CN1032012C - Spherical vinyl chloride resin granules and process for producing same - Google Patents
Spherical vinyl chloride resin granules and process for producing same Download PDFInfo
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- CN1032012C CN1032012C CN 89109262 CN89109262A CN1032012C CN 1032012 C CN1032012 C CN 1032012C CN 89109262 CN89109262 CN 89109262 CN 89109262 A CN89109262 A CN 89109262A CN 1032012 C CN1032012 C CN 1032012C
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Abstract
Spherical vinyl chloride resin granules and a process for producing the same are disclosed. The granules exhibit excellent particle characteristics and sol-forming properties and are therefore useful as resins for paste.
Description
The present invention relates to the spherical vinyl chloride resin granules that the water dispersion (it is obtained by suspension polymerization or emulsion polymerization) by vinyl chloride resin makes, also relate to the method for preparing this product.
Normally used vinyl chloride resin granules, be by with vinylchlorid or will be in the presence of tensio-active agent based on the monomer mixture of vinylchlorid, carry out suspension polymerization or emulsion polymerization and obtain aqueous resin dispersion, subsequently this aqueous resin dispersion is made by the spraying drying granulating.
When this vinyl chloride resin granules is used to for example prepare thickener, this particle mixes to generate a kind of colloidal sol (this is referred to as solation) mutually with softening agent, resulting colloidal sol (thickener) carries out molding, and heating makes it sclerosis (being called pectisation) to obtain a kind of final solidifying product.If this vinyl chloride resin granules does not possess the performance of sufficient formation colloidal sol, if perhaps this colloidal sol contains still not dispersive macrobead, then the workability of sticking with paste when moulding can become bad, and perhaps the performance of its finished product can reduce.Therefore, in the colloidal sol forming process, the vinyl chloride resin of use is by levigate.So, when this vinyl chloride resin by levigate with after producing thickener, its particle shape is considered to directly not influence the finished product, and seldom coating of particles is noted.
But, as the result to the vinyl chloride resin granules shape research, the inventor finds, and various erose particles for example have the hollow bead of macropore and the hollow bead of fragmentation, must not have satisfied material characteristic, for example flow characteristics.And these particles have low bulk specific gravity, and the weight of per unit volume is little, have therefore increased the cost of transportation.
In addition, be used to prepare the vinyl chloride resin of thickener, when the resin sack is opened, can have caused dust, and influence Working environment, nor can weigh automatically and charging by levigated.
In order to address the above problem, done and made great efforts to obtain being used for preparing thickener, and the granular vinyl chloride resin that does not need to carry out fine grinding, for example, (term used herein " JP-A " is meant unexamined Japanese patent publication) is disclosed among (term used herein " JP-B " is meant the Japanese patent publication of having examined) and the JP-A-60-120726 in JP-B-57-5815, advised in the spraying drying of aqueous resin dispersion, when charging and spraying, reduce the temperature of dry air, to obtain having the performance of the good particle characteristics and the formation colloidal sol of satisfaction.
Yet, the reduction of drying air temperature, the rate of drying that slowed down, the result, the moisture that is kept in the particle has increased.The gel that obtains from the prepared colloidal sol of the particle with high residual moisture content, the surface properties of the moulded work that it generated is bad.
It is little during to about 20 μ m when average particle size such as control that JP-B-57-5815 advised, and then rate of drying has improved, and its residual moisture content can reduce.But, conversely, its particle characteristics has then degenerated.On the other hand, it is big during to about 80～120 μ m by control that JP-A-60-120726 advised when mean particle size, and this particle characteristics is improved, but that its residual moisture content becomes is big, needs extra drying step.
In addition, these granulation process still exist and contain a large amount of not problems of discrete particles in the colloidal sol.In addition, at lay up period, the performance that these particulate form colloidal sol can further reduce, and the ratio of discrete particles does not increase in resulting colloidal sol, and finally becoming is unsuitable for using in paste molding.
In order to prevent that its performance that forms colloidal sol from reducing, recommended to add gylcol ether or nonionogenic tenside, at Kunstoffe (plastics), p.3 Vol64 is introduced in (1974) as F.Ponizil.Therefore and be not suitable for general purposes but, these additives make the performance depreciation of the finished product sometimes.
An object of the present invention is to provide a kind of vinyl chloride resin granules, particularly prepare its thickener, this vinylchlorid particle shows good particle characteristics and the performance of the formation colloidal sol that improved.
Another object of the present invention provides adding can not cause dust man-hour, and can be used for the vinyl chloride resin granules of automatic weighing and charging.
A further object of the present invention provides the vinyl chloride resin granules with shelf characteric of having improved.
A further object of the present invention provides the method for the above-mentioned vinyl chloride resin granules of preparation.
The inventor carried out deep research, has been found that consequently above-mentioned purpose of the present invention can be by reaching with spherical vinyl chloride resin granules (preferably having special particle size dispersion).Also find, be used for preparing the good granular vinyl chloride resin of thickener, can be under special conditions, with spray-dryer the water dispersion of vinyl chloride resin is carried out drying and granulating and make.Further determined the following fact, if promptly by the inwall of spray-dired particle adhesion to spray-dryer, and be heated the long time when it adheres on the wall, then by in such colloidal sol that particle generated, the ratio regular meeting of discrete particles does not increase; And particle reduces in this adhesion of moisture eliminator inwall, and the vinyl chloride resin grain husk grain that then can cause the paste molding that generates to be used has the performance of good formation colloidal sol, and generates the not little a kind of colloidal sol of ratio of discrete particles.
It is involved in the present invention from this spherical vinyl chloride resin granules that Here it is.
The invention further relates to the preparation method of the vinyl chloride resin granules that is used to prepare thickener, this method comprises that the water dispersion of the vinyl chloride resin that paste molding is used carries out drying and granulating in spray-dryer, the absolute humidity of employed dry air is 0.008～0.012 kg/kg, and the temperature in the moisture eliminator ingress is not higher than 100 ℃, be not higher than 50 ℃ in the exit temperature, to obtain water content is 0.1～0.5% weight, and mean particle size is 30～100 microns a particle.
