more in ritalin, vinyl acetic monomer, acetone, butanone, toluene, ethylbenzene, ethanol, propyl carbinol, the trimethyl carbinol or Virahol etc., and consumption is the 5-40wt% of monomer.Also letex polymerization or suspension polymerization can be adopted.Feed way as the second solvent can be disposablely to add at the polymerization initial stage, also can be add in the course of the polymerization process in batches, can also be the mode such as to add continuously.Reduce molecular weight, obtain the polyvinyl alcohol of the better ultra low polymerization degree of solvability, can suitably increase intermolecular sterically hindered in addition, weaken intermolecular hydrogen bonding, stablizing effectively in viscosity.
In above-mentioned preparation method during polyreaction, can properties-correcting agent be added, with the molecular weight of telomerized polymer, the aldehydes such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral can be adopted; Also can be the thio-alcohols such as lauryl mercaptan, preferred aldehydes, more preferably acetaldehyde, propionic aldehyde, valeral and phenyl aldehyde.Properties-correcting agent can be used alone and also can combinationally use.Its consumption mainly decides according to molecular weight of product, and general consumption is less than or equal to the 12wt% of monomer, is preferably less than or equal to 10wt%.Can add in batches or add continuously between polymerization period, can regulate according to the polymerization degree of product.
In above-mentioned preparation method, the monomer of polyreaction comprises vinyl ester, as one or more in vinyl formate, vinyl acetate, propionate, vinyl butyrate, vinyl isobutyrate ester, vinyl pivalate, vinyl-acetic ester, sad vinyl acetate, vinyl laurate, stearic acid vinyl ester or phenmethyl vinyl acetate, preferred vinyl acetate.As the feed way of monomer, can be one part or all add, start polymerization, again by remaining vinyl ester between polymerization period continuously or secondary property add, also can be add in batches, also can be semicontinuous adding, adding in batches before this by vinyl ester, also can adopt the disposable mode such as to add.
In the present invention except above-mentioned principal monomer, also other second comonomer available and vinyl ester monomers carry out copolymerization and, this kind of monomer comprises vinyl unsaturated carboxylic acid class, as acrylate, vinylformic acid, methacrylic acid, butenoic acid, Maleic Acid, Anhydrous, fumaric acid, methylene-succinic acid and alkaline metal salt thereof; This kind of monomer also comprises alkyl vinyl ether, as third class vinyl ether, octyl vinyl ether, decave, dodecyl vinyl etc.; This kind of monomer also comprises vinyl unsaturated sulfonic acid and alkyl ester thereof etc., as M Cr, butenoic acid ethyl, methylene-succinic acid methyl esters, methylene-succinic acid ethyl ester, Sorbic Acid methyl esters, sthyl sorbate, maleic acid mono alkyl ester, dialkyl maleate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, methacrylic heptyl heptylate etc.; This kind of monomer also comprises the allyl ester of saturated carboxylic acid, as stearic acid allyl ester, lauric acid allyl ester, sad allyl ester etc.
Above-mentioned polyreaction also comprises initiator, optionally selects azo, peroxide, redox type initiators etc.Wherein, azo-initiator has azo-bis-isobutyl cyanide (ABIN) or azo two cyanogen in different heptan (ABVN); The initiator of peroxide has peroxy dicarbonate two (4-tertiary butyl cyclohexyl) (Perkadox16), peroxidation PIVALIC ACID CRUDE (25)-Te pentyl ester, peroxy dicarbonate two (2-ethylhexyl) (EHP), peroxidation two (3,5,5-trimethyl acetyl) (Trigonox36) or dipropyl peroxydicarbonate (NPP-50); Redox type initiators has the reductive agent such as the peroxide oxidant such as Potassium Persulphate or ammonium persulphate and sodium bisulfite, sodium bicarbonate, tartrate or rongalite.
The temperature of reaction of being polymerized in above-mentioned preparation method is 50 ~ 75 DEG C, is preferably 55 ~ 70 DEG C.
