CN1863847A - Pigment and filler and a method of manufacturing it - Google Patents
Pigment and filler and a method of manufacturing it Download PDFInfo
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- CN1863847A CN1863847A CN 200480028790 CN200480028790A CN1863847A CN 1863847 A CN1863847 A CN 1863847A CN 200480028790 CN200480028790 CN 200480028790 CN 200480028790 A CN200480028790 A CN 200480028790A CN 1863847 A CN1863847 A CN 1863847A
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Abstract
The present invention relates to a light, biodegradable, organic pigment and filler, and a method of manufacturing it. According to the present invention, a solution comprising a starch derivative is first prepared by dissolving the starch derivative into a suitable solvent, and, after that, the solution is brought into contact with a non-solvent to precipitate the starch derivative from the solvent, and, as a result, a dispersion is obtained, one which comprises a precipitate consisting of starch derivative and a liquid phase formed of the solvent and the non-solvent, after which the solvent is removed from the liquid phase and the precipitate is separated from the non-solvent and recovered. The present invention can be used to manufacture both a product comprising 100-300 nm spherical particles, which is suitable for use as a pigment, and a coral-like, porous product which is particularly suitable as a filler.
Description
The present invention relates to the method that a kind of preamble according to claim 1 prepares starch base pigment or filler.
The invention still further relates to respectively pigment or filler according to the preamble of claim 22 and 25.
Used now printing paper quality and cardboard through applying comprise suitable content with filler or the inorganic mineral that exists with the coating pigment form.This causes problem during in the burning of fiber recovery, paper with at composting.Mineral have equally significantly increased the weight of paper product, but this is very tangible when for example producing printed apcksging material.
Synthetic organic pigment is known equally.Because the ability of their scatter visible light has the good optical performance usually.This ability or come from little particle size (preferred visible wavelength 1/2) perhaps comes from the fact that in prepared technology particulate forms hollow.Usually, can stipulate to be suitable as coating pigment, and the particle between 1000-5000nm is suitable as filler less than the particle of 1000nm.The optical property of pigment is not only relevant with particle size, and is also relevant with particle shape.Ideal form is that the wave optics particle of spheroid is with efficient way scattered light and therefore give paper high brightness and opacity through applying.Yet the shortcoming of known synthetic dyestuff is that they are not suitable for independent coating pigment as paper, but they mix use usually with mineral color.
The objective of the invention is to produce biodegradable pigment dyestuff of lightweight and filler, but it can be used for for example producing white printing paper goods.
In patent documentation, known using with itself or through the form of chemical modification acts on the filler of paper or the small size starch particle of coating.Aspect the optical property of improving them at inside formation cavity, making an effort.Yet even starch is subjected to natural obtainable minimum starch particle also greater than the restriction of 1 micron the fact as the purposes of coating pigment, therefore, they can not be as the coating pigment of the printing paper that requires smooth quality smooth finish.
The preparation of starch granules is documented in the following patent specification:
Proposed a kind of method among the US Patent specification No.6582509, wherein, still kept particle structure to prepare pigment dyestuff simultaneously by starch particle is expanded with volume (2-4 originally doubly) and the plasticity-that increases them.Expansion is carried out in water being lower than under the gelation temperature.Volume and shape stability by crosslinked increase particle.Particle surface also can be made into hydrophobic.In particle, form bubble or cavity with light scattering property.By vaporize water or solvent, perhaps by discharging the gas that is absorbed, perhaps by using solvent to replace the water generates bubble that is absorbed.Be of a size of 0.1-5 μ m at particle cavity through expansion and stabilization.
Known pigment has the particle shape identical with starch, and this can not give product good light scattering ability.
EP application open source literature No.1254939 has put down in writing a kind of method that is used to produce based on the nanoparticle of biopolymer, its by extrude under the condition that exists at the cross-linking chemistry material plastifying biopolymer for example starch carry out.Described glue prepares by being extruded by starch, glycerine, glyoxal reaction under the condition that exists at water, and obtains the dispersion in water.This nano particle is of a size of less than 1000nm (50-250), and the amylopectin percentage composition height in the preferred starch.This latex is used as glue in producing corrugated cardboard.
Application open source literature WO 00/69916 has proposed the nano particle of biopolymer.The average particle size particle size of these nanoparticles is less than 400nm.These biopolymers are starch, starch derivative or the polymer adulterant that contains at least 50% starch.By use dialdehyde or polyaldehyde for example oxalic dialdehyde come to realize crosslinked.In this treating processes, there are softening agent such as glycerine.According to embodiment, this dispersion is by polishing particles and sieve out to be blended in the water greater than the particle of 150 μ m and with the gained powder and prepare.Formed the light brown dispersion of homogeneous transparent after stage in viscous gel.The shortcoming of following described already known processes is that this dispersion forms transparent film when drying.Therefore, known nano particle is not suitable as coating pigment or the filler that is used for paper or cardboard, and their purposes are not in this respect mentioned in described publication yet.
US patent specification No.6562459 has proposed the preparation of all or part of circular particulate that is made of at least a water-fast polysaccharide.This polysaccharide is dissolved in also precipitation, cooling optionally in the organic solvent, thus separating particles.These particulates are used as filler in polymkeric substance, in material separation and the diagnostic test.Wherein do not mention the pigment applications or the application that are used for paper.
The starch of rich amylose starch or line style poly-(1,4-α-D-dextran) are used for this preparation.Wherein, glycogen and amylopectin by hybridization in the straight chain poly-dextrose.In a kind of known solution, utilized the water insoluble character of the starch of amylose starch/rich amylose starch, thereby must only use amylose starch.The solvent for use methyl-sulphoxide is toxic chemical substance and is ebullient material at high temperature that it is difficult to remove from product, this has limited the operability of product.
FI patent specification No.98943 has proposed a kind of method of improving paper or cardboard character, is specifically related to wherein come with the mixture that comprises tackiness agent and pigment component the method for handling of paper or paperboard surface.Part pigment is formed by the moisture phase-polymerization product of polymerization single polymerization monomer and treated starch.In the method, vinyl monomer polymerization under the condition that starch exists.In reaction, monomeric compound is grafted to starch this product that neutralizes and is used for part and is substituted in the mineral color of coating slurry.
Graft process is that complicated and gained pigment are the mixtures of crude substance and synthetic polymer.This has limited the recovery and the biological degradation of this pigment.
Target of the present invention be to eliminate in known technology with shortcoming and produce brand-new pigment or filler product based on starch.
The present invention is based on following design: the pigment of starch base and filler can prepare by two-stage process, wherein starch-based material are dissolved in organic solvent earlier or replacedly in the uniform mixture of organic solvent and non-solvent (for example water).By dilute this solvent with non-solvent starch ingredients is precipitated from this mixture then.
Be surprisingly found out that, can prepare the almost spheroidal particle of ideal form by starch by aforesaid method.In addition, find that also a characteristic properties of these starch is its size, it can change in being generally the tolerance value of 90-1000nm.Yet described particle size distribution can be very narrow.By observing the specific refractory power of starch ester, can calculate in theory in the particle size range of 100-300nm, the optical property of spherical starch ester particle (particles) is better than the optical property of normally used for example PCC pigment.
According to the present invention, starch ester, for example the starch acetate mode that can produce the lightweight nano-porous materials is precipitated out from organic solvent or water.In this article, nano-porous materials is meant that the light scattering property of material is derived from its microtexture particulate less than 500nm.The initial particle size of nano-porous materials, particle size can change in the wide limit value of 1-100 micron.If desired, it also can be used as coating pigment or filler.
More specifically, the method according to this invention is characterised in that in the characteristic according to claim 1 listed.
And then, be characterised in that according to pigment of the present invention and stuffing product the characteristic in claim 22 and 25 is listed respectively.