Owing to is spheroidal particle by resin particle of the present invention, needn't grind and obtain, these particles roll easily or flow, and show the satisfied particle characteristics that illustrates with the slope of repose.Because these particles do not carry out fine grinding, therefore reduced the ratio of fine powder, and this fine powder when opening, pocket can cause that Working environment becomes bad owing to producing dust.According to method for making of carrying out under given conditions of the present invention, resulting granules has the performance of satisfied formation colloidal sol.
Fig. 1 is expression by the electron photomicrograph of the embodiment of the invention 1 resulting spherical vinyl chloride resin granules granular texture (about 900 * magnification).
Fig. 2 is the electron photomicrograph that is illustrated in embodiment 1 resulting non-spherical vinyl chloride resin granular texture (about 130 * magnification).
Fig. 3 is illustrated in the comparing embodiment 2, grinds the electron photomicrograph (about 900 * magnification) of the vinyl chloride resin granular texture with 50 ° at slope of repose that obtains by the spherical particle with embodiment 1
Term used herein " spheric granules " has not only comprised real spheroid, and bag The ratio of having drawn together major axis/minor axis is about 1.1 or smaller round, and a little distortion Real spheroid or orbicule.
Term used herein " particle " refers to be dispersed in vinyl chloride resin in the aqueous dispersion Aggregation.
Not special to the vinyl chloride resin that consists of spherical vinyl chloride resin granules of the present invention Restriction, the homopolymers of vinyl chloride or the general copolymer resin that mainly contains vinyl chloride can be used In the present invention.
According to spherical vinyl chloride resin granules of the present invention, so long as spherical, big to its size Little not restriction, but its diameter upper limit is approximately 1000 microns. From particle characteristics Viewpoint has diameter and is 20 microns or greater than the preferred value of the particle ratio of this value, with The total amount of particle is calculated, and is at least 60% weight; And have diameter be 40 microns or Greater than the more preferably value of the particle ratio of this value, calculate with the total amount of grain husk grain, be at least 70% weight.
Can be used for the comonomer that mainly comprises the copolymer resin of vinyl chloride of the present invention, Comprise α-alkene, ethene for example, propylene and butylene; Vinyl carboxylates, for example vinyl acetate Ester, vinyl benzoate, and stearic acid vinyl ester, the ethenylidene of halo, for example 1,1-dichloroethylene; The acrylate or the methyl-prop that generate with the alcohol that contains 1～20 carbon atom The olefin(e) acid ester, methyl methacrylate for example, methyl acrylate, ethyl acrylate, acrylic acid fourth Ester, acrylic acid 2-ethylhexyl, and dodecylacrylate; With benzylalcohol or with by halogen Benzylalcohol plain or that replaced by nitro and the acrylate or the methacrylate that generate, for example propylene Acid benzyl ester and acrylic acid 2-chloro benzyl ester; The olefinic unsaturated monocarboxylic is such as acrylic acid and first Base acrylic acid; Ethylenically unsaturated dicarboxylic, and acid anhydrides, perhaps with contain 1～20 carbon The alcohol of atom generates their monoalkyl or dialkyl, aconitic acid for example, fumaric acid, Maleic acid, itaconic acid, citraconic acid, maleic anhydride, dibutyl fumarate, and maleic acid list second Ester; The ethylenically unsaturated carboxylic acids acid amides, acrylamide for example, Methacrylamide; The olefinic insatiable hunger With the carboxylic acid nitrile, such as acrylonitrile and methacrylonitrile; Vinyl pyrrolidone, for example N-second Thiazolinyl-2-pyrrolidones; The alkyl ethene that 1～20 carbon atom is arranged at its moieties Base ether, methyl vinyl ether for example, ethyl vinyl ether, octadecyl vinyl ether; Diene Class, such as isoprene, butadiene; Vinyl phosphonate, for example phosphonic acids two (2-chloroethyl) Vinyl acetate; And other vinyl comonomer that can close with chloroethylene copolymer, at these altogether In the poly-monomer, vinyl acetate is particularly useful for making for example a kind of emulsion of a kind of aqueous dispersion. Content of vinylchloride preferred value in copolymer resin more preferably is worth for being not less than 80% weight Be 90～95% weight.
Can prepare with a kind of method according to granular resin of the present invention, the method comprises usefulness Aqueous dispersion in the vinyl chloride resin of paste mo(u)lding carries out drying and granulating in spray dryer. This aqueous dispersion is by with vinyl chloride or mainly comprise the monomer mixture of vinyl chloride, on the surface Under the existence of activating agent, carry out suspension polymerisation or emulsion polymerisation and make.
The Surfactant that is used for polymerisation is not subjected to especially strict restriction, and it comprises general Anion surfactant or non-ionic surface active agent.
The example of the anion surfactant that is suitable for is alkyl sulfonate esters, alkyl sodium sulfate ester, carbon Acid alkyl ester, alkylphosphonate, butanedioic acid Arrcostab, polyxyethylated sulfuric ester, polyoxy The vinyl alkyl aromatic yl acid ester. The example of the non-ionic surface active agent that is suitable for is polyoxyethylene alkane Base ether, polyoxyethylene alkylaryl ether, sorbitan fatty acid esters, polyoxyethylene dehydration D-sorbite fatty acid ester, and polyoxyethylene fatty acid ester.
The concentration that can carry out spray-dired water dispersion is not restricted, and its concentration is generally about 20～65% weight, is preferably about 40～60% weight.