Alcoholysis described in above-mentioned preparation method, solvent for use can be ester class: as methyl acetate, ethyl acetate, n-butyl acetate, methoxy ethyl acetate, ethoxyethyl acetate(EA), Isoamyl Acetate FCC, butoxy acetic acid ethyl ester, 1,2-diacetoxy ethane, acetic acid fourth oxygen ethoxy ethyl ester etc.; Also can be ketone: as acetone, ethyl methyl ketone, hexone, mesityl oxide, acetonyl-acetone, pimelinketone, methylcyclohexanone, fenchone etc.; Also can be hydro carbons: as benzene, toluene, ethylbenzene etc.; Can be alcohols: as methyl alcohol, ethanol, Virahol, propyl carbinol, vinyl carbinol, phenylcarbinol, Pyranton etc.; Can be ethers: as ethoxyethoxy ethanol, bu-toxyethoxy, two (ethoxyethyl) ether, dimethyl furan, tetrahydrofuran (THF), propylene oxide, diox etc.; Can be acids: as acetic acid, butanic acid, diacetyl oxide etc.; Also can be muriate: as tetracol phenixin, chloroform, methylene dichloride, 1,2-methylene dichloride, trieline etc.; Can also be aldehydes: as acetaldehyde, trichlorine formaldehyde, phenyl aldehyde etc.; Can be in above-mentioned solvent any one or multiple.Preferably, methyl alcohol, ethanol, Virahol, ritalin, vinyl acetic monomer, in acetone, benzene, toluene one or more.Most preferably be methanol as solvent.Solvent can be used alone also can be used in combination.
When after adopting solution polymerization in above-mentioned preparation method, products therefrom carries out alcoholysis, used catalyst is basic catalyst, alkali can be known sodium hydroxide, potassium hydroxide etc., and the consumption of catalyzer is generally 3 ~ 15 mmole equivalents of polymer resin, and optimum is 4.5 ~ 12.0 mmole equivalents.
The temperature of alcoholysis reaction is 20 ~ 45 DEG C, preferably 35 ~ 40 DEG C, and alcoholysis mode can any one technology mode such as intermittent type, semi continuous, continous way.
Preferably, in polyreaction, Conventional solvents is methyl alcohol, second solvent is toluene, ethanol or Virahol, monomer is VAC, initiator is Perkadox16, EHP, peroxidation PIVALIC ACID CRUDE (25)-Te pentyl ester, dipropyl peroxydicarbonate or AIBN, catalyzer is sodium hydroxide, properties-correcting agent is acetaldehyde, valeral or lauryl mercaptan, second comonomer is methylene-succinic acid, properties-correcting agent consumption is less than or equal to the 10wt% of monomer total amount, solvent total amount is the 100-150wt% of monomer total amount, second solvent is the 5-40wt% of solvent total amount, initiator amount is the 0.6-2.1wt% of monomer total amount, polymerization temperature is 55-75 DEG C, to polymerisate be obtained through de-residual single and to add concentration after thickening process with methyl alcohol be again that the sodium hydrate methanol solution of 40g/L carries out alcoholysis, sodium hydroxide concentration is the 4.5-12.0 mmole equivalent relative to polyvinyl acetate resin (PVAc), this optimum combination is adopted to obtain stable viscosity, cloud point is 1 DEG C≤cloud point <15 DEG C, dispersed auxiliary dispersants excellent especially.
Another object of the present invention is to provide the application of above-mentioned polyvinyl alcohol in the auxiliary dispersants for the preparation of vinylic polymers suspension polymerization.This application is that make it dispersing and dissolving in water, the method vacuumized by middle high temperature carries out solvent exchange using polyvinyl alcohol of the present invention as dispersate, and obtained concentration is that the aqueous solution of 30wt% ~ 50wt% becomes aid dispersion auxiliary agent.Both improve the shelf-stability of aq. type dispersion agent, and made it again to keep good mobility, improve operability.
Above-mentioned solvent exchange of stating adopts the modes such as heating in water bath, steam heating or electrically heated to be cemented out by the organic solvent water such as alcohol during alcoholysis.
