CN101210053B - Amphiphilic starch derivative fine particles and preparing method thereof - Google Patents
Amphiphilic starch derivative fine particles and preparing method thereof Download PDFInfo
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Abstract
The invention belongs to the fine particle preparation field of natural high polymer material, in particular to fine particle of amphiphilic starch derivative and a preparation method thereof. the invention controls group with hydrophobic property to be connected to part of hydroxyl (group) of starch macromolecule, or be grafted and copolymerizated small amount of lipophilic polymer chain on part of hydroxyl (group) of starch macromolecule; therefore, the hydrophobic property of starch macromolecule is kept while the substituting group with hydrophobic property or the polymer chain provides lipophilicity. The amphiphilic starch derivative has special property; the amphiphilic starch derivative still has hydrophobic property, but the water-absorbing swelling property of the starch is inhibited. The existence of the group with hydrophobic property or the polymer chain with hydrophobic property breaks the hydrogen bond and the crystallinity of starch macromolecule. The interfacial compatibility between the prepared fine particle of amphiphilic starch derivative and polymeric matrix such as rubber is improved; the prepared fine particle of amphiphilic starch derivative can be used in materials of green tire to be taken as functionalized filling to substitute for carbon black and white carbon black, and also can be used in environmental-friendly materials and the products thereof, thus having broad applying prospect.
Description
Technical field
The invention belongs to the preparation field of natural macromolecular material subparticle, be particularly related to particle diameter at amphiphilic starch derivative fine particles of 50～500nm and preparation method thereof, this amphiphilic starch derivative fine particles is mainly used in the green tire goods, as the functionalization filler, also can be used in environment-friendly material and the goods thereof.
Background technology
Starch is reproducible, the resourceful poly-polyose natural polymer of nature.In China, unedible industrial starch has up to ten million tons every year, also has wide starch resource leaved for development in addition.
Native starch particles is at 5～80 microns, and the sample of particle diameter only plays filling effect in material like this, does not have the functionalization effect, also just is unfavorable for the utilization of starch product.And particle diameter just can show good enhancement at the starch below 1 micron.Nano-starch has very fine micro-scale, at present, several few patents is arranged both at home and abroad, as US 6677386 (2004), US 6921430 (2005) etc., adopt gel crosslinked-preparation starch nano particles such as hot water dispersion method, acid-hydrolysis method.
Nano-starch is mainly used in the enhancing of rubber and thermoplastics at present.People [Angellier H, Molina-Boisseau S, Lebrun L such as Angellier H, et al.Macromolecules, 2005,38 (9): 3783～3792] natural rubber latex is added in the nano-starch solution, co-precipitation obtains the nano-starch matrix material.In addition, also utilize nano-starch to strengthen polystyrene-butyl acrylate copolymer [Angellier H, Putaux J L, Molina-Boisseau S, et al.Macromolecular Symposia, 2005,221:95～104].
Document [Qing Qi, Youping Wu, Ming Tian, et al.Polymer, 2006,47 (11): 3896～3903] has been studied the dispersiveness of common nano-starch particle in rubber latex.
Starch is that special admittedly company proposes [US6269858 first in calendar year 2001 in the application of green tire, Rubber containing starch reinforcement and tire having component thereof, 2001], be a kind of weighting agent---BioTred based on starch, mixture for starch and softening agent (w/w is 60/40), replace the part white carbon black, and use a large amount of silane coupling agents, goods have been used for the green tire product.
Existing bibliographical information, be the preparation of paying close attention to nano-starch and very fine starch mostly, and chemically modified starch is only considered the change of the chemical property of starch, also there is not document that amphiphilic starch derivative fine particles is studied, because the wetting ability and the strong polar characteristics of starch particle itself, so and polymeric matrix, relatively poor as the consistency of rubber etc., influence the dispersion of starch granules, cause strengthening action to weaken.
Summary of the invention
The object of the present invention is to provide amphiphilic starch derivative fine particles, with might be as present international research focus green tire material with new property.So-called green tire should have low energy expenditure (oil consumption), high security, few CO
2Discharging helps environmental protection.