The present invention can obtain significant advantage.Therefore, but lightweight of the present invention and biodegradable pigment dyestuff and filler can for example be used to produce white printing paper goods.Although when the substitution value of esterified group was 0.5-3, described starch ester was water-fast, they still have polarization characteristic, thereby can they be adhered to from the teeth outwards by strong hydrogen bond.As a result, when filler content increased, the intensity of paper did not have weakened, and this is common when using mineral dye.With regard to filler retention, compare nanoporous starch ester particulate with synthetic dyestuff with mineral color attractive advantage is provided: can increase the size of porous particle in principle, and can the technology of paper smooth surfaceization be thrown into question being used to.
Pure starch ester is the biodegradable polymers of color white (white coloured) with elevated oxygen level, and its glass transition point is+159～+ 162 ℃.Therefore, the same with inorganic mineral, they can be ground to required particle size.Beat all is that we find not need to use self-contained process to come the bleaching starch material.The ISO brightness that is pressed high-quality starch acetate in blocks this means that for greater than 94 it and most of industrial pigment have comparability.Pigment according to the present invention is characterised in that the following fact: even (be lower than 5g/m at little addition
2) starch pigment in the brightness of paper product and opacity, produced remarkable improvement.
Starch ester disperses from solution, need not to use additive simultaneously and according to the reactor engineering in water, and starch ester forms spherical particle or nanoporous particulate.The high molecular desirable properties of starch is achieved by the molar mass of control starch ester according to the present invention.The raw-material production technique of starch makes that for example ionic group can be attached on the glucose polymer, and described ionic group influences the surface property of particulate.The initial particle size of nanoporous micro chip can be set to required degree by apply mechanical energy or ultrasonic energy to suspension.
The difference of the present invention and the above-mentioned open source literature of quoting do not need to be plastification material when preparation goods of the present invention.Can use various starch as starting material; Do not need in the method as in the known technology it being defined as for example amylose starch.All starch can be esterified and be used for the preparation of pigment.By this way, obtain required degree of esterification, even also can obtain high substitution value.Can use in the present invention because its lower boiling (being usually less than 100 ℃) and the solvent can be from pigment easily removed.
Hereinafter, with reference to how implementing embodiments of the invention the present invention is investigated in further detail and illustrate.
Fig. 1 has shown the electron micrograph (SEM photo) according to the cardboard that applies through pigment of embodiment 1 preparation;
Fig. 2 has shown the SEM photo for preparing and be applied to subsequently the pigment on the paperboard surface according to embodiment 2 similarly;
Fig. 3 is to use the SEM photo of the goods of thermal process preparation;
Fig. 4 shows the particle size distribution of using the pigment of acetone-ethanol preparation at pilot-scale;
Fig. 5 shows according to the particle size distribution of the pigment of embodiment 6 (three parallel testings);
Fig. 6 shows the SEM photo according to the pigment of embodiment 6 in paperboard surface-should be understood that minimum particulate (particles) is the present latex particulate that is used as tackiness agent in coating;
Fig. 7 is the SEM photo by the coralliform pigment of water precipitation method preparation;
Fig. 8 is the SEM photo by the coralliform pigment of solvent deposition method preparation;
Fig. 9 shows and uses different particle size measuring results of adding the pigment of speed preparation, wherein tests 1=AT2-105-1, test 2=AT2-105-2, and test 3=AT2-105-3;
Figure 10 shows the particle size distribution according to the pigment of embodiment 10, the pigment among the wherein superincumbent embodiment of there is shown 1 and below there is shown pigment among the embodiment 2;
Figure 11 shows the influence of mixing rate to the particle size distribution of filler pigments (embodiment 11);
Figure 12 shows the particle size distribution that has the pigment for preparing under the different starting material percentage compositions in embodiment 12;
Figure 13 shows the brightness value of the pigment that records from coating, and wherein reduced pigment is PCC;
Figure 14 correspondingly shows the opacity value of the pigment that records from the paper through applying, and wherein reduced pigment is PCC; With
Figure 15 a and 15b show by the quality and the funtcional relationship that be coated with slurry body applied amount of surface coating technology with the paper of pigment coloring.
The present invention has produced the starch base pigment and the filler of new kind, and their particularly suitables are in paper and paper board product.Yet they also can use elsewhere, for example in coating, plastics and rubber with common replacement mineral and correspondingly polymer pigment and filler.Described product also is suitable for washing composition and makeup.
Described pigment and filler prepare by following method: starch-based component is dissolved in the solvent, therefrom precipitates this component by this solution is contacted with precipitation agent (it is also referred to as " non-solvent " below).For example, reclaim subsequently with throw out being separated from precipitation agent also by evaporating from the dispersion that precipitate phase produced, removing described solvent.
Be " functionalized " starch derivative as raw-material starch-based component in the present invention.
In other words, this is the product that is produced by starch by chemical reaction, and its dehydrated glucose unit to small part has the group that changes hydroxyl-functional.Usually, described starch derivative is the starch ester by native starch, hydrolyzed starch, Sumstar 190, bridging starch (bridged starch) or jelling starch preparation.
Used starch and then can be that 0-100% and amylopectin percentage composition are the native starch of 100-0% based on any its amylose starch percentage composition.Therefore, described starch can come from barley, potato, wheat, oat, pea, corn, cassava, sago, rice or similar tuberous plant or cereal crop.
Have been found that and use derive free starch and one or more aliphatic C
2-24The starch-based component of the ester of both formation of carboxylic acid is suitable.In this case, the carboxyl acid component of this ester can be derived from lower alkanols alkanoic acid (alcanoic acid), for example acetate, propionic acid or butyric acid or their mixture.According to preferred embodiment, this starch ingredients is an esterification starch, most preferably starch acetate, its substitution value are 0.5-3, preferred 1.5-3 and optimum be 2-3.Select the substitution value of starch ester to make this product be insoluble to used in the present invention precipitation agent basically.
If the glass transition point of starch ester is enough high for required application, carboxyl acid component also can be from naturally occurring saturated or unsaturated fatty acids in principle.Typical example is palmitinic acid, stearic acid, oleic acid, linolic acid and their mixture.Ester can also be made of long-chain and short chain carboxy acid's component.The mixed ester of acetic ester and stearate is typical example.According to known method, not only acid but also corresponding acid anhydrides and acyl chlorides and other corresponding reactive acid derivatives also can be used to form ester.
The preparation example of the fatty acid ester of starch is as carrying out according to the record at commercial press's thing: Wolff, I.A., Olds, D.W. and Hilbert, G.E., The acylation of Corn Starch, Amylose and Amylopectin, J.Amer.Chem.Soc.73 (1952) 346-349 or Gros, A.T. and Feuge, R.O., Properties of Fatty Acid Esters of Amylose, J.Amer.Oil Chemists ' Soc 39 (1962) 19-24.
The lower member ester derivative for example starch acetate can by make starch and acid anhydrides for example diacetyl oxide (corresponding to ester group) in the presence of catalyzer, react and prepare.For example, 50% sodium hydroxide solution is used as catalyzer.In addition, other knownly also are suitable for preparing starch acetate in the method for preparing acetic ester described in the technical literature.By the consumption that changes diacetyl oxide, consumption and the reaction times that is used as the alkali of catalyzer, can prepare starch acetate with different degree of substitution.That describes in FI patent 107386 wherein under stress carries out the good embodiment that esterification method is an appropriate preparation method.
The character of the starch ester preferably product of the transglycosylation by forming them changes.
According to another embodiment preferred, starch ingredients is the ester of hydroxy alkylated starch.In this case, hydroxypropyl starch ester more preferably, its molar substitution mostly is 2 most, preferably mostly is most 1 and 0.1-0.8 more preferably, and substitution value minimum be 1, only be minimum be 2, preferred 2.5-3.