Water-based auxiliary dispersants of the present invention and other dispersion stabilizers are added to the water, make vinyl monomer be dispersed in wherein, be polymerized under the existence of oil-soluble initiator.As other such dispersion stabilizers, there are methylcellulose gum, hydroxypropylcellulose, Vltra tears and cellulosic derivative, gelatin or the water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone, the wherein the most suitable use of polyvinyl alcohol of alcoholysis degree to be the polymerization degree of 70-88mol% be 500-2500, kind as dispersion agent cannot treat different things as the same, but the weight ratio of the addition of dispersion stabilizer and auxiliary dispersants aqueous solution should be 95/5 ~ 20/80, is preferably 80/20 ~ 30/60.This dispersion aids aqueous solution disposablely can to add at the polymerization initial stage, also can add in batches or continuously in the course of the polymerization process.
As the monomer of suspension polymerization object, the not independent polymerization of still vinylchlorid, also can be can with it copolymerization and monomer, such as the multipolymer of vinyl acetate between to for plastic, vinyl ether, vinylformic acid, methacrylic acid, vinylbenzene etc. is also suitable for, in addition, be not only vinylchlorid use, also may be used for any one suspension polymerization of the vinyl monomers such as vinylbenzene, methacrylic ester, vinyl acetate between to for plastic.
The present invention has following beneficial effect:
1. polyvinyl alcohol of the present invention, its mean polymerisation degree 50 ~ 500, viscosity is≤1500mPa.s, alcoholysis degree is 30mol% ~ 65mol%, be made into the auxiliary dispersants of the aqueous solution as vinylic polymers suspension polymerization, its concentration is the cloud point of the 5wt% aqueous solution is 1 DEG C≤cloud point <15 DEG C, its concentration is viscosity≤1500mpa.s that 40wt% aqueous solution records 25 DEG C time, its concentration is that the aqueous solution of 30wt% ~ 50wt% at least there will not be gel, layering within 1 year, and the stability of its aqueous solution is excellent especially.
2. polyvinyl alcohol of the present invention be used for strong to the dispersive ability of monomer oil droplet in vinylic polymers suspension polymerization, dispersion stabilization good, not by the impact of vinylic chemical compound polymerizing condition; The porosity distribution of obtained vinylic polymers is homogeneous, porosity is high, good to the detachability of reaction residual monomer, the particle form of gained resin is regular, size distribution is homogeneous, in following process process, make the plasticizer absorption ability that adds excellent, processing characteristics is excellent, and can fusion time be shortened, reduce fish-eye number.
3. the preparation method of polyvinyl alcohol provided by the invention is simple, is convenient to suitability for industrialized production.
4. the present invention is applied to auxiliary dispersants and has good viscosity stability, uses this dispersion agent can obtain the polyvinyl chloride resin of excellent in workability.
Accompanying drawing explanation
Fig. 1 is the infrared analysis spectrogram of the polyvinyl alcohol that embodiment 1 obtains, Fourier IR spectrogram.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is; following examples are only for being further detailed the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to foregoing invention content to the present invention.Add a concrete explanation to the present invention according to embodiment below, " % ", " part " in embodiment, does not have specified otherwise to be then benchmark with weight.
Embodiment 1
By 100 parts of vinyl acetate between to for plastics under the existence of 2.0 parts of AIBN, at 100 parts of methyl alcohol, solution polymerization is carried out in the mixed solvent of 40 parts of acetone, polymerization temperature is 60 DEG C, at the end of polyreaction, switch the residual list of blowout, obtain polyvinyl acetate resin, getting a part of polyvinyl acetate resin furnishing concentration is the methanol solution of 46wt%, alcoholysis is carried out again with the methanol solution that concentration is 40g/L sodium hydroxide, when alcoholysis degree reaches required value, adopt and the equimolar Glacial acetic acid termination reaction of sodium hydroxide, obtain low polymerization degree polyvinyl alcohol with low alcoholysis level of the present invention, its polymerization degree is 218, alcoholysis degree is 58.4 (mol/mol) %, its concentration is the cloud point of the aqueous solution of 4wt% is 12.5 DEG C, the viscosity that the aqueous solution of its concentration 40wt% records 25 DEG C time is 1100mPa.s, and the having good stability of product viscosity under this concentration.