A further object of the present invention provides the amphiphilic starch derivative fine particles of particle diameter at 50～500nm.
Another object of the present invention provides the preparation method of amphiphilic starch derivative fine particles.
Because natural polymer starch is made of possess hydrophilic property glucose unit.The present invention is controlledly on the part of hydroxyl of starch polymer, connect hydrophobic group, or a small amount of lipophilicity macromolecular chain of graft copolymerization, thereby still keep the hydrophilicity of starch polymer, hydrophobic substituent or macromolecular chain then provide lipophilicity, and this amphipathic starch derivant has special performances, though they still have a wetting ability, suppressed the water absorption and swelling of starch.The existence of hydrophobic group or hydrophobic polymer chain has destroyed hydrogen bond and crystallinity between starch polymer.The starch polymer chain stretches when medium is water, and the hydrophobic polymer chain then curls, and is then opposite in hydrophobic medium.When with blend rubber, the hydrophobic polymer chain stretches, and has increased the interface compatibility with rubber, therefore can make the little multi-phase composites with property.
Amphiphilic starch derivative fine particles of the present invention is to be connected to hydrophobic group on the part of hydroxyl of starch polymer, or partially grafted copolymerization lipophilicity macromolecular chain arranged, make the starch derivative fine particles that obtains possess hydrophilic property and oil loving amphiphilic simultaneously.
Described amphiphilic starch derivative fine particles particle diameter is at 50～500nm.
The described hydrophobic group that is connected on the part of hydroxyl of starch polymer is C
2～C
18Carbalkoxy, benzyl or C
3～C
18Hydroxyalkyl etc.
The described copolymerization lipophilicity macromolecular chain that is grafted with on the part of hydroxyl of starch polymer is polystyrene or polyvinyl acetate (PVA) etc.
Described amphipathic starch derivant comprises the C of low degree of substitution or low percentage of grafting
2～C
18Alkyl esterification starch, benzyl starch, C
3～C
18Hydroxyalkyl starch ether, grafted polystyrene starch or grafting polyvinyl acetate (PVA) starch etc.
Patent CN99815309.5 utilizes the two-phase system method to prepare the starch granules of particle diameter less than 600nm.The present invention takes to be different from the method for existing patent, be in-situ modified technology, replace or graft copolymerization by group, in starch, introduce hydrophobic group, as benzyl, carbalkoxy etc. and hydrophobic polymer chain, as polystyrene or poly(propylene oxide) etc., the control substitution value is also regulated parents' performance, preparation amphipathic starch subparticle.
The present invention adopts the method for in-situ modified prepared amphiphilic starch derivative fine particles may further comprise the steps:
(1) starch is scattered in carries out acid hydrolysis in the acid, stir, through centrifugation, washing obtains the starch subparticle; Or
Starch is obtained starch solution in the water-soluble or dimethyl sulfoxide solvent, add the linking agent glutaraldehyde water solution, stir, obtain the starch subparticle;
(2) the starch subparticle that step (1) is obtained mixes with properties-correcting agent, wherein properties-correcting agent is 0.1～0.5:1 with the amount of substance ratio of starch, stir, the original position radical reaction takes place on starch subparticle surface, obtain amphiphilic starch derivative fine particles through centrifugation, particle diameter is at 50～500nm; Or
The starch subparticle that step (1) is obtained mixes with properties-correcting agent and initiator, wherein properties-correcting agent is 0.1～0.5:1 with the amount of substance ratio of starch, stir, the free radical grafting copolymerization reaction takes place on starch subparticle surface, obtain amphiphilic starch derivative fine particles through centrifugation, particle diameter is at 50～500nm.
The starch acid hydrolysis that the present invention utilized, be that starch is scattered in the aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid etc. that concentration is 1.5～3mol/L, 30～50 ℃ of stirrings, handled continuously 7～21 days, obtain the starch subparticle through centrifugation, washing again.This mainly is that to utilize starch granules itself be the composite structure that is formed by crystallizing field and non-crystalline region, and non-crystalline region can be in hydrolysis under the strong acid condition, and crystallizing field can be more stable existence, can obtain the starch crystallite of particle diameter like this at 50～100nm, further reaction in can obtain the amphiphilic starch derivative fine particles of particle diameter at 50～500nm.