When the preparation water dispersion, the consumption of initiators for polymerization in monomer or monomer mixture, is about 0.01～5% weight.The example that can be used in the initiators for polymerization in the suspension polymerization has comprised oil-soluble compounds, for example cross two carbonic ethers, cross as diethyl that two carbonic ethers, two-2-ethylhexyl are two peroxodicarbonate, two-2-ethoxyethyl group is crossed two carbonic ethers, di-isopropyl crosses two carbonic ethers and diisobutyl is crossed two carbonic ethers; Diacetyl peroxide, as benzoyl peroxide, peroxidation is to the mono chloro benzene formyl, peroxidation 2,4-dichloro-benzoyl, peroxidation decoyl, decanoyl peroxide, lauroyl peroxide and peroxidation 3,5,5-trimethyl acetyl; And azo-compound, as Diisopropyl azodicarboxylate, the two valeronitriles of azo.The polymerization starter example that can be used for emulsion polymerization comprises water-soluble cpds, ammonium peroxydisulfate for example, Sodium persulfate and Potassium Persulfate, hydrogen peroxide, and reductionoxidation polymerization reaction initiator system, this system comprises a kind of peroxydisulfate and a kind of alkali-metal hydrosulfate, thiosulphate, or hydrosulphite.
To being used for that this aqueous resin dispersion that makes is carried out drying and granulated spray-dryer has no particular limits, it comprises normally used various types of spray-dryer.The example of the spray-dryer that is suitable for is at for example K.Masters, Spray dryingHandbook (spraying drying handbook) (3rd Ed), P.121, and Fig.4,10, be described among the George Godwin Limited (1979).
Aqueous vinyl chloride resin dispersion, the spraying gun that at first is installed on the spray-dryer atomizes, and carries out drying then to generate spheroidal particle, spheroidal particle is taken out from this system at last again.
When resulting granules was used to paste molding, drying temperature was high more, disperseed the required time then long more in plasticising these particles.Therefore, for obtaining being applicable to the spherical vinyl chloride resin granules of making thickener, in spray-dryer, carry out drying and granulating, the absolute humidity of employed dry air is 0.008～0.012 kg/kg, controlling the temperature of dry air in the ingress simultaneously is 100～60 ℃, the temperature of preferably controlling the exit is 50～40 ℃, then is ideal.Moisture eliminator can be measured with common thermometer in the temperature in ingress and exit, and the absolute humidity of dry air can be measured with Ceramic Humidity Meter, for example the 6802 type Ceramic Humidity Meter of being made with Japan-Canomax Co., Ltd..
Consider that from the viewpoint of drying efficiency the absolute humidity of dry air may be best less than 0.008 kg/kg.But obtained particulate forms the performance of colloidal sol and can degenerate.On the other hand, if use the dry air of absolute humidity greater than 0.012 kg/kg, then resulting granules contains considerable moisture content, with the prepared colloidal sol of such particle, contain high moisture content, can not as desirable, demonstrate satisfied characteristic, ropy the finished product can only be provided, for example the film of surface smoothness difference.
If drying air temperature surpasses 100 ℃ in the ingress, perhaps surpass 50 ℃ in the exit, then for to obtain being dispersed to the particle that being used in the softening agent prepares thickener, the needed time can extend.
If only, will increase greatly yet be used for carrying out dry needed air quantity from particles dispersed is considered that it is desirable using lower drying temperature to the time the softening agent.Particularly, when dry air humidity was high, the moisture content that remains in the particle can become greatly, and therefore this feasible colloidal sol that is difficult to obtain having desirable characteristics, preferably avoid making the temperature of dry air too to reduce.
Because resulting granules is thermo-labile, and it tends to make it to form the performance depreciation of colloidal sol when placing oneself in the midst of in the hot environment as fruit granule, in order to make the particle that obtains have the performance of good formation colloidal sol, it is long-time that particle is stopped at spray-dryer, for example stopped 4 hours or the longer time at 50 ℃.
When dry and granulation, the part that particle contacts with spray-dryer, typically comprise bottom the spray-dryer cone partly internal surface and the upper wall of moisture eliminator, and the sidewall of moisture eliminator.In the present invention, to the surface of this cone of major general part with 100
#It is desirable that polishing wheel or thinner polishing wheel carry out precision work.The effect of the cone part of spray-dryer is to collect dry granules in its bottom, and particle is discharged from moisture eliminator.If the slickness on surface is 100
#Polishing wheel or thinner slickness, then particle can reduce the adhesion of cone part, that is to say that the numbers of particles that stands long-time heating has tailed off, and has therefore improved the performance that collected particulate forms colloidal sol.
For reducing the adhesion of particle on spray-dryer, form the performance of colloidal sol with the resultant particulate of further improvement, except the cone of spray-dryer surface partly being polished or the like, use the method for common eliminating particle adhesion to the spray-dryer inwall, the moisture eliminator body is vibrated, with inwall of air jet stream directive atomizer or the like, also can guarantee to achieve the goal.
Has such average particle size by the prepared grain husk grain of aqueous resin dispersion, this average particle size does not cause any problem when lappingout, and the performance of the formation colloidal sol of this average particle size demonstration satisfaction, promptly average particle size is 30～100 microns, 40～60 microns of preferred values.
Because they are spheric, has satisfied flow characteristics according to spherical vinyl chloride particle of the present invention, unlike common vinylchlorid particle, they can transport them with pneumatic transport method or tank body truck at an easy rate and can weigh automatically and charging; And they also have high bulk specific gravity and high weight/unit volume, have therefore reduced transportation cost.In addition, because spherical vinyl chloride resin granules of the present invention can be used to stick with paste mould, therefore can avoid with the general paste producing of levigated with the caused problem of vinyl chloride resin,, and can not be suitable for and weigh automatically and automatic feed promptly owing to the dust effect and aggravating working environment.
When being used as the paste moulding material according to spherical vinyl chloride resin granules of the present invention, even when they do not possess the performance of enough formation colloidal sol and situation about need grind when generating colloidal sol, because above-mentioned flow characteristics and easily transportation property, can be reduced to the particle that obtains porphyrize and the trouble that runs into, also can reduce its required cost, so just make it be suitable for adopting advanced automatization system.