The high molecular preferred selection of starch in the present invention is water-fast starch, and this starch has at least+and 60 ℃ and preferred 150-170 ℃ or higher, but be usually less than 350 ℃ second-order transition temperature, perhaps under these temperature, can not decompose the starch polymer of (break down).Selecting one of glass transition point and corresponding durothermic basic demand is preparation and the service temperature of the second-order transition temperature (perhaps decomposition temperature) of goods at pigment or filler, perhaps in the preparation process of end article not by-not only temporarily-surpass, otherwise this pigment and filler will be lost its favourable scattering of light optical property.
Polymer chain comprises at least 10 glucose units and at least one acetyl group of each glucose unit.According to preferred implementation method, described polymer chain comprises 100-150 glucose unit and each glucose unit 2-3 acetyl group.According to another embodiment, it is spherical particle from solution separating that the disintegration of the basic structure of starch makes it spontaneous.The high molecular molecular weight distribution of starch can broad.According to preferred embodiment, the high molecular polydispersity index of starch is 1.5-2.0.
In fs according to the inventive method, with the starch macromolecule dissolution in the mixture of solvent, particularly one or more organic solvents or they and water, the result has obtained solution, and its starch polymer concentration is at least 1 weight %, preferably be about 40 weight % and be generally about 10-30 weight % to the maximum.
Preferably, described starch polymer is dissolved in the selected solvent fully, but the present invention also comprises following application: wherein a part of starting material (starch derivative) are dissolved in the solvent and part remains with insoluble form.In this case; in the precipitate phase after dissolution phase (vide infra); dissolved partly is deposited upon in the insoluble part, has produced the combination product that comprises the material that contains the initiating particle structure and comprise the deposited material of spheroidal particle or poromerics.Insolublely can be about 10: 90～90: 10, be preferably about 20: 80～80: 20, be most suitably about 30: 70～70: 30 with the raw-material relative percentage composition of dissolved (as weight quota).
According to embodiment preferred, the viscosity of solution (perhaps solution part) is the viscosity near water, perhaps the most about 1.5-5, and maximum is that 4-5 is doubly high usually.
For the plain mode that satisfies that above-mentioned solubleness and viscosity requires is with for example with enzyme or acid oxidase, hydrolytic scission starch or by transglycosylation, etherificate or ultrasonic to its modification.
Wherein wishing to dissolve in the embodiment preferred of all raw material according to of the present invention, having used can be with the desirable suitable solvent of any ratio and water blending.Preferably, this solvent is volatile and therefore is easy to distillatory.The solvent that " ideal solvent " of starch is meant wherein to be considered is as the agent of plasticating (Plasticator) of starch.In other words, they can mix with the starch polymer by all ratios.
The solvent of recommending is straight chain, branching and cyclic ketone, for example acetone and tetrahydrofuran (THF) and paraffinic acid such as acetate.Possible solvent is monohydroxy-alcohol, dibasic alcohol and polyvalent alcohol, for example the organic solvent of ethylene glycol, diethyl two pure and mild ethoxyethyl group two pure and mild other types, for example ethyl formate and methyl-formiate, pyrrolidone and methyl-sulphoxide.
According to the present invention, should avoid excessive solvent.Usually, use the just consoluet solution of sufficient to guarantee starting material, perhaps excessive at most a little, for example maximum 20-30 weight %'s is excessive, just is enough to prepare starch derivative solution.
Can use another can not be used as the solvent of solvent separately with desirable starch solvent.Therefore, the suitable solvent that can use with acetone or tetrahydrofuran (THF) is for example methyl alcohol, ethanol, propyl alcohol and Virahol.
In principle, also can consider other solvent system.Mark S=starch and give symbol: A (starch solvent) below the compatible each other solvent orange 2 A BC, B or C are that starch can not be dissolved in solvent wherein.The gained function combinations is AS+B, AS+C, ABS+B, ABS+C and ACS+B.(for example acetone/starch+ethanol or acetone/starch+Virahol).
As mentioned above, the present invention can be used to prepare two kinds of pigment and filler reagent, and they can be goods or the nanoporous goods that comprise spherical particle, and it is also referred to as " coralloid " hereinafter.They all are to be prepared by starch derivative solution is contacted with precipitation agent (non-solvent).In this case, non-solvent is the material that does not meet the definition of top starch derivative solvent, and this is meant when have this solution of enough volumes in liquid system the time, the reagent of the starch derivative in can complete as far as possible precipitation solution.Usually, in solution at least 70 weight %, preferred at least 80 weight %, more preferably the starch derivative of 90 weight % even at least 95 weight % is precipitated.Depend on solvent or solvent solution, the 0.1-100 that the amount of non-solvent is generally the amount of solvent or solvent solution doubly (calculates) by weight, and preferably about 0.5-10 doubly is most suitably about 0.7-5 doubly.
Conventional precipitation agent is water or corresponding polar liquid, for example C
1-6Alkanol or non-polar hydrocarbon be C for example
4-20Alkane, preferred C
5-10Alkane, the perhaps mixture of alkane.
When above-mentioned starch solution water or the dilution of corresponding non-solvent, particle size (average particle size particle size) is 90-1000nm, preferably less than about 500nm, be more preferably less than about 400nm, particularly the spherical particle less than 350nm spontaneously forms.Described dilution can promptly and tempestuously be carried out.It also can carry out lentamente, is mixed for two kinds of liquid in this case and mixes mutually, with the frictional belt of for example having avoided by the different generations of fluid density.
According to embodiment preferred, the dilution of starch solution percentage composition of water from solution system reaches its peaked point to begin.Here, maximum value is meant and surpasses this point that the starch polymer just is dissolved in the solvent systems no longer fully.Nature, this point depends on used polymer.
The preparation of particle dispersion is not the auxiliary dispersants that necessarily requires to use independently.Yet described auxiliary may be useful to the storage stability of this dispersion and further possibly the processing.Further processing can be for example to wash, be dried to powder or preparation is coated with slurry body.
In the preparation of spherical pigment, depend on mixing condition, temperature and the concentration of starch solution, the interpolation speed of water is generally 50-4000ml/s, preferred 80-450ml/s, most preferably 100-250ml/s.In coralliform pigment and the preparation that is used for filler material level pigment, starch solution is added to the water with remarkable lower interpolation speed: 0.05-90ml/s, preferably 0.1-20ml/s and most preferably 0.3-3ml/s.
Behind precipitate phase, organic solvent (multiple organic solvent) is removed from dispersion.
It is deleterious that described solvent precipitates for further processing, and the solvent residues of pigment or filler may make particle plasticizing, and causes the particulate optical property to reduce.Describe in more detail in these features comparative examples below.Usually, target is the amount of solvent residues is reduced to the degree of the detectability that is lower than used NMR technology.As a result, after removing solvent from solution mutually in the isolating precipitation, not existing can detected organic solvent residual volume by 300MHz NMR equipment.
According to embodiment preferred, the pigment purity of measuring by the NMR technology at least 98% to have acetyl substitution value (DS) be 2 and demonstrate dissolvent residual concentration and be lower than 0.5% starch polymer.
When forming particle or form after the particle, the homogeneity that mechanical energy that solution is applied or ultrasonic energy can be used for influencing particle size distribution.For example this means that particulate bunch is decomposed.Can make coating of particles change elliposoidal into by using the rotation of intensive laminar flow by sphere.
Described particle use for example filtration of known method itself, micro-filtration, decantation or centrifugal method separate.