The present invention obtains starch solution with starch in the water-soluble or dimethyl sulfoxide (DMSO), is to utilize starch can obviously weaken the hydrogen bond that exists in the starch molecule in this two media, thereby causes ative starch particulate composite structure to disintegrate, and further obtains the starch subparticle.Adopt the linking agent glutaraldehyde, can with the hydroxyl reaction in the starch molecular chain, weaken hydrogen bond action between starch molecule, and the motion of restriction starch molecular chain, thereby make the prepared starch granules can stable existence.Concrete preparation technology: with the starch dispersed with stirring in water, concentration is 1wt%～15wt%, 80～100 ℃ were stirred 0.5～1 hour down, the concentration that adds starch weight 1%～5% then is the glutaraldehyde water solution of 40wt%～60wt%, continue to stir about 1 hour, the starch pasty state solution that obtains being translucent, the grain breakage of microscopic examination ative starch obtains the starch subparticle; Also can be in dimethyl sulfoxide solvent with the starch dispersed with stirring, concentration is 5wt%～10wt%, 100～120 ℃ were stirred 1～1.5 hour down, the concentration that adds starch weight 1%～5% then is the glutaraldehyde water solution of 40wt%～60wt%, continue to stir about 1 hour, the starch pasty state solution that obtains being translucent, starch disperses wherein with subparticle.
In the reaction mixture of step (2), can further add mineral alkali, as sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate etc., to promote reaction.
In the reaction mixture of step (2), tensio-active agent can be further added,, graft reaction efficient can be improved as Sodium dodecylbenzene sulfonate (SDBS), sodium lauryl sulphate, tween-80 etc.
The used initiator of the present invention is Potassium Persulphate (KPS), ammonium persulphate etc., and its consumption is generally the 0.5wt%～5wt% of properties-correcting agent weight.
The properties-correcting agent that the present invention is used is as aceticanhydride, C
2～C
18Alkyl acyl chloride, benzyl chloride, C
3～C
18Alkyl epoxide, vinylbenzene or vinyl acetate etc.
The starch that the present invention is used is as one or more the mixture in W-Gum, wheat starch, sorghum starch, yam starch or the tapioca (flour).
Original position radical reaction or graft copolymerization are carried out in the surface of the starch subparticle of the present invention's preparation, prepared amphiphilic starch derivative fine particles is possess hydrophilic property not only, and has certain lipophilicity, help the stability of particle in solution, can be in solution stable existence, but also stable at low temperatures preservation the after the centrifugation can be directly used in the blend with rubber latex.
The present invention adopts in-situ modified technology to realize the preparation of amphiphilic starch derivative fine particles on the basis of existing starch conversion technology.Prepared amphiphilic starch derivative fine particles has increased the interface compatibility with polymeric matrix such as rubber, can be used for green tire material, as an alternative the functionalization filler of carbon black, white carbon black; Also can be used for being used for fields such as tire industry, packing in environment-friendly material and the goods thereof, be with a wide range of applications.
Description of drawings
Fig. 1. the sem photograph of the benzyl starch subparticle of the embodiment of the invention 1 preparation, particle diameter is at 100～300nm.
Fig. 2. the fine grain sem photograph of benzyl starch of the embodiment of the invention 2 preparations, particle diameter is at 100～500nm.
Fig. 3. the sem photograph of the polystyrene graft starch subparticle of the embodiment of the invention 5 preparations, particle diameter is at 100～300nm.
Embodiment
Embodiment 1
At first, W-Gum 50g is added in the phosphoric acid solution of 2.5mol/L, under 45 ℃ of temperature, stirred 10～15 days, obtain starch subparticle, yield 10%～15% through centrifugation, washing again.In the 250ml there-necked flask of taking back the stream prolong, add the starch subparticle aqueous dispersions that is equivalent to 5g over dry starch weight, stir and add aqueous sodium hydroxide solution and the benzyl chloride that weight concentration is 15wt% down in batches, the amount of substance of the two is than being 2:1～3:1, benzyl chloride is 0.1～0.2:1 with the amount of substance ratio of starch, add the back and heat up 50～60 ℃, reaction 5～10h, cooling then, centrifugation obtains the aqueous dispersions of amphipathic starch.Scanning electron microscope (SEM) test shows, the particle diameter of benzyl starch is seen Fig. 1 at 100～300nm.Nuclear magnetic resonance spectrum shows that substitution value is lower than 0.05.