When making thickener with spherical vinyl chloride resin granules of the present invention, in order to make them show the performance of enough formation colloidal sol, preferred scheme is, the diameter of particle is not more than 200 microns, wherein diameter be 20 microns or greater than this value (more preferably 40 microns or greater than this value, most preferably 50 microns or greater than this value) proportion of particles, totally calculate with particulate, at least should be 60% weight, preferred 70% weight that is at least, most preferred 90% weight that is at least.This particle size dispersion situation (its particle rolls or flowability is gratifying, also is easy to obtain satisfied particle properties) is confirmed by its slope of repose, and is not given rise to trouble when weighing with charging automatically.Because they are not carefully ground, so can reduce those make the little powder of Working environment deterioration because of playing dirt ratio.In general, when running into above-mentioned size distribution situation, be in as the slope of repose of particle characteristics sign in 30～38 ° the scope (method of measuring the slope of repose will be mentioned below).
In general, consider that having big spheroidal particle is preferably, and consider to have little spheroidal particle for well from the angle of the performance that improve to form colloidal sol from the angle of good particle characteristics.In this contact, as long as above-mentioned particle size dispersion meets the requirements, this particle will satisfy particle characteristics and form the requirement of this two aspect of performance of colloidal sol.
Spherical vinyl chloride particulate water content of the present invention is 0.01～1% weight, and under particular case, when particle is used to stick with paste when moulding, its water content is preferably 0.1～0.5% weight.The particulate water content then can reduce the performance that it forms colloidal sol as less than 0.1% weight.Water content makes the colloidal sol of generation have bigger moisture greater than the particle of 0.5% weight, and this moisture content can perhaps can make the poor quality of the finished product that generated by colloidal sol to the viscosity plays injurious effects of colloidal sol, and is for example rough.Therefore, the drying process of aqueous resin dispersion is preferably carried out like this, promptly makes resulting granules contain above-mentioned water content, thereby produces the particle of the performance with excellent generation colloidal sol reposefully.The particulate water content can be measured with Karl Fischer moisture content tester or with infrared moisture meter.
As mentioned above, according to the vinyl chloride resin grain husk grain that is used to prepare thickener of the present invention, shown the performance of excellent formation colloidal sol.The terminology used here performance of formation colloidal sol " excellent " is meant that this particle mixes with softening agent when it, and when forming a kind of colloidal sol, the aggregate of not discrete particles wherein or the diameter of caking are measured according to following method and to be not more than 60 microns.
As long as the diameter of caking aggregate in colloidal sol is 60 microns or less than this value, then there is not surperficial false defect (for example flake) in the resulting product of colloidal sol topped thing of wallpaper and floor or the like for example thus, good quality basically.
Consider from this angle of good particle characteristics, the average particulate diameter of this spheroidal particle is preferably 20 microns or greater than this value, and from easily not dry and improve its angle that forms the performance of colloidal sol and consider, its mean particle size is preferably 100 microns or less than this value.Mean particle size can satisfy this two aspect of particle characteristics and drying property simultaneously at the particle of above-mentioned scope.
The inventor has continued their research, result of study is found, be carried out dry and granulating character with the water dispersion that obtains being used to stick with paste the vinyl chloride resin granules of moulding, the character of paste being moulded the finished product of gained has very big influence, perhaps the workability in the moulding process that is carried out is with the following methods had very big influence.
1) water dispersion of vinyl chloride resin partly contains aggregate.This aggregate can disappear when stirring, but when this water dispersion leaves standstill, then partly reproduces in water dispersion again.
2) by the vinyl chloride resin dispersion liquid resulting granules that contains aggregate, its performance that forms colloidal sol is bad.When these particles were saved, its performance that forms colloidal sol can further worsen.
3) particle that is obtained by the vinyl chloride resin aqueous solution (aggregate in this aqueous solution disappears by stirring) shows the satisfied performance that forms colloidal sol, and, even when preserving, the performance that particulate forms colloidal sol does not degenerate.
Therefore, the vinyl chloride resin aqueous dispersions should stir, and delivers in the spray-dryer without a break then, and finishes dry in the short time and granulation is necessary.That is to say, have found that, when sending into the vinyl chloride resin water-dispersion in the spray-dryer, the water dispersion of per kilogram is imposed the powerful stirring action that power is at least 100 watts, just can obtain the vinyl chloride resin granules that is used for the paste producing material of incomparable excellent.
Vinyl chloride resin water dispersion for being used for preparing thickener has no particular limits, and is similar to the general water dispersion that is used for paste producing material usefulness vinylchlorid.
Water dispersion is being carried out sending in the spray-dryer under the powerful condition of stirring with 100 watts power with respect to the water dispersion of per kilogram at least.
Stir water dispersion and it is sent in the spray-dryer by brute force, then the part aggregate that is present in water dispersion can reduce, because water dispersion is in this state by spraying drying, the particle that then obtains will generate the low colloidal sol of coarse particles content.
Above-mentioned water dispersion has a kind of character, and promptly when temperature was 70～80 ℃ or higher temperature, the reversible aggregation effect had taken place.If stirring intensity is greater than 1000 watts/kg of water dispersion, then water dispersion easily experiences the reversible aggregation effect.In order to prevent that temperature from raising, when cooling, stir to do and obtain (though effect is little).
Be preferably in 5 minutes of stirring water dispersion is sent in the spray-dryer.
The equipment that can be used to stir is not subjected to special restriction, and it comprises for example common paddle stirrer, propeller type stirrer, steam turbine formula agitator, high speed rotating homogenizer, and ultrasonic homogenizer.
Be not particularly limited carrying out drying and granulated spray-dryer being used for through the water dispersion of so handling.Any common spray-dryer can adopt, to spray condition also without limits.
Now will be in the mode of the following examples and comparing embodiment, a more detailed description of the present invention is to do.But should be appreciated that this is not a limitation of the present invention.Except as otherwise noted, all percentage ratio, umber and ratio among the present invention all measured by weight.
In these embodiments, the characteristic of resulting vinyl chloride resin granules is all forming the performance of colloidal sol, mean particle size, and the slope of repose, keepabilities etc. are estimated according to following method.