Except with the above-mentioned single phase precipitation forms, described precipitation also can be carried out in two stages, this means after using first precipitation agent to carry out post precipitation and possible precipitate and separate, be dispersed in particulate in this liquid and separate therefrom by salt solution that (prerequisite is, for example, water is as non-solvent, and added salt is soluble in water) or separate from liquid phase in some other mode.As a result, as described in the following examples, obtained very little spheroidal particle.For saltouing, can use sodium sulfate etc. for example can be easy to be dissolved in the suitable inorganic salt of liquid phase.The addition of salt is generally about 0.1-20 weight % of solution, preferably about 1-10 weight %.
Above-mentioned solution is particularly suitable for starch-based material wherein and is dissolved in situation in the uniform mixture of organic solvent and water.(about 15-25 ℃) obtained the particle dispersion of milk shape when of this sort solution adds more water when for example at room temperature.By utilizing centrifugation that less component is separated with larger particles, obtained to have the particle of narrow granules of pigments distribution (the about 200nm of average out to).
Utilize two stage precipitation methods, produced two parts thus, promptly the spherical particle size thicker part that is generally 300-1000nm divide and spherical particle size less than the carefully part of 300nm.
If being used for sedimentary non-solvent is water, the starting point for preparing above-mentioned other materials (being micropore starch pigment) can be with above-mentioned identical.But operation is opposite: the solution that contains the dissolved starch derivative is added in the non-solvent.
According to embodiment preferred, 0.1: 10, preferred about 1: 3 ratio in water, to mix (combination) acetone: water/starch solution, it obtains particle and concentrates on greater than 1 micron, and common 5-30 micron is in for example about 12.3 microns original dimension scopes.Usually, relatively lentamente organic phase is joined aqueous phase and help forming such very porous coralliform pigment structure.
Also can apply ultrasonic energy to this system.This can make initial particle size reach 1 micron of average out to.
In a kind of alternative solution, produce coralloid structure by system with an organic solvent.At the starting point place, according to dissolving starch ingredients mentioned above and never dissolve in the solvent of starch and precipitate.Mix and guaranteed solvent fusion each other.Mixing can be the quick laminar flow rotation of implementing by injection, perhaps by the dropwise slow mixing of charging.The porousness of the described solution influenced starch that produces, and the result has variation to a certain degree, this depends on that whether precipitation solvent is for example sherwood oil, normal hexane or technical grade LIAV type hydrocarbon solution.
Aforesaid method carries out under room temperature (about 15-25 ℃) usually.But it also can be at higher temperature still is lower than under the temperature of boiling point of solvent and non-solvent and operates.Be the example of thermal process below.Can confirm that thus this temperature can be about 30-80 ℃, this means and to keep more low temperature and raise at precipitate phase subsequently in dissolution phase.It also is possible putting upside down working order at this.
Method of the present invention can possess the starch base pigment and the filler product of following character in order to generation:
1. spheroidal particle, its size are generally about 100-500 nanometer and its ISO brightness greater than 80 and corresponding
2. micrometer/nanometer porous particle, its size is for about 1-100 micron and comprise (being generally sphere) hole, and its mean sizes is about 100-500 nanometer.
The ISO brightness of first kind of goods can be up to 92-96, and the brightness of second kind of goods most suitably is at least 82 also at least up to 80, and preferably at least 84.
The particle size distribution of spheroidal particle is rather narrow usually.At least 50 weight %, preferred at least 70 weight %, the particularly particle of at least 80 weight % are included in the described scope (100-500nm).
Spheroidal particle is particularly useful as pigment, and coralloid particle is as filler.Application Areas is above mentioned, i.e. paper and cardboard, coating, plastics, rubber, makeup, hygienic articles and washing composition and other chemical preparationss.
Use the coating pigment of acetone method preparation based on starch acetate
Under mixed uniformly condition, starch acetate (6g, ISO brightness 68.7) is dissolved in the acetone (200ml).After starch acetate is dissolved fully, in 5 minutes, 120ml water is added in this solution, be precipitated out from solution to avoid starch acetate.Subsequently, water is with the volume of this solution dilution to 600ml.Water very rapidly added in about 6 second time, and while this mixture of intense mixing.Formed white emulsion after the interpolation.By evaporative removal acetone.To this product carry out centrifugation (15 minutes, 5000rpm), make maximum particle deposition.Described subsequently throw out is by decantation and washing with water.At last, product is stored with 20% slurry.Output is 10g.
During centrifugation, do not have sedimentary milk shape emulsion to use metabisulfite solution (3% solution quality) to handle mutually, obtain particle from liquid phase separation.Throw out is through decantation and wash with water three times.The product amount is about 2g (being converted into dry-matter).With this pigment coated paper (10g/m
2), the ISO brightness of goods is through being measured as 70.
Fig. 1 shows the electron micrograph of the cardboard of using the pigment coating for preparing according to present embodiment.
The comparative example 1
Use acetone method, only part is evaporated acetone and is prepared pigment (comparative examples of embodiment 1)
Identical among operation and the embodiment 1, difference is at room temperature to evaporate acetone, it only is close to fully evaporates from watch-glass.Product such as embodiment 1 handle.Product is applied on the paperboard surface and drying after because the plastification and the solvency action of residual acetone are observed granules of pigments and have been formed Clear coating.Therefore, the described pigment coated brightness that does not improve cardboard.
Based on this comparative examples, clearly illustrate that very much: the good solvent of starch acetate (for example acetone) must almost entirely be removed from pigment dispersion before these goods are as acceptable pigment.
Use the coating pigment of acetone-ethanol method preparation based on starch acetate
Solution is formed by ethanol (500ml), water (250ml) and acetone (200ml).Starch acetate (60g, ISO brightness 68.7) with particulate under mixing condition joins in this adulterant.Behind described macromolecule dissolution, 2500ml water is added in this adulterant, mixed very consumingly about 5 minutes simultaneously.This has produced white dispersion, allows it mix 10 minutes.
Solvent is evaporated out from dispersion.After solvent is evaporated, to dispersion carry out centrifugation (15 minutes/5000rpm).Minimum particulate be retained in emulsion mutually in.Three washing precipitates of water in centrifuge tube.After centrifugal the last time, throw out is retained with about 20% slurry form.Product is about 30g.
By using Na
2SO
4, the pigment with low particle size is precipitated out from the milk shape solution of removing during the centrifugation in the first time.Added the Na of 3% consumption that is about solution quality
2SO
4Throw out was by centrifugation (15 minutes/5000rpm) be separated and wash with water three times.Output is about 10g.
Apply electron micrograph that cardboard obtains by pigment and show that described particle is to be close to circular and to have size (referring to Fig. 2) less than 300nm.
Use the coating pigment of by the use of thermal means preparation based on starch acetate.
Solution is formed by ethanol (200ml), water (50ml) and acetone (300ml).The mixing tank that uses motor to drive joins starch acetate (60g, ISO brightness 89.1) in this solution.Behind described macromolecule dissolution, solution is heated to 40 ℃.Add 300ml ethanol (40 ℃) with small volume then.Afterwards, add 100ml water (40 ℃) or begin to become muddy with small volume up to solution.Then, this solution is added in the 2000ml water (60 ℃).5g protective colloid polymkeric substance (Kemira A41) is added in the water.Cool off described emulsion form product.
Na with solution quality 3% consumption
2SO
4Add in the described solution.The throw out decantation from solution that produces comes out.Carry out centrifugation (15 minutes/4000rpm), succeeded by in centrifuge tube, washing with water twice.Output is the pigment products with dry matter content of 32% of about 120g.
Based on the electron micrograph (SEM) of product, observing described particle is that spheric and its mean sizes are 200nm (referring to Fig. 3).
Use acetone method to prepare starch acetate pigment at pilot-scale (pilot scale)
The starch acetate (ISO brightness 68.7) of 2.1kg amount is dissolved in 49kg acetone and the 10kg water.(homogenizer 1500rpm) adds the water that 60kg measures under intensively mixed condition then.After adding entry, formed white emulsion.Acetone is evaporated out from the refrigerative emulsion, and product is concentrated to 10 liters by the micro-filtration method.