Embodiment 2
With the tapioca (flour) dispersed with stirring in water, weight concentration is 8%, 80～100 ℃ were stirred 0.5～1 hour down, the concentration that adds starch weight 2% then is the glutaraldehyde water solution of 40wt%, continue to stir 1 hour, the starch pasty state solution that obtains being translucent, the grain breakage of microscopic examination ative starch obtains the starch subparticle; Get the solution that is equivalent to starch dry weight 16.2g, add in the 500ml there-necked flask of taking back the stream prolong, stir that to add weight concentration down be 15% aqueous sodium hydroxide solution and benzyl chloride in batches, the amount of substance of the two is than being 2:1～3:1, benzyl chloride is 0.1～0.2:1 with the amount of substance ratio of starch, adds the back and heats up 50～55 ℃, reaction 5～10h, cooling then, centrifugation obtains the aqueous dispersions of benzyl starch.Sem test shows that product cut size is seen Fig. 2 at 100～500nm.Nuclear magnetic resonance spectrum shows that substitution value is lower than 0.05.
Embodiment 3
Under agitation, the 16.2g W-Gum is dispersed in the 162g dimethyl sulfoxide (DMSO), 100～120 ℃ were stirred 1～1.5 hour down, cool to 60 ℃ then, the concentration that adds starch weight 1%～5% is the glutaraldehyde water solution of 40wt%, continue to stir 1 hour, the starch pasty state solution that obtains being translucent, starch disperses wherein with subparticle.In solution, add 0.2g sodium hydroxide, continue to stir 1 hour, in there-necked flask, feed nitrogen, and solution temperature is reduced to 18～25 ℃; (propylene oxide is 0.1～0.5:1) with the ratio of the amount of starch substance, reacts 2～3 hours under 18 ℃, nitrogen protection to add propylene oxide; Solution slowly is warming up to 38～40 ℃, continues reaction 4 hours; The solution cooling under constantly stirring, adds the 50wt% aqueous ethanolic solution, centrifugation, and the 50wt% aqueous ethanolic solution washs, and obtains introducing the amphipathic starch subparticle of hydroxypropyl.Sem test shows, the particle diameter of hydroxypropylated starch ether is at 100～500nm, nuclear magnetic resonance spectrum (
1HNMR) show that molar substitution is not higher than 0.05.
Embodiment 4
Under agitation, the 16.2g wheat starch is dispersed in the 162g dimethyl sulfoxide (DMSO), 100～120 ℃ were stirred 1～1.5 hour down, cool to 50～60 ℃ then, the concentration that adds starch weight 1%～5% is the glutaraldehyde water solution of 40wt%, continue to stir 1 hour, the starch pasty state solution that obtains being translucent, starch disperses wherein with subparticle.Earlier solution for vacuum is dewatered, then under 50～60 ℃, add Octadecyl chloride (with the amount of substance ratio of starch be 0.1～0.3:1), continue to stir 8～10 hours, during constantly drip triethylamine (amount of substance of triethylamine and Octadecyl chloride is than being 1:1), solution temperature is reduced to 18～25 ℃ then, under constantly stirring, add the 50wt% aqueous ethanolic solution, centrifugation, with the washing of 50wt% aqueous ethanolic solution, obtain introducing the amphipathic starch subparticle of stearyl.Scanning electron microscope (SEM) test shows, the particle diameter of octadecyl esterification starch be at 100～500nm, nuclear magnetic resonance spectrum (
1HNMR) show that molar substitution is not higher than 0.05.