1) performance of formation colloidal sol
The size of not disperseing aggregate in 1-a) colloidal sol
In the Hobart of 5 liters of volumes mixing tank (by the mining industry manufacturing of product river, model is 5DMV), pack into 500 gram particles and 325 gram dioctyl phthalate (DOP)s.This mixture was stirred 10 minutes at 25 ℃ with 141rpm (from revolution) and 67rpm (revolution number) with hook-shaped propeller type stirrer, make it to mix, with preparation colloidal sol.The size of dispersive aggregate not in colloidal sol is according to JISK
5400" the general survey method of coating---particle check 4.4 " measured with the grinding test device, and estimated with scale card.More particularly, colloidal sol can be poured in the groove of the degree of depth by 25 microns to 0 micron the grinding test device that descends gradually, and colloidal sol be wipeed off, read the striped that does not disperse aggregate to occur, calculate the diameter of aggregate with this with scraper.
The number of dispersive aggregate not in 1-b) film
With the colloidal sol in above-mentioned 1-a), be that 152 microns thin film cladding machine spreads over it on the sheet glass with having the space.With this coating in stove in 200 ℃ of heating 4 minutes, make it gelation, to form film.Take out the sample of 3 centimetres of a slice 3 cm x from film, the method that detects by an unaided eye is calculated its flake number.
2) mean particle size of particle
Measure 100 microns or with sieve, measure the mean particle size of littler particle with the Coulter counter greater than the mean particle size of the particle of this number.
3) slope of repose
Powder check meter with the powder optical research manufacturing of thin river is measured the slope of repose.
4) become mealiness matter
20 gram particles are put into the glass sample hose of the band plug of 100 ml volumes, and after pipe close was good, it is carried out frequency was per 5 seconds 10 times, and the amplitude of oscillation is 20 centimetres shaking for 30 seconds.Remove unstopper, the one-tenth powder situation in the pipe that detects by an unaided eye.
5) keepability
It is in 30 ℃ the thermostatted 3 months that particle is stored in temperature, uses then and above-mentioned 1-a), 1-b) identical method is estimated its performance that forms colloidal sol.
Embodiment 1～3
With solids content is 47%, contains the water dispersion of 100 parts of vinyl chloride resins and 1.0 parts of sodium lauryl sulphate, with the spray-dryer (diameter of tower: 2.75 meters; The length of tower: cylinder part is divided into 3.0 meters, tapered segment: 2.2 meters; The angle of cone part: 60 °) carries out drying and granulating.This spray-dryer has rotating disk spraying gun (8.4 centimetres of diameters), and the revolution of this rotating disk is transferred in 18000rpm (embodiment 1), 16000rpm (embodiment 2) or 5000rpm (embodiment 3).To then it be heated to 80 ℃ air so that its absolute humidity is 0.01 kg/kg through moisture extractor, send in the spray-dryer.The amount of control dry air is so that the temperature of dryer export is 45 ℃.Carry out spray-dired other condition and resultant particulate evaluation result is shown in the following table 1.
Observe with electron microscope (magnification be approximately 900 *), proved conclusively that resulting granules is a spheric in embodiment 1 to 3.Resulting electron photomicrograph is shown in Fig. 1 among the embodiment 1.
Comparing embodiment 1
Except the revolution of rotating disk is changed into the 22000rpm, all prepare particle by the method identical with embodiment 1.That estimates the results are shown in the following table 1, and by this table as can be seen, its slope of repose is brought up to 40 ° significantly.
Electron microscope observation (magnification be approximately 130 *) shows that resulting granules is not a spheric, as shown in Figure 2.
Comparing embodiment 2
Embodiment 1 resulting spheroidal particle is ground and estimated, resulting the results are shown in the following table 1.As what obviously find out by table 1, resulting granules the slope of repose with become mealiness can aspect poorer than the particle of embodiment 1-5.Particulate electron photomicrograph (magnification about 900 *) as shown in Figure 3.
Table 1
Relatively fullsized is more real for EXAMPLE Example embodiment
123 execute example 1 execute example 2 drying condition rotating disc revolution 18,000 16,000 5,000 22,000 18000 (rpm) particle characteristics average grains large 38 50 100 20 * little (μ m) 20 μ m or 88 95.5 99.5 50 5 greater than particle percentage (%) the 40 μ m of this value or 52 65 96 10 1 particle percentage (%) angles of repose greater than this value (°) 37 33 32 40 50 one-tenth powders observe (g/cc) water content (%) 0.20 0.21 0.40 0.20 0.20 of bulk specific weight 0.56 0.55 0.56 0.49 0.31 (bulk packing)
Embodiment 4
With solids content is 47%, contains 100 parts and is used to prepare the vinyl chloride resin of slurry and water dispersion spray-dryer (the tower diameter: 2.75 meters that has rotating disk spraying gun (8.4 centimetres of diameters) of 1.0 parts of Sodium dodecylbenzene sulfonatees; Tower is long: cylinder part is divided into 3.0 meters, and cone partly is 2.2 meters; The angle of cone part: 60 °) carries out drying and granulating.The rotating disk revolution is set up at 12000rpm, will be through moisture extractor so that its absolute humidity be 0.01 kg/kg, and the air that is heated 80 ℃ is then sent in the spray-dryer.The amount of dry air will be controlled so that the temperature of its outlet is 45 ℃, and spray-dired other condition reaches gained particulate evaluation result is shown in following table 2.The particulate water content is measured with Karl Fischer wet bulb thermometer (model MKA-3P is made by capital of a country electronic industry Co., Ltd.).The model that the humidity of dry air is made with Japanese Canomax Co., Ltd. is that 6802 instrument is measured.
Embodiment 5
Except the absolute humidity of regulating dry air is 0.012 kg/kg, all prepare particle according to the method identical with embodiment 4, gained particulate evaluation result is shown in following table 2.
Comparing embodiment 3
Except the absolute humidity of regulating dry air is 0.022 kg/kg, prepare particle according to the method identical with embodiment 4, gained particulate evaluation result is shown in down tabulates 2.