In order to the polymerization degree to obtained polyvinyl alcohol, alcoholysis degree and block value, viscosity etc. carry out analysis confirmation, following detection is carried out to the polymkeric substance that embodiment 1 is synthesized:
1. infrared qualitative analysis: after first air-dry to products therefrom masking, adopt the TENSOR of German Bruker company
tMseries FT-IR (laboratory study level infrared spectrometer) measures.As shown in Figure 1, its infrared spectrum is at 3381.33cm for result
-1(-OH hydroxyl peak), 2941.33cm
-1(-CH
3,-CH
2-methyl and methylene peak), 1734.30cm
-1the characteristic peak at places such as (-CO carbonyl peaks) can be found out, the main component of this auxiliary dispersants is the PVA that a kind of alcoholysis degree is very low.
2, the mensuration of the polymerization degree: according to GB12010.9-89, the PVA obtained to embodiment 1 carries out polymerization degree measurement, and the polymerization degree recording PVA is 218.
3, the mensuration of alcoholysis degree
According to GB12010.5-89 method, test its alcoholysis degree:
Its calculation formula is:
Ac in formula
-represent remaining acetate, can calculate according to GB12010.5-89 method, the final product alcoholysis degree calculated is 58.4%.
4, cloud point test
Adopt Switzerland plum Teller-Tuo benefit LABMAX full-automatic reactor, and supporting plum Teller-Tuo benefit TRB800 turbidimeter is to the PVA obtained by embodiment A l, being mixed with concentration is that the aqueous solution of 4wt% is tested, and recording its cloud point is 12.5 DEG C.
5. shelf-stability test
Obtained polyvinyl alcohol being undertaken by leading to steam in the reactor stirred as dispersate, adding water that to be modulated into concentration be 40% aqueous solution, place 6 months at normal temperatures, dispersate (or dissolving) state before and after placing with eye observation, check the change such as generation having gel-free, layering, test the shelf-stability of this aq. type dispersion agent.
Embodiment 2
The aqueous solution that low polymerization degree polyvinyl alcohol with low alcoholysis level obtained for embodiment 1 is made into respectively is used as the auxiliary dispersants of vinylic polymers suspension polymerization; Suspension polymerization for vinylchlorid: add 180 parts of soft water in autoclave, under 400rpm, add above-mentioned dispersion aids 0.05 part while stirring, alcoholysis degree to be the 70mol% polymerization degree be 800 polyvinyl alcohol 0.06 part, 0.2 part of dilauroyl peroxide, add 150 parts of vinyl chloride monomers again, suspension polymerization is carried out, obtained polyvinyl chloride (PVC) RESINS when being warming up to 60 DEG C.Adopt embodiment A l gained resin, its apparent density is respectively 0.54g/ml, 0.51g/ml, and fish-eye number is respectively 4/400cm
2, 6/400cm
2, plasticizer absorption rate is respectively 25g/100g, 27g/100g, and 250um screenings is all less than 2.0, residual vinyl chloride for being respectively 1.8mg/Kg, 1.6mg/Kg, the requirement of the premium grads that meets international standards.
The analytical procedure of the correlated performance of auxiliary dispersants of the present invention is carried out in the following manner:
1, mean polymerisation degree: measure according to GB12010.9-89
2, alcoholysis degree: measure according to GB12010.5-89
Its calculation formula is:
Wherein Ac
----be the concentration of remaining acetate, its unit is mol/g.
3, viscosity: sample is placed in 25 DEG C of waters bath with thermostatic control, constant temperature, after 30 minutes, measures the viscosity (2# rotor, 12 turns) of solution with BrookfieLd rotational viscosimeter ((1 ~ 105mPa.s precision 0.01mPa.s)).
4, cloud point: measure by turbidity probe tip on the full-automatic reactor of 101Matlab.
5, outward appearance evaluation: visual observation.
6, the mensuration of screenings: carry out according to GB4611.
7, the mensuration of plasticizer absorption: undertaken by GB/T3400-1993.
8, the mensuration of apparent density: undertaken by GB/T3402 appendix A.
9, the mensuration of residual monomers: a certain amount of PVC particle is dissolved in tetrahydrofuran (THF), quantitatively measures remaining vinyl chloride monomer with chromatography of gases.