Embodiment 5
At first, be the starch subparticle dispersion liquid of 16.2g according to embodiment 1 preparation W-Gum dry weight, add and be equipped with in the 1000ml there-necked flask of prolong, stir add down vinylbenzene (with the ratio of the amount of substance of starch be 0.1～0.5:1), 150mgNaHCO
3Add in the flask, bath temperature keeps 40 ℃, feeds N
2, behind the 10min, adding 250mg Sodium dodecylbenzene sulfonate (SDBS), 20mg Potassium Persulphate (KPS) rises to 55～60 ℃ with bath temperature, and stopped reaction after 8 hours is cooled to room temperature.With the centrifugation of gained emulsion, use toluene wash, obtain the subparticle of the amphipathic starch derivant of grafted polystyrene.Scanning electron microscope (SEM) test shows, the particle diameter of polystyrene graft starch subparticle is seen Fig. 3 at 100～300nm, nuclear magnetic resonance spectrum (
1HNMR) show that the mol ratio of graft phenylethene and starch is lower than 0.05.
Embodiment 6
The 16.2g W-Gum is dispersed in the water, weight concentration is 8%, 80～100 ℃ were stirred 0.5～1 hour down, the concentration that adds starch weight 2% then is the glutaraldehyde water solution of 40wt%, continue to stir 1 hour, the starch pasty state solution that cooling obtains being translucent, the grain breakage of microscopic examination ative starch obtains the starch subparticle.When bath temperature keeps 40 ℃, stir add down vinylbenzene (with the ratio of the amount of substance of starch be 0.1～0.5:1), 150mgNaHCO
3Add in the flask, feed N
2, behind the 10min, adding 250mg Sodium dodecylbenzene sulfonate (SDBS), 20mg Potassium Persulphate (KPS) rises to 55～60 ℃ with bath temperature, and stopped reaction after 8～12 hours is cooled to room temperature.With the centrifugation of gained emulsion, use toluene wash, obtain the subparticle of the amphipathic starch derivant of grafted polystyrene.Scanning electron microscope (SEM) test shows, the particle diameter of polystyrene graft starch subparticle be at 50～500nm, nuclear magnetic resonance spectrum (
1HNMR) show that the mol ratio of graft phenylethene and starch is lower than 0.05.
Embodiment 7
Press the pasty state solution of embodiment 6 preparation W-Gums, then in room temperature, (with the ratio of the amount of substance of starch is 0.1～0.5:1) to add in the prepared starch pasty liquid, stirs 0.5 hour, until mixture is stirred with vinyl acetate; Again 250mg yellow soda ash is added in the there-necked flask, and beginning feeds nitrogen (N in flask
2); Stir after 10 minutes, add 20～30mg initiator potassium persulfate (K
2S
2O
8), add 250～300mg Sodium dodecylbenzene sulfonate (SDBS) after 10 minutes; Slowly the rising bath temperature reaches 55～60 ℃ until temperature, keep this temperature to make reactant continue reaction 8～12 hours, when being cooled to 20 ℃, with the centrifugation of gained emulsion, with the washing of 70wt% aqueous ethanolic solution, obtain the subparticle of the amphipathic starch derivant of grafting polyvinyl acetate (PVA).Scanning electron microscope (SEM) test shows, the particle diameter of polyvinyl acetate (PVA) graft starch subparticle be at 50～500nm, nuclear magnetic resonance spectrum (
1HNMR) show that the mol ratio of grafting vinyl acetate and starch is lower than 0.05.
Claims (7)
1. amphiphilic starch derivative fine particles, it is characterized in that: on the part of hydroxyl of starch polymer, be connected to hydrophobic group, or partially grafted copolymerization lipophilicity macromolecular chain, make the starch derivative fine particles while possess hydrophilic property and oil loving amphiphilic that obtains;
Described amphiphilic starch derivative fine particles particle diameter is at 50～500nm;
The described hydrophobic group that is connected on the part of hydroxyl of starch polymer is C
2～C
18Carbalkoxy, benzyl or C
3～C
18Hydroxyalkyl;
The described copolymerization lipophilicity macromolecular chain that is grafted with on starch polymer is polystyrene or polyvinyl acetate (PVA).
2. amphiphilic starch derivative fine particles according to claim 1 is characterized in that: described starch is one or more the mixture in W-Gum, wheat starch, sorghum starch, yam starch or the tapioca (flour).