By the result of table 2 as can be seen, the particulate water content surpasses 1%.Can not test by the aggregate size of not disperseing in the prepared colloidal sol of particle, because when colloidal sol was scattered in the grinding test device, this colloidal sol can not generate level and smooth one deck.Because the water that is contained in the colloidal sol has been evaporated, when therefore making film, can not obtain a kind of normal film significantly when heating by this colloidal sol.
Comparing embodiment 4
Except the absolute humidity of regulating dry air is 0.006 kg/kg, prepare particle according to the method identical with embodiment 4.Particulate evaluation result to gained is shown in down in the tabulation 2.
Table 2
Relatively fullsized is more real for EXAMPLE Example
Drying conditions 45 is executed the amount (Nm that example 3 is executed the drying air temperature of the absolute humidity of example 4 dry airs (kg/kg) 0.01 0.012 0.022 0.006 ingress (℃) drying air temperature in 80 80 80 80 exits (℃) 45 45 45 45 dry airs
3/ hr) 880 880 880 880 the input aqueous dispersions, (kg/hr) 30 30 30 30 rotating disc revolutions, (rpm) 12,000 12,000 12,000 12000 particle characteristics water content, (%) 0.12 0.45 1.05 0.08 mean particle size, (μ m) 45 45 45 45 angles of repose, (°) performance of 33 32 32 33 colloidal sols that the form size of in colloidal sol, not disperseing aggregation, (μ m) 25 25 * 80 do not disperse the number 00 * * 50 of aggregation in film
Annotate: *: because colloidal sol does not generate smooth layer on the grinding test device, so can't measure.
*: do not generate normal film.
From the result of table 2 as can be seen, in colloidal sol, do not disperse the size of aggregate can control to, and be 0.008 to 0.012 kg/kg, can obtain not have the film that lumps by the absolute humidity of regulating dry air less than 50 microns.Compare with embodiment 4, generated the not discrete particles of showed increased in the colloidal sol of comparing embodiment 4.
Embodiment 6
Be respectively 70 ℃ and 40 ℃ except regulating the temperature of dry air, use the method identical to prepare particle with embodiment 4 at the entrance and exit place.Gained particulate evaluation result is shown in down tabulation 3.
Embodiment 7
Be respectively 90 ℃ and 45 ℃ except regulating the temperature of dry air, with preparing particle with embodiment 4 identical methods at the entrance and exit place.Gained particulate evaluation result is shown in down tabulation 3.
Comparing embodiment 5
Be respectively 110 ℃ and 55 ℃ except regulating the temperature of dry air, with preparing particle with all mutually methods of embodiment 4 at the entrance and exit place.Gained particulate evaluation result is shown in down tabulation 3.
Comparing embodiment 6
Be respectively 80 ℃ and 55 ℃ except regulating the temperature of dry air,, gained particulate evaluation result be shown in down tabulation 3 with preparing particle with embodiment 4 identical methods at the entrance and exit place.
Comparing embodiment 7
Be respectively 110 ℃ and 45 ℃ except regulating the temperature of dry air,, gained particulate evaluation result be shown in down tabulation 3 with preparing particle with embodiment 4 identical methods at the entrance and exit place.
Table 3
Relatively fullsized is more real than fullsized for EXAMPLE Example
67 execute example 5 executes example 6 and executes absolute 0.01 0.01 0.01 0.01 0.01 humidity of example 7 drying conditions dry airs, (kg/kg) the dry empty 70 90 100 80 110 temperature degree in ingress, (℃) the dry empty 40 45 55 55 45 temperature degree in exit, (℃) amount 1,280 850 940 1,500 510 of dry air, (Nm
3/ hr) aqueous dispersion 30 30 30 30 30 bodies (kg/hr) rotating disc revolution 12,000 12,000 12,000 12,000 12000 (rpm) particle characteristics water content (%) 0.22 0.21 0.20 0.20 0.21 average grain large 45 45 45 45 45 little (μ m) angle of repose of input (°) performance of 33 33 33 33 33 colloidal sols that form in colloidal sol not the 25 30 100 85 100 aggregations sizes (μ m) of disperseing in film, be not more than greater than greater than the gathering 01 100 100 100 body numbers that disperse
As can be seen from Table 3, the size of not disperseing aggregate in colloidal sol, can be controlled at below 50 μ, and be respectively 100 ℃ (or less than 100 ℃) and 50 ℃ (or below 50 ℃), can obtain not having basically the film of caking by regulating the temperature of dry air at the entrance and exit place.
Embodiment 8
Except the solid content of the employed vinyl chloride resin water dispersion of using for paste molding is 49%, per 100 parts of vinyl chloride resins contain 1 part of sodium lauryl sulphate, and to set up the rotating disk revolution be outside the 8000rpm, all prepare particle by the method identical with embodiment 4.Gained particulate evaluation result is shown in following table 4.
Comparing embodiment 8
Except the revolution of setting up rotating disk is the 22000rpm, all prepare particle by the method identical with embodiment 8.Gained particulate evaluation result is shown in following table 4.
Comparing embodiment 9
Except the revolution of setting up rotating disk is the 6000rpm, all prepare particle by the method identical with embodiment 8.Gained particulate evaluation result is shown in down tabulation 4.
Table 4
Relatively fullsized is more real for embodiment
8 execute the amount (Nm that example 8 is executed the drying air temperature of the absolute humidity of example 9 drying conditions dry airs (kg/kg) 0.01 0.01 0.01 ingress (℃) drying air temperature in 80 80 80 exits (℃) 45 45 45 dry airs
3/ hr) aqueous dispersion (kg/hr) 30 30 30 rotating disc revolution (rpm) 8,000 22,000 6000 particle characteristics water content (%), 0.22 0.20 0.73 mean particle sizes (μ m) 60 25 80 bodies of 880 880 880 inputs end the angle (°) number 00 10 of the aggregation that in film, do not disperse of the size 35 20 70 (μ m) of the aggregation that in colloidal sol, do not disperse of the performance of 35 40 32 colloidal sols that form
The result of the embodiment 8 that table 4 is listed shows that the particle that obtains according to the present invention has little slope of repose, thereby processed at an easy rate.