10, the mensuration of fish-eye number: by 100 parts, gained PVC particle, DOP50 part, dioctyl tin dilaurate 3 parts, with the rollers of 155 DEG C mixing 3 minutes, becomes the thin slice that 0.3mm is thick, measures the number of flake on 20cm*20cm area.
Embodiment 3 ~ 8
The second solvent in table 1 in embodiment 3-4 is toluene, and the second solvent in embodiment 5-6 is ethanol, and the second solvent in embodiment 7-8 is Virahol; Initiator in embodiment 5-8 is respectively Perkadox16, EHP, peroxidation PIVALIC ACID CRUDE (25)-Te pentyl ester, (embodiment is 4 to dipropyl peroxydicarbonate, and initiator is 3, not corresponding), the initiator in other embodiments, comparative example is AIBN; Catalyzer in embodiment and comparative example is sodium hydroxide; Properties-correcting agent in reference examples 2-4 is respectively acetaldehyde, valeral and lauryl mercaptan.Properties-correcting agent in embodiment 3-4 is respectively acetaldehyde, valeral; Second comonomer in embodiment and comparative example is methylene-succinic acid.Adopt the correlation parameter described in following table 1,2, according to the preparation method of embodiment 1,2, be prepared low polymerization degree polyvinyl alcohol with low alcoholysis level auxiliary dispersants aqueous solution, and polyvinyl chloride particles product.
Except eight low polymerization degree polyvinyl alcohol with low alcoholysis level that the invention described above auxiliary dispersants adopts, solvent chain-transfer agent, catalyzer and chain-transfer agent used are all not identical, it can adopt the method described in embodiment 1 to obtain, according to the analytical procedure in embodiment 1, its Structure and Properties is analyzed, result shows: its polymerization degree is 50 ~ 500, alcoholysis degree is 30mol% ~ 65mol%, 1 DEG C≤cloud point <15 DEG C, meet feature request of the present invention by ordinary method checking, these low polymerization degree polyvinyl alcohol with low alcoholysis level of the present invention are passed through solvent exchange, add water again and be deployed into the aqueous solution (its shelf-stability (>1) is good) that concentration is 40wt%, the water-based auxiliary dispersants obtained adopts the method identical with embodiment 2 to evaluate, test as embodiment 2 is carried out to gained polyvinyl chloride resin, test result shows: adopt the dispersion aids of these low polymerization degree polyvinyl alcohol with low alcoholysis level gained of the present invention when for suspension polymerization of VC, plasticizer absorption rate is 23 ~ 27g/100g, residual vinyl chloride is 0 ~ 2mg/Kg, apparent density is 0.50 ~ 0.55g/ml, fish eyes is 2 ~ 6/400cm
2, 250um screenings is 0 ~ 1.2 (%), without attachment fouling, reaches result of use of the present invention.
Claims (25)
1. a polyvinyl alcohol, is characterized in that: mean polymerisation degree is 50 ~ 500, and alcoholysis degree is 30mol% ~ 65mol%, and to be made into concentration be its cloud point of the 5wt% aqueous solution is: 1 DEG C≤cloud point < 15 DEG C.
2. polyvinyl alcohol as claimed in claim 1, it is characterized in that: mean polymerisation degree is 50 ~ 300, alcoholysis degree is 30mol% ~ 60mol%, viscosity≤1500mPa.s.
3. polyvinyl alcohol as claimed in claim 1 or 2, it is characterized in that: mean polymerisation degree is 50 ~ 300, alcoholysis degree is 35mol% ~ 60mol%, viscosity≤1200mPa.s.
4. the preparation method of polyvinyl alcohol as described in claim 1,2 or 3, comprises polymerization, Alcoholysis Step, it is characterized in that: described polymerization adopts solvent pairs, and with chain transfer constant C
s: 1.0 × 10
4~ 80.0 × 10
4the solvent of (60 DEG C) is as the second solvent.
5. the preparation method of polyvinyl alcohol as claimed in claim 4, described second solvent is one or more in ritalin, vinyl acetic monomer, acetone, toluene, ethylbenzene, ethanol, the trimethyl carbinol or Virahol etc., and consumption is the 5-40wt% of monomer.
6. the preparation method of polyvinyl alcohol as claimed in claim 5, the monomer of described polymerization comprises vinyl ester.