Product passes through the spraying drying drying with two batches.Polyvinyl alcohol (Mowiol 10-88) adds in first batch of material as protective colloid.Second batch of material is not having drying under the condition of auxiliary.
The ISO brightness that is recorded the product that does not add Mowiol by compressed tablet is 83.7, and the ISO brightness with product of Mowiol is 83.8.
The percentage composition of remaining acetone uses the NMR technical measurement in the product.This percentage composition is lower than detectability.
The comparative example 2
Use acetone method to prepare pigment, before concentrating pigment, do not evaporate acetone (comparative examples of embodiment 4)
Operation is as among the embodiment 4, and its difference is not remove acetone before micro-filtration.
The result observes: the emulsion particle that is produced is attached to each other and forms the macrobead throw out that blocks micro-filter.
Based on present embodiment, draw the conclusion that acetone makes that further processing becomes complicated.
Embodiment 5
Use acetone-ethanol method to prepare starch acetate pigment at pilot-scale
The starch acetate (ISO brightness 89.1) of 0.75kg amount is dissolved in the 20kg acetone.Add-on is the water of 12.5kg and the ethanol of 20kg in this solution.Check to guarantee that whole starch acetates dissolve.In 20 fens clock times, add the water of 125kg amount and as the 62.5g Kemira A41 polymkeric substance of protective colloid.Formed milk shape emulsion, in 3 hours, in vacuum (112 millibars/40 ℃), acetone evaporated has been come out.Product uses micro-filtration method (50 hours) to be concentrated to 10%.
The particle size distribution of the pigment that is made by this mode is shown among Fig. 4.
Use greater concn to prepare coating pigment at pilot-scale by starch acetate
Amount is the acetone of 16.8kg, and the ethanol of 11.2kg and the water of 3.5kg mix.Solution is heated to 60 ℃, adds 4.2kg starch acetate (ISO brightness 89.1).Solution temperature is reduced to 40 ℃.Then, at room temperature add the ethanol of 16.8kg, be dissolved with the water of protective colloid (Kemira A41) succeeded by interpolation, the consumption of this protective colloid is calculated as 2.4% with starch acetate.This is to carry out in 20 minutes time period, and to keep temperature simultaneously be uniform mixing between 40-50 ℃ and in the whole time period.Subsequently, in a vacuum acetone evaporated is come out.The dry-matter percentage composition of described emulsion form product is 2.8% after evaporating acetone.Afterwards, product through micro-filtration with concentrate, and washes with water in micro-filtration.The amount of final product is 16.3kg, and the dry-matter percentage composition is 23%.The ISO brightness that is recorded by desciccate is 94.4.
The residual volume of organic solvent uses 300MHz NMR technology to measure in product.The percentage composition of resistates is lower than 0.5 weight %, and this is lower than the detectability of this technology.
Fig. 5 shows the particle size distribution (three replicate(determination)s) of pigment, and based on the SEM photo of described product, described pigment is spherical form.The minimum particulate of visible is the present latex particulate as the tackiness agent of coating in the SEM photo.
Embodiment 7
Use the water precipitation method to prepare coralloid starch acetate pigment
Formed solution by ethanol (500ml), water (250ml) and acetone (200ml).
Under mixing condition, starch acetate (60g, ISO brightness 68.7) is joined in this solution.Behind this starch dissolution, this solution was poured in the 2500ml water with constant rate of speed in 6 minutes.In whole toppling process, carry out uniform mixing.During adding, produced white dispersion.After interpolation, continue again to stir 10 minutes.Be settled out starch acetate and result subsequently and formed second dispersion.
Solvent is evaporated out from dispersion.Product process centrifugation (15 minutes/5000rpm).Water washs separated throw out three times in centrifuge tube.After centrifugal the last time, product is retained with 20% slurry form.Product is about 35g.
By utilizing Na
2SO
4(salt of solution quality 3%) saltouts, and fine-particle pigments is precipitated out in (being milk shape liquid phase) from the supernatant liquid solution of centrifugation.Decant settled solution, three washing precipitates of water centrifugation.Output is about 15g.
Fig. 7 shows the SEM photo that uses the water precipitation method to prepare coralloid pigment.
The coating pigment that uses the solvent deposition preparation to have the coralliform pore structure
With consumption is that the starch acetone (ISO brightness 68.7) of 26g is dissolved in (400ml) in the acetone.The LIAV that will measure in about 10 minutes time period to 1000ml under mixed uniformly condition is fed in the described solution.Formed white depositions and allowed its deposition.Decant supernatant liquid.
LIAV (about 500ml) is poured on the settling to cover settling with solvent.Mixed about 10 minutes.Under low pressure use glass sintering body (pore opening is 3) filtering precipitate.Use strainer to rinse again and wash throw out with LIAV (about 400ml).
Throw out drying through washing.Output is about 20g.
The ISO brightness of repressed pigment that records is 87.7.Based on SEM photo (referring to Fig. 8), described as can be known product has vesicular structure.
Embodiment 9
Filler pigments by the starch acetate preparation
Starch derivative (dry matter content is 6% of a total mass, ISO brightness 89.1) is dissolved in the mixture of ethanol (500ml), acetone (200ml) and water (250ml).Described solution is divided into three parts (about 300ml/ batches).Use the mixing velocity of 750rpm, each is poured the solution of 1-3 part in the 1200ml water into down under the intense mixing condition and at 8-12 ℃, and the interpolation time is: 1) 50 minutes (test 1), 2) 45 minutes (test 2) and 3) 60 minutes (testing 3).
Evaporation organic solvent from dispersions obtained.Afterwards, sodium sulfate (15g/2l) is added to cause the separation of particles in dispersion in this solution and be deposited in the substrate of described container.Throw out separates by decantation and washes with water twice.At last, throw out through centrifugation (10 minutes/2500rpm).The gathering pigment that may produce in described process uses Dispermat to handle and removes.
Fig. 9 shows and adds the influence of speed to the particle size distribution of pigment.As shown in the figure, utilize the lower feed rate of higher feed rate can obtain narrower particle size distribution.
The filler pigments of starch acetate.Throw out concentration is to the influence of the particle size distribution of filler pigments
Starch derivative (dry matter content is 6% of a total mass, ISO brightness 89.1) is dissolved in the mixture of ethanol (500ml), acetone (200ml) and water (250ml).In test for the first time (test 1), take out 425ml solution and it was poured in the 850ml water under the intense mixing condition in 25 minutes.(test 2) was poured into equal volume in the 750ml water in 25 minutes under the intense mixing condition in test for the second time.Evaporation organic solvent from dispersions obtained.After this, sodium sulfate (15g/2l) is added in the described solution, this causes the separation of particles in the dispersion and is deposited in the substrate of container.By decantation sediment separate out and washing with water twice.At last, throw out through centrifugation (10 minutes/2500rpm).The gathering pigment that may produce in described process uses Dispermat to handle and removes.
Figure 10 shows the particle size distribution of described pigment.Based on this test, observe the influence of the variation of concentration for the particle size distribution of filler pigments.
Embodiment 11
Filler pigments by the starch acetate preparation.Rotating speed is to the influence of the particle size distribution of filler pigments
Starch derivative (dry matter content is 6% of a total mass, ISO brightness 89.1) is dissolved in the mixture of ethanol (500ml), acetone (200ml) and water (250ml).This solution is divided into three parts.Mixing under the situation of water, use 1) rotating speed (test 1), 2 of 500rpm) 1000rpm (test 2) and 3) 1500rpm (testing 3), added each part in the 1200ml water in the clock time at 2 minutes.