In the particle technical field, the slope of repose usually is used as the sign of processing complexity.Please note such fact, the slope of repose that promptly is used for the vinyl chloride resin of automatic feed system is not more than 35 °.In an embodiment, the resulting vinylchlorid particle that is used for paste molding as long as its slope of repose of having is 35 ° or less than this value, can think that then this vinylchlorid particle has satisfied particle characteristics.
Embodiment 9,10 and 12
Except the revolution of setting up its rotation is 10000rpm (embodiment 9), 14000rpm (embodiment 10), or outside the 22000rpm (embodiment 12) all prepares particle by the method identical with embodiment 1, and gained particulate evaluation result is shown in following table 5.
Expression embodiment 9 with 10 separately the electron photomicrograph of the structure of gained grain husk grain show they respectively with shown identical of Fig. 1 (magnification be approximately 900 *) and Fig. 2 (magnification be approximately 130 *).
Embodiment 11
Except the revolution of setting up rotating disk is 7000rpm and regulates dry air the temperature at its entrance and exit place is respectively 90 ℃ and 48 ℃, all prepare particle by the method identical with embodiment 9.Gained particulate evaluation result is shown in following table 5.Can see that prepared particulate mean particle size increases, and the size of not disperseing aggregate in colloidal sol prepared therefrom does not increase significantly.
Comparing embodiment 10
Except regulate the temperature of dry air at the entrance and exit place be respectively 120 ℃ with 55 ℃ with preparing particle with embodiment 9 identical methods.Gained particulate evaluation result is shown in following table 5.Though prepared particulate slope of repose is identical with embodiment 9, contain bigger not scatter-gather body in the prepared colloidal sol of particle thus.
Comparing embodiment 11
With embodiment 11 resulting granules, sieve (mesh size: 105 μ m) to obtain bigger particle with 145 purpose screen clothes.Shown in following table 5, contain not scatter-gather body greater than embodiment 11 by the prepared colloidal sol of this particle.
Table 5
The drying air temperature of revolution (rpm) 10,000 14,000 7000 porch of EXAMPLE Example embodiment drying condition 9 10 11 rotating discs (℃) drying air temperature in 80 80 90 exits (℃) 45 45 48 particle characteristics water content (%), 0.12 0.45 0.15 mean particle sizes (μ m), 45 36 80 angles of repose (°) size 000 (μ m) of the aggregation that in film, do not disperse of the size 50 45 55 (μ m) of the aggregation that in colloidal sol, do not disperse of the 33 34 32 particle size distribution performance of not observing the colloidal sol of formation greater than particle ratio (%) 5.2 9.1 0.5 one-tenth powder of 20 μ m greater than the particle ratio (%) 8.2 3.3 35.0 of 100 μ m
Table 5 (continuing)
It is more real than fullsized to implement fullsized
12 execute example 10 execute the drying air temperature of the revolution of example 11 drying condition rotating discs (rpm) 22,000 10000-porch (℃) drying air temperature in 80 120-exit (℃) 45 55-particle characteristics water content (%), 0.15 0.15 0.18 mean particle size (μ m), 30 45-angle of repose (°) size 0 40 10 (μ m) of the aggregation that in film, do not disperse of the size 40 100 70 (μ m) of the aggregation that in colloidal sol, do not disperse of the 38 33 32 particle size distribution performance of not observing the colloidal sol of formation greater than particle ratio (%) 40 4.0 0 one-tenth powder of 20 μ m greater than the particle ratio (%) 1.5 9.0 80 of 100 μ m
Comparing embodiment 12
With solid content is 47%, be used for the spray-dryer of the vinyl chloride resin water dispersion of paste molding with rotating disk type, temperature in its ingress is 80 ℃, the temperature in exit is under 45 ℃ the situation, carry out drying and granulating, this spray-dired inwall carried out precision work (tower diameter: 2.75 meters according to JISG4305 No 2B; Tower length: cylinder part is divided into 3.0 meters, and cone partly is 2.2 meters; The angle of cone part: 60 °).When carrying out drying, make the air hammer that is fixed on the moisture eliminator body be in swing state, its frequency be per 20 seconds once.
Finish after the drying, the inside of moisture eliminator is observed found to have in a large number from particle adhesion on the inwall in the cone part.Part to adhered particles is observed with microscope, has found to comprise some particulate blocks in the place, many places.This class block is also with 2% or be present in the collected particle greater than the ratio of this value.The performance of the colloidal sol of other drying conditions and gained particulate particle characteristics and formation all is shown in the following table 6.
Embodiment 13
Used 240 except using its cone part
#Polishing wheel carried out all preparing particle by the same procedure with comparing embodiment 12 outside the accurately machined spray-dryer.
After finishing drying, on the inwall of tapered segment, do not observe particulate basically and adhere to, the results are shown in the following table 6 of its evaluation.
Table 6
Embodiment relatively implements
Amount (the Nm of the drying air temperature of absolute humidity (kg/kg) 0.01 0.01 ingress of 13 examples, 12 drying conditions dry airs (℃) drying air temperature in 80 80 exits (℃) 45 45 dry airs
3/ hr) input of 880 880 aqueous dispersions (kg/hr) 30 30 particle properties water content (%), 0.22 0.22 mean particle sizes (μ m) 45 45 angles of repose (°) number 0 10 of size (μ m) 25 70 aggregations that in film, do not disperse of the aggregation that in colloidal sol, do not disperse of the performance of 33 32 colloidal sols that form
From the result of table 6 as can be seen, in embodiment 13, size of not disperseing aggregate in the colloidal sol and the number that does not disperse aggregate in film all compare little than embodiment 12.