7. the preparation method of polyvinyl alcohol as claimed in claim 6, described vinyl ester is one or more in vinyl formate, vinyl acetate, propionate, vinyl butyrate, vinyl isobutyrate ester, vinyl pivalate, vinyl-acetic ester, sad vinyl acetate, vinyl laurate, stearic acid vinyl ester or phenmethyl vinyl acetate.
8. the preparation method of polyvinyl alcohol as claimed in claims 6 or 7, described polymerization also comprise second comonomer and vinyl ester monomers carry out copolymerization and, second comonomer is vinyl unsaturated carboxylic acid, alkyl vinyl ether, one or more in the allyl ester of vinyl unsaturated sulfonic acid, alkyl ester, saturated carboxylic acid.
9. the preparation method of polyvinyl alcohol as claimed in claim 8, described vinyl unsaturated carboxylic acid is one or more in acrylate, vinylformic acid, methacrylic acid, butenoic acid, Maleic Acid, Anhydrous, fumaric acid, methylene-succinic acid or its an alkali metal salt; Alkyl vinyl ether is one or more in third class vinyl ether, octyl vinyl ether, decave, dodecyl vinyl; Vinyl unsaturated sulfonic acid and alkyl ester thereof are one or more in M Cr, butenoic acid ethyl, methylene-succinic acid methyl esters, methylene-succinic acid ethyl ester, Sorbic Acid methyl esters, sthyl sorbate, maleic acid mono alkyl ester, dialkyl maleate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, pentylmethacrylate, methacrylic heptyl heptylate; The allyl ester of saturated carboxylic acid is one or more in stearic acid allyl ester, lauric acid allyl ester, sad allyl ester.
10. the preparation method of polyvinyl alcohol as claimed in claim 4, properties-correcting agent is added during polyreaction, described properties-correcting agent is one or more in acetaldehyde, propionic aldehyde, butyraldehyde, valeral, acetone, ethyl ketone, lauryl mercaptan, formaldehyde, propionic aldehyde, valeral or phenyl aldehyde, and consumption is less than or equal to the 12wt% of monomer.
11. as described in claim 4 or 10 preparation method of polyvinyl alcohol, described polyreaction also comprises initiator, and described initiator is azo, peroxide or redox class.
The preparation method of 12. polyvinyl alcohol as claimed in claim 11, described azo-initiator is azo-bis-isobutyl cyanide (ABIN) or azo two cyanogen in different heptan (ABVN); Described peroxide type initiators is peroxy dicarbonate two (4-tertiary butyl cyclohexyl) (Perkadox16), peroxidation PIVALIC ACID CRUDE (25)-Te pentyl ester, peroxy dicarbonate two (2-ethylhexyl) (EHP), peroxidation two (3,5,5-trimethyl acetyl) one or more in (Trigonox36) or dipropyl peroxydicarbonate (NPP-50); Described redox type initiators is peroxide oxidant, sodium bisulfite, sodium bicarbonate, tartrate or rongalite.
13. as described in claim 4 or 10 preparation method of polyvinyl alcohol, the temperature of reaction of described polymerization is 50 ~ 75 DEG C.
The preparation method of 14. polyvinyl alcohol as claimed in claim 13, the temperature of reaction of described polymerization is 55 ~ 70 DEG C.
The preparation method of 15. polyvinyl alcohol as claimed in claim 4, described alcoholysis solvent is ester, ketone, hydrocarbon, alcohol, ether, acid, muriate or aldehyde.