Evaporation organic solvent from dispersions obtained.Subsequently, (15g/2l) adds in the solution with sodium sulfate, and this causes the separation of particles in the dispersion and is deposited in the substrate of container.By decantation sediment separate out and washing with water twice.At last, throw out through centrifugation (10 minutes/2500rpm).
The gathering pigment that may produce in described process uses Dispermat to handle and removes.
Figure 10 illustrates the influence of mixing velocity to the particle size distribution of filler pigments.
Filler pigments by the starch acetate preparation.Starting material concentration is to the influence of the particle size distribution of filler pigments
1) 60g starch acetate (ISO brightness 89.1) (test 1), 2) 30g starch acetate (ISO brightness 89.1) (test 2), 3) 15g starch acetate (ISO brightness 89.1) (test 3), 4) 120g starch acetate (ISO brightness 89.1) (test 4) and 5) 180g starch acetate (ISO brightness 89.1) (testing 5) was dissolved in ethanol, acetone and water (5: 2: in mixture 2.5w/w/w).
In 5 times in second, under condition, respectively, in test 1-3, solution is added in the 1250ml water with the rotating speed mixing water of 350rpm, in test 4, solution is added in the 2500ml water, in test 5, solution is added in the 3750ml water.Organic solvent is evaporated from dispersions obtained.Afterwards, (15g/2l) adds in the solution with sodium sulfate, and this causes the particle separation in the dispersion and is deposited in the substrate of container.By decantation sediment separate out and washing with water twice.Throw out process centrifugation at last, (10 minutes/5000rpm).The dry matter content of product is 13% (test 1), 30% (test 2), 36% (test 3), 10% (test 4) and 10% (test 5).
Figure 12 illustrates the particle size distribution of the pigment that under different starting material concentration, prepares.
Measure based on particle size, the concentration of observing base mateiral has remarkably influenced to the particle size distribution of filler pigments.
Embodiment 13
Successive reaction form with the acetylize method prepares pigment
In when beginning, with 3.0kg (as dry-matter) chemistry or enzymatic splitted potato starch, 24.7kg acetate (100%), 4.07kg diacetyl oxide and mix as the 0.2kg sodium acetate of catalyzer.Acetylize is carried out under 100-115 ℃ temperature, and the reaction times is 3 hours.Subsequently, make liquid reaction mixture be cooled to 20 ℃ temperature, and add 15kg cold water.Continue to mix and check the uniformity coefficient of reaction mixture.Afterwards, continue dilution by adding 8.8kg cold water, it is muddy to make solution continue.Subsequently, 130kg water is pumped into solution rapidly, make to produce white dispersion.Described dispersion partly neutralizes by 50% the NaOH solution that adds 15kg, and cools off this dispersion simultaneously.After neutralization stage, the pH value of described starch dispersions is 4.0-4.5.
Utilize centrifugation to make pigment from solution separating.By it being mixed with 50kg water once more and repeating to eluriate and centrifugal at least twice cleaning pigment slurries.After cleaning, utilize the Dispermat mixing tank that pigment is mixed in water and homogenization reaches the operation concentration of 10-30%.
Perhaps, described pigment can use the micro-filtration method to separate with water dispersion.Based on this test, the preparation of pigment also can use acetic acid solvent to carry out, and need not to separate the stage with the dry starch acetic ester.
Ultrasonic wave is assisted and is prepared pigment
As described in embodiment 11, starch acetate is dissolved in the mixture of ethanol, acetone and water.Described solution is fed in the 2500ml water with constant speed, and its temperature is 14 ℃ and carries out in ultrasound reactor.Frequency of ultrasonic is that 22.2kHz and power are 500W.Used two kinds to add speed to each supersound process: 2 minutes and 5 minutes.Subsequently, solvent is evaporated the particle size of having removed and measured product.The average particle size particle size of handling in 2 minutes is 281nm, and the average particle size particle size of handling in 5 minutes is 187nm.
Embodiment 15
Use grinding and classification technique to prepare filler pigments
In order to reduce particle size, three kinds of starch qualities (potato starch triacetate, oat starch and crosslinked oat starch) pulverizing and classification test have been carried out.Usually, use dual stage process to prepare thin particulate part: grind with jet grinding machine, then (Outokumpu Research Oy, Pori Finland) carry out classification with air trap.Also tested the ball mill grinding.Use the combination of jet grinding machine and air trap, adopt the potato starch triacetate to obtain minimum particle size (d
50Be 4.6 μ m; d
90Be 9.2 μ m).
Shown the influence of treatment process in the bottom to the starch sample particle size distribution.d
90The particle of value representation 90 weight % is less than or equal to this size (μ m).
The air classifying of table 1 starch and the result of pulverizing
C6N100 (potato starch triacetate)
| d 10(μm) | d 50(μm) | d 90(μm) | |
| Initially | 3.3 | 57.6 | 451 |
| Jet grinding machine grinds under 4000rpm | 2.9 | 12.7 | 35.5 |
| Air separation, 10000rpm | 2.3 | 6.0 | 15.3 |
| Air separation, 13000rpm | 1.8 | 4.6 | 9.2 |
| Air separation, 18000rpm | 1.7 | 3.7 | 11.3 |
| Ball mill grinds * | 2.1 | 8.6 | 30.1 |
*) charging: the 13000rpm thicker part divides oat starch (basis)
| d 10(μm) | d 50(μm) | d 90(μm) | |
| Initially | 1.4 | 9.8 | 20.7 |
| Air separation, 8000rpm | 1.7 | 7.2 | 15.3 |
| Air separation, 10000rpm | 1.5 | 5.6 | 10.8 |
| Air separation, 18000rpm | 2.1 | 5.9 | 17.2 |
Prepare pigment by the hydroxypropyl starch ester
Identical among operation and the embodiment 1, its difference is to use the hydroxypropyl starch acetate as parent material (test 1) and propionic ester (testing 2).Products therefrom is a white emulsion in both cases, and it is further handled and carries out according to embodiment 1.
Embodiment 17
The lightness properties of pigment and opacity
The lightness properties of pigment is by being determined by the exsiccant product compacting sample button and the ISO brightness of measuring them.Table 2 shows the brightness results of repressed sheet.Sample 250 TG 8-9 are starch acetates, by this specimen preparation AP type pigment and AT type pigment.
Table 2 is by the brightness of the product that records of compacting button
| Sample | Brightness |
| Embodiment | |
| 4 products that do not have protective colloid | ISO br.83.7 |
| With | ISO br.83.8 |
| | ISO br.87.7 |
| | ISO br.89.1 |
| | ISO br.94.4 |
| Potato starch | ISO br.87.4 |
With respect to the ISO brightness value of the common pigments of being put down in writing in the literature, the brightness value of obtained pigment has good specification:
Kaolin 80-90
GCC 87-97
Talc 85-90
PCC 96-99
Calcined kaolin 93
Titanium dioxide 97-99
Plastic pigments (the most frequently used is polystyrene) 93-94
(reference: Papermaking Science and Technology, the 11st part of book, 65 pages)
Also studied through the paper of coating and the brightness and the opaqueness of cardboard.Coating prepares with K-Coater in the laboratory, and is coated in 53.4g/m
2The paper of books level on.
Figure 13 has shown that how the brightness of books level paper increase with the variation of coat weight, wherein uses different test pigment, and use filler PCC (FR-120, Huber) in contrast.Under optimal situation, when coat weight hour described AP2 type pigment has obtained the brightness much at one with the PCC with identical coat weight.When bigger coat weight, the brightness of PCC is more excellent.Yet, the brightness by improving product and particularly by making that particle size distribution is narrower and make it more approach the optimal size grade of scattering of light that the starch base pigment effect can also significantly rise.