Embodiment 14～16 and comparing embodiment 13,14
Except will having according to JISG4305, No.2D (not finishing polish), No.2B (not finishing polish) is with 100
#Polishing wheel is with 150
#Polishing wheel or with 240
#Outside the test parts that polishing wheel carried out the surface of finishing polish was connected on the inwall of spray-dryer cone part, all the same terms according to embodiment 13 carried out drying test.After the drying, these test parts are taken out and observed.Find that consequently a large amount of particle adhesions was not carrying out on the test parts of polished finish through 100#, #150 and #240 polishing wheel and observe particle adhesion on the test parts of No.2D and No.2B.
From these results as can be seen, by precision work is carried out on the surface of cone part, make it have 100
#The polishing wheel or the slickness of fine polishing wheel more just can prevent particle adhesion on the cone part, prepare the grain husk of the performance with better formation colloidal sol thus.
Embodiment 17
(this water dispersion solid content is 47% with 1 kilogram the vinyl chloride resin water dispersion that is used for paste molding, per 100 parts of vinyl chloride resins contain 1 fen Sodium dodecylbenzene sulfonate) put into 1 liter of stainless steel beaker, and be to stir (average retention time: 120 seconds) under 200 watts the situation at power with a high speed rotating homogenizer (producing by Silverson).This aqueous dispersions is sent into (tower diameter: 2.75 meters in the spray-dryer that the rotating disk spraying gun is housed; Tower height: 3.0 meters of barrel portions, 2.2 meters of cone parts; The angle of cone: 60 °), and simultaneously stir.To pass through a moisture extractor so that the absolute humidity of air is 0.01 kg/kg, again it be heated to 80 ℃ air then, be delivered in the spray-dryer.The revolution of rotating disk is 14000rpm.Spray-dired other conditions reach gained particulate evaluation result are shown in the following table 7.Particulate water content model is measured for the Karl Fischer aquametry apparatus (manufacturing of capital of a country electronic industry Co., Ltd.) of " MKA-3P ".
Embodiment 18
Except under 150 watts power, disperse phase being stirred (residue residence time: 120 seconds), use the method identical to prepare particle with embodiment 7 with ultrasonic homogenizer " US-300 " (doing manufacturing) by the smart mechanism of Japan.That estimates the results are shown in table 7.
Comparing embodiment 15
Except under condition of stirring not, being delivered to the atomizer, use the method identical to prepare particle with embodiment 17 with the used same vinylchlorid aqueous dispersions of embodiment 17.That estimates the results are shown in table 7.
Table 7
EXAMPLE Example is more real
17 18 execute the amount (Nm of example 15 drying conditions absolute humidity (kg/kg) 0.01 0.01 0.01 drying air temperature in the ingress (℃) 80 80 80 drying air temperatures in the exit (℃) 45 45 45 dry airs
3/ hr) aqueous dispersion (kg/hr) 30 30 30 particle properties water content (%), 0.22 0.22 0.22 mean particle sizes (μ m) 45 45 45 angles of repose of 880 880 880 inputs (°) size 20 20 70 (μ m) of the aggregation that in colloidal sol, do not disperse of the performance of 33 32 32 colloidal sols that form but the number 23 20 of the aggregation that the size 30 30 90 (μ m) of the aggregation that number 00 10 keeping qualities of the aggregation that do not disperse in film do not disperse in colloidal sol is not disperseed in film
Annotate: after preservation, the particulate water content, mean particle size and slope of repose in fact do not change.
By the result of table 7 as can be seen, with the prepared colloidal sol of the particle of comparing embodiment 15, contain the big aggregate that do not disperse, contain a large amount of aggregates that do not disperse by this colloidal sol prepared film, in addition, as preservation one segment length after the time, the particle of comparing embodiment 15 demonstrates the performance that generates colloidal sol the visible trend that is worsened.
Although the present invention has been had been described in detail and spoken of special embodiment, the present technique art skilled person will understand, can the present invention do not broken away from the various changes and improvements of spirit of the present invention and scope.
Claims (5)
1. method for preparing the vinyl chloride resin granules that can be used for making thickener, this method comprises in the presence of tensio-active agent, mainly the monomer mixture of being made up of vinylchlorid carries out drying and granulating with dry air through the vinyl chloride resin water dispersion of suspension polymerization or letex polymerization acquisition in spray-dryer, the absolute humidity of employed dry air is 0.008 to 0.012 kg/kg, and the temperature in the ingress is not higher than 100 ℃, temperature in the exit is not higher than 50 ℃, to obtain moisture content is 0.1～0.5% weight, and mean particle size is the particle of 30～100 μ m.
2. when the process of claim 1 wherein that this water dispersion is admitted to spray-dryer, be that 100 watts stirring intensity is stirred with the per kilogram aqueous dispersions.
3. according to the method for claim 2, wherein this stirring is to carry out in a high speed rotating homogenizer.
4. according to the method for claim 2, wherein this stirring is to carry out in a ultrasonic homogenizer.
5. according to the process of claim 1 wherein that the surface flatness of this spray-dryer is the slickness of 100# polishing wheel or the slickness of fine polishing more.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP288607/88 | 1988-11-14 | ||
| JP288605/88 | 1988-11-14 | ||
| JP63288608A JPH0672169B2 (en) | 1988-11-14 | 1988-11-14 | Spherical vinyl chloride resin granules |
| JP288604/88 | 1988-11-14 | ||
| JP28860488A JPH02134215A (en) | 1988-11-14 | 1988-11-14 | Manufacture of vinyl chloride resin for use in processing of granular paste |
| JP288606/88 | 1988-11-14 | ||
| JP288608/88 | 1988-11-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1043946A CN1043946A (en) | 1990-07-18 |
| CN1032012C true CN1032012C (en) | 1996-06-12 |
Family
ID=26557244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109262 Expired - Lifetime CN1032012C (en) | 1988-11-14 | 1989-11-14 | Spherical vinyl chloride resin granules and process for producing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1032012C (en) |
-
1989
- 1989-11-14 CN CN 89109262 patent/CN1032012C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1043946A (en) | 1990-07-18 |
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Granted publication date: 19960612 |