The preparation method of 16. polyvinyl alcohol as claimed in claim 13, described alcoholysis solvent ester class is one or more in methyl acetate, ethyl acetate, n-butyl acetate, methoxy ethyl acetate, ethoxyethyl acetate(EA), Isoamyl Acetate FCC, butoxy acetic acid ethyl ester, 1,2-diacetoxy ethane, acetic acid fourth oxygen ethoxy ethyl ester; Described alcoholysis solvent ketone is one or more in acetone, ethyl methyl ketone, hexone, mesityl oxide, acetonyl-acetone, pimelinketone, methylcyclohexanone, fenchone; Described alcoholysis solvent hydro carbons is one or more in benzene, toluene, ethylbenzene; Described alcoholysis solvent alcohols is one or more in methyl alcohol, ethanol, Virahol, propyl carbinol, vinyl carbinol, phenylcarbinol, Pyranton; Described alcoholysis solvent ethers is one or more in ethoxyethoxy ethanol, bu-toxyethoxy, two (ethoxyethyl) ether, dimethyl furan, tetrahydrofuran (THF), propylene oxide, diox; Described acids is one or more in acetic acid, butanic acid, diacetyl oxide; Described alcoholysis solvent muriate is one or more in tetracol phenixin, chloroform, methylene dichloride, 1,2-methylene dichloride, trieline; Described alcoholysis solvent aldehydes be in acetaldehyde, trichlorine formaldehyde, phenyl aldehyde one or more.
The preparation method of 17. polyvinyl alcohol as claimed in claim 15, described alcoholysis uses catalyzer, and catalyzer is basic catalyst, and its consumption is 3 ~ 15 mmole equivalents of polymer resin.
The preparation method of 18. polyvinyl alcohol as claimed in claim 17, described alcoholysis catalysts is basic catalyst, and alkali is sodium hydroxide or potassium hydroxide.
The preparation method of 19. polyvinyl alcohol as claimed in claim 4, the temperature of alcoholysis reaction is 20 ~ 45 DEG C.
The preparation method of 20. polyvinyl alcohol as claimed in claim 4, in described polyreaction, Conventional solvents is methyl alcohol, second solvent is toluene, ethanol or Virahol, monomer is VAC, initiator is Perkadox16, EHP, peroxidation PIVALIC ACID CRUDE (25)-Te pentyl ester, dipropyl peroxydicarbonate or AIBN, catalyzer is sodium hydroxide, properties-correcting agent is acetaldehyde, valeral or lauryl mercaptan, second comonomer is methylene-succinic acid, properties-correcting agent consumption is less than or equal to the 10wt% of monomer total amount, solvent total amount is the 100-150wt% of monomer total amount, second solvent is the 5-40wt% of solvent total amount, initiator amount is the 0.6-2.1wt% of monomer total amount, polymerization temperature is 55-75 DEG C, to polymerisate be obtained through de-residual single and to add concentration after thickening process with methyl alcohol be again that the sodium hydrate methanol solution of 40g/L carries out alcoholysis, sodium hydroxide concentration is the 4.5-12.0 mmole equivalent relative to polyvinyl acetate resin (PVAc).
21. as arbitrary in claim 1-3 as described in the application of polyvinyl alcohol in the auxiliary dispersants for the preparation of vinylic polymers suspension polymerization.
22. application of polyvinyl alcohol in the auxiliary dispersants for the preparation of vinylic polymers suspension polymerization as claimed in claim 21, described polyvinyl alcohol is dissolved in water as dispersate, the method vacuumized by middle high temperature carries out solvent exchange, and obtained concentration is that the aqueous solution of 30wt% ~ 50wt% becomes aid dispersion auxiliary agent.
23. application of polyvinyl alcohol in the auxiliary dispersants for the preparation of vinylic polymers suspension polymerization as claimed in claim 22, described aid dispersion auxiliary agent and dispersion stabilizer are added to the water, vinyl monomer is made to be dispersed in wherein, be polymerized under the existence of oil-soluble initiator, other dispersion stabilizers described are water-soluble polymer, and the weight ratio of dispersion stabilizer and aid dispersion auxiliary agent aqueous solution is 95/5 ~ 20/80.
24. application of polyvinyl alcohol in the auxiliary dispersants for the preparation of vinylic polymers suspension polymerization as claimed in claim 23, described water-soluble polymer is methylcellulose gum, hydroxypropylcellulose, Vltra tears or cellulosic derivative, gelatin, polyvinyl alcohol or polyvinylpyrrolidone, and dispersion stabilizer and aid dispersion auxiliary agent aqueous solution weight ratio are 80/20 ~ 30/60.
25. application of polyvinyl alcohol in the auxiliary dispersants for the preparation of vinylic polymers suspension polymerization as claimed in claim 23, the polymerization degree of other dispersion agent described to be alcoholysis degree be 70-88mol% is the polyvinyl alcohol of 500-2500.
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