Accordingly, Figure 14 shows coat weight to 53.4g/m
2The influence of paper opacity.Currently, PCC remains excellent slightly filler, and when using identical coat weight, adopting PCC to use starch pigment to have on the paper opacity preferably increases.Calculating according to University of Helsinki, by optimizing particle size and the particle size distribution by enough stricturizations, can be so that prepared starch base test pigment be better than the PCC filler, wherein the PCC filler in light scattering efficiency with comparing, therefore, although the specific refractory power of PCC is higher than prepared test pigment a little, to compare with PCC with identical coat weight, these pigment more can improve the opacity of paper.
Use paper web applying glue (web-sizing) test of pigment
Be applied on the books level paper by the PCC that uses the paper web glue-applying technique will test pigment and contrast and tested the pigment property that is used for the filler purpose.Why using this technology, is because adopt this method to be easy to determine to be applied to amount of pigment on the paper.Different with the amount of mineral color, in fact the amount of starch pigment can not be determined by calcining.The difference on effect that very different retention performance and goods are had in forming page shows: the paper web glue-applying technique is the simplest method of testing in the packing type purposes at pigment.
Implemented described application with 10% solid content, 10% latex has wherein fed intake.
Figure 15 a and 15b show the result of paper web sizing test.NFP 2 is the pigment from embodiment 2, and NEP 3 is to use the pigment according to the technology preparation of embodiment 7.
Described page is repeatedly transmitted by the top sizing press, makes the grammes per square metre of paper be increased to the degree corresponding to different applied amounts.At test point 4+4gsm place, at first, 4 grams are applied on the one side, then, other 4 grams are applied on the another side.The latex point contains the latex with other test point same amount, the number of times that applies and NFP 2 test point apply number of times identical (this means, 2,4 or 4+4gsm of reinforced latex).
From this result, as can be seen, total trend is: with respect to the test point that contains PCC, the test point that contains starch pigment has excellent intensity.Because the paper utmost point repeatedly must be transmitted by the top sizing press obtaining required applied amount, paper is easy to generate loss and little gauffer, and paper expands and its intensity reduction.On the other hand, the latex of interpolation increases intensity, although this effect of latex is arranged, notices on the 4+4 level that especially intensity begins to descend.Owing to corresponding reason, the intensity of starch pigment begins to descend in level 3 (4+4gsm) equally.Infer that when directly joining filler in the paper pulp, when comparing with the paper that uses PCC, these strength propertys through improving of paper with starch pigment are more obvious when in papermaking.This conclusion is based on the following fact: when making the width of cloth (webbing) and produce hydrogen bond between fiber, the formation of these keys has been disturbed in a large amount of mineral fillers unfriendly, but described starch pigment can not disturb the formation of these keys.
The preparation of the starch derivative that in preparation pigment and filler, uses
With starch, acetate (acetate: the ratio of starch is 2), part diacetyl oxide (based on the dry matter content of starch and the water-content of other reagent, calculate from obtaining up to the required amount of 1.7 substitution value) and catalyzer (sodium acetate, amount of starch 7%) mix mutually, and this adulterant heated in closed reactor begin gelation up to starch.
Gelation causes thermopositive reaction, and the temperature of reaction mixture rises rapidly.Described temperature remains on 125 ℃ and reacts up to the diacetyl oxide that begins to add.Afterwards, add remaining diacetyl oxide (consumption calculates according to the required DS of final product), this is reflected at 125 ℃ and continues 3.5 hours down, begins to calculate from gelation point.
After esterification, make reaction mixture be cooled to and from 2.5 times of big water yields, be precipitated out less than 100 ℃.Precipitated product after filtration and wash with water up to pH value of filtrate greater than 5.Product vacuum contact drying device (Drais TurbuDry T250) drying.The substitution value of described product or measure or after starch acetate disintegrates in the basic metal hydrolysis, with acetate titration method mensuration with NMR.
Depend on used diacetyl oxide, according to the quality of initial starch, the DS that makes product changes in the 1.7-3.0 scope, and second-order transition temperature (Tg) is 155-162 ℃ of change.
Described operation is identical in 1 with test, but the starch that is to use enzymatic or chemical hydrolysis is as initial starch.Along with the hydrolysis degree increase of initial starch, the solubleness of starch acetate in organic solvent increases, and making to increase concentration in pigment prepared.The molecular weight of initial starch influences the second-order transition temperature of product.When the molecular weight of initial starch was Mw 537000g/mol, Tg was 159 ℃, and substitution value is 3, and when the degree of molecular weight at Mw 22000g/mol, Tg is 134, and substitution value equates.
Starting material (with the dry-matter form)
Natural potato starch (Periva) 33.0kg
Acetate (technical grade 99%) 49.5kg
Sodium acetate (VTT 100%) 2.5kg
Diacetyl oxide (technical grade 97%) 115.5kg
Water (from reagent) 7.5kg
Preparation process:
-will pump in the reactor according to the liquid of prescription volume
-add dry substance from filler unit
-reactor is filled nitrogen (nitrified)
-reactor is heated to 125 ℃ temperature, and cold water is remained in the chuck of reactor Filter column
-under about 115 ℃, make the starch gel gel
-begin acetate-diacetyl oxide mixture was refluxed 5 hours from gelation point
When-reaction finished, product was precipitated out from about 1000kg water
-use wet wheeling machine that throw out is washed and grinds
-grinding product is filtered and carry out drying with Larox vacuum drums strainer with vacuum drier
-during drying, the temperature range of product is about 45-70 ℃.
The replacement degree of product or measure or after starch acetate disintegrates in basic hydrolysis, through the acetate titration determination through NMR.Find that substitution value is 2.2.The color that makes the potato starch acetic ester becomes clear.The ISO brightness of the starch acetate that makes with less similar reactor with the same manner is 88.
Use is according to the method for the patent application FI 20020313 of VTT Research Centre of Finland, by becoming batch reaction or being prepared by extruding technology.The transglycosylation product of starch acetate increases with respect to the native starch acetic ester in the solubleness of organic solvent.According to the efficient and the initial starch of purifying, the ISO brightness of described product changes between 67-89.
Used dibasic alcohol/polyvalent alcohol is connected on the starch by ehter bond in changeing glycosylation, and in pigment prepared, dibasic alcohol/polyvalent alcohol can influence the dispersity of product.The second-order transition temperature of this product is 155-157 ℃, and substitution value changes between 2-2.5.
Test the preparation of 5. hydroxypropyl starch acetates and hydroxypropyl starch propionate
The preparation method who is described in FI patent application 107930 and 107386 is used to prepare the hydroxypropyl starch ester.In the preparation propionic ester, acetate substitutes with propionic acid, and diacetyl oxide substitutes with propionic anhydride.
When using acetone-ethanol, rotating speed and add speed to the amount of the product part of pigment and the influence of particle size
The starch acetate (embodiment 19, test 4) of 120g amount is dissolved in the solvent blends by 1000ml ethanol, 40ml acetone and 400ml water.Gained solution is divided into the quartern, and adopts following interpolation time and rotating speed to add 1250ml water to each part:
Test 1: rotating speed is 300rpm, and the water interpolation time is 6 seconds
Test 2: rotating speed is 300rpm, and the water interpolation time is 3 minutes
Test 3: rotating speed is 150rpm, and the water interpolation time is 6 seconds
Test 4: rotating speed is 150rpm, and the water interpolation time is 3 minutes
As described in embodiment 2, the gained pigment dispersion is further handled.
Separate thick pigment part by centrifugation, by adding the thinner part of sodium sulfate precipitation.Wash according to embodiment 2.
The relative quantity of each several part is following in different tests lists:
Test 1: the amount that the gained thicker part divides is four times of thin amount partly
Test 2: the amount that the gained thicker part divides is 11 times of thin part amount
Test 3: the amount of the thin part of gained is 93 times of thicker part component
Test 4: the amount of the thin part of gained is 9 times of thicker part component
The particle size that thicker part divides is 300-1000nm, and the particle size of thin part is less than 300nm.
Based on test, can clearly be seen that preparation condition influences the particle size distribution of pigment.
Claims (30)
1. method for preparing starch base pigment or filler is characterized in that:
-by being dissolved in, starch derivative forms the solution that contains starch derivative in the appropriate solution,
-this solution is contacted with the non-solvent that starch derivative can not be dissolved in wherein, make this starch derivative from this solvent, precipitate, cause producing dispersion, this dispersion comprises throw out that is made of starch derivative and the liquid phase that comprises solvent and non-solvent,
-this solvent removed from liquid phase and
-sediment separate out and recovery from this non-solvent.
2. the method for claim 1 is characterized in that, the mixture of solvent and non-solvent is as described solvent.
3. claim 1 or 2 method is characterized in that, only use the solvent of dissolving starch derivative aequum or use the amount that surpasses aequum 20 weight % at most.
4. each method is characterized in that in the aforementioned claim, has formed the solution that can apply following at least one criterion to it:
The concentration of-solution is at least 1 weight %, preferably about 10-30 weight % and
The viscosity of-solution is 1-5 times of water viscosity.
5. each method among the claim 1-4 is characterized in that, the glass transition point of used starch derivative is at least 60 ℃, preferably at least 100 ℃, and perhaps this starch derivative can not decompose under described temperature.
6. each method among the claim 1-5 is characterized in that, uses starch ester as starch derivative.
7. the method for claim 5 is characterized in that, described starch ester is by starch and C
1-4The ester that alkyl acid forms, the preferred starch acetic ester.
8. claim 6 or 7 method is characterized in that, described starch ester is through changeing glycosylation or hydroxy alkylated.
9. each method is characterized in that in the aforementioned claim, makes water, C
1-4Alkanol or based on the solvent of non-polar hydrocarbon as non-solvent.
10. each method is characterized in that in the aforementioned claim, uses straight chain, branching or cyclic ketone or aldehyde as solvent.
11. each method is characterized in that in the aforementioned claim, as the ester group substitution value of the ester of starch derivative so that this starch derivative is insoluble to the form of non-solvent basically selects.
12. each method is characterized in that in the aforementioned claim, after removing solvent, the throw out that goes out from liquid phase separation does not contain the detected organic solvent residual volume of useful 300MHz NMR equipment energy.
13. each method is characterized in that in the aforementioned claim, described solvent and non-solvent with they each other fully the blended mode select.
14. each method is characterized in that in the aforementioned claim, the amount of non-solvent be solvent or solvent mixture amount about 0.1-100 doubly, preferably about 0.5-10 doubly, optimum about 0.7-5 times, calculation by weight.
15. each method is characterized in that in the aforementioned claim, under mixing condition non-solvent is joined in the starch derivative solution, thereby produces spherical granules of pigments.
16. the method for claim 15 is characterized in that, has prepared to comprise that average particle size particle size is the pigment or the stuffing product of the spherical pigment of about 90-1000 nanometer.
17. the method for claim 15 or 16 is characterized in that, described starch derivative precipitated from solution in two stages, this means that the particulate that is dispersed in the liquid phase for example passes through salt precipitation after with water precipitation and possible sediment separate out.
18. each method is characterized in that among the claim 1-15, under mixing condition starch derivative solution is added in the non-solvent to produce coralloid porous pigment goods.
19. the method for claim 18 is characterized in that, has prepared to comprise that particle size is about 1-100 micron and has pigment or the stuffing product of mean diameter for the material in the hole of about 100-500 nanometer.
20. each method is characterized in that in the aforementioned claim, and the solution that contains starch derivative is contacted with non-solvent under disturbed conditions.
21. each method is characterized in that in the aforementioned claim, depends on solvent or solvent mixture, the amount of non-solvent be generally solvent or solvent mixture amount 0.1-100 doubly, preferably about 0.5-10 doubly is most suitably about 0.7-5 times, by weight calculation.
22. pigment or stuffing product based on a starch is characterized in that,
-its constitute by starch derivative and
-it comprises that average particle size particle size is the spherical starch derivative particle of about 90-1000 nanometer.
23. the pigment of claim 22 or stuffing product is characterized in that, its ISO brightness is at least 80.
24. the pigment of claim 22 or 23 or stuffing product is characterized in that, it uses, and each method prepares among the claim 1-21.
25. pigment or stuffing product is characterized in that,
-its constitute by starch derivative and
-it comprises the coralliform material of nanoporous, its particle size is about 1-100 micron.
26. the pigment of claim 25 or stuffing product is characterized in that, it uses, and each method prepares among the claim 1-21.
27. the pigment of claim 25 or 26 or stuffing product is characterized in that, described starch derivative is a starch ester.
28. the pigment of claim 27 or stuffing product is characterized in that, described starch ester is by starch and C
1-4The ester that alkyl acid forms, the preferred starch acetic ester.
29. the pigment of claim 27 or 28 or stuffing product is characterized in that, described starch ester is through changeing glycosylation or hydroxy alkylated.
30. the purposes of each pigment or stuffing product among the claim 22-29 is used in the manufacturing, coating of paper and cardboard, in the plastics, in the rubber and in the makeup, in the sanitary product and/or in the washing composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20035173A FI20035173A0 (en) | 2003-10-02 | 2003-10-02 | Tailor-made organic paper and paperboard coating pigment or filler and its manufacturing process |
| FI20035173 | 2003-10-02 | ||
| FI20040741 | 2004-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1863847A true CN1863847A (en) | 2006-11-15 |
| CN100503696C CN100503696C (en) | 2009-06-24 |
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|---|---|---|---|
| CNB2004800287909A Expired - Fee Related CN100503696C (en) | 2003-10-02 | 2004-10-01 | Pigment and filler and a method of manufacturing it |
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|---|---|
| CN (1) | CN100503696C (en) |
| FI (1) | FI20035173A0 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275372B (en) * | 2008-03-18 | 2010-06-09 | 陕西科技大学 | Preparation for starch-fatty acid modified micro-particles papermaking filler |
| CN104812777A (en) * | 2012-10-24 | 2015-07-29 | 塞拉尼斯醋酸纤维有限公司 | Polysaccharide ester microspheres and methods and articles relating thereto |
| CN110054741A (en) * | 2019-04-02 | 2019-07-26 | 深圳市华星光电技术有限公司 | The preparation method of dispersible pigment dispersion |
| CN112960764A (en) * | 2021-02-07 | 2021-06-15 | 杭州楠大环保科技有限公司 | Landfill leachate denitrification method |
-
2003
- 2003-10-02 FI FI20035173A patent/FI20035173A0/en unknown
-
2004
- 2004-10-01 CN CNB2004800287909A patent/CN100503696C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275372B (en) * | 2008-03-18 | 2010-06-09 | 陕西科技大学 | Preparation for starch-fatty acid modified micro-particles papermaking filler |
| CN104812777A (en) * | 2012-10-24 | 2015-07-29 | 塞拉尼斯醋酸纤维有限公司 | Polysaccharide ester microspheres and methods and articles relating thereto |
| CN110054741A (en) * | 2019-04-02 | 2019-07-26 | 深圳市华星光电技术有限公司 | The preparation method of dispersible pigment dispersion |
| CN112960764A (en) * | 2021-02-07 | 2021-06-15 | 杭州楠大环保科技有限公司 | Landfill leachate denitrification method |
| CN112960764B (en) * | 2021-02-07 | 2022-05-24 | 杭州楠大环保科技有限公司 | Landfill leachate denitrification method |
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| Publication number | Publication date |
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| FI20035173A0 (en) | 2003-10-02 |
| CN100503696C (en) | 2009-06-24 |
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