3. amphiphilic starch derivative fine particles according to claim 1 is characterized in that: described amphipathic starch derivant comprises C
2～C
18Alkyl esterification starch, benzyl starch, C
3～C
18Hydroxyalkyl starch ether, grafted polystyrene starch or grafting polyvinyl acetate (PVA) starch;
Described starch is one or more the mixture in W-Gum, wheat starch, sorghum starch, yam starch or the tapioca (flour).
4. the preparation method of an amphiphilic starch derivative fine particles according to claim 1 is characterized in that, adopts the method for in-situ modified prepared amphiphilic starch derivative fine particles may further comprise the steps:
(1) starch is scattered in carries out acid hydrolysis in the acid, stir, through centrifugation, washing obtains the starch subparticle; Or starch obtained starch solution in the water-soluble or dimethyl sulfoxide solvent, and add the linking agent glutaraldehyde water solution, stir, obtain the starch subparticle;
(2) the starch subparticle that step (1) is obtained mixes with properties-correcting agent, wherein properties-correcting agent is 0.1～0.5: 1 with the amount of substance ratio of starch, stir, the original position radical reaction takes place, obtain amphiphilic starch derivative fine particles through centrifugation on starch subparticle surface; Or
The starch subparticle that step (1) is obtained mixes with properties-correcting agent and initiator, wherein properties-correcting agent is 0.1～0.5: 1 with the amount of substance ratio of starch, stir, the free radical grafting copolymerization reaction takes place, obtain amphiphilic starch derivative fine particles through centrifugation on starch subparticle surface.
5. method according to claim 4, it is characterized in that: described starch is scattered in carried out acid hydrolysis in the acid, be that starch is scattered in the aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid that concentration is 1.5～3mol/L, 30～50 ℃ of stirrings, obtain the starch subparticle through centrifugation, washing again.
6. method according to claim 4, it is characterized in that: described the starch starch solution that obtains soluble in water, be with the starch dispersed with stirring in water, concentration is 1wt%～15wt%, 80～100 ℃ are stirred down, the concentration that adds starch weight 1%～5% then is the glutaraldehyde water solution of 40wt%～60wt%, continues to stir the starch pasty state solution that obtains being translucent;
Described starch is dissolved in obtains starch solution in the dimethyl sulfoxide (DMSO), be with the starch dispersed with stirring in dimethyl sulfoxide solvent, concentration is 5wt%～10wt%, 100～120 ℃ are stirred down, the concentration that adds starch weight 1%～5% then is the glutaraldehyde water solution of 40wt%～60wt%, continue to stir the starch pasty state solution that obtains being translucent.
7. method according to claim 4 is characterized in that: described properties-correcting agent is aceticanhydride, C
2～C
18Alkyl acyl chloride, benzyl chloride, C
3～C
18Alkyl epoxide, vinylbenzene or vinyl acetate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011035978A1 (en) | 2009-09-23 | 2011-03-31 | Basf Se | Oligosaccharides and their preparation by acidic hydrolysis of starch |
| CN102199222A (en) * | 2010-03-26 | 2011-09-28 | 中国石油大学(北京) | Amphiphilic starch and preparation method thereof |
| CN102161729B (en) * | 2011-02-25 | 2013-01-16 | 上海交通大学 | Preparation method of water-soluble polysaccharide/hydrophobic monomer formed nanoparticles |
| CN103232550A (en) * | 2013-05-11 | 2013-08-07 | 郑桂富 | Preparation method of benzyl starch |
| CN103554564A (en) * | 2013-11-18 | 2014-02-05 | 常州化学研究所 | Preparation method of grafted starch modified rubber |
| KR101801931B1 (en) | 2016-01-19 | 2017-11-28 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
| CN106832342B (en) * | 2016-12-14 | 2018-12-25 | 北京化工大学 | A kind of preparation method of the aldehyde hydrazine cross-linking type injectable PNIPAM hydrogel of nano-starch particle reinforcement |
| CN108610430A (en) * | 2018-05-14 | 2018-10-02 | 南通通地生物技术有限公司 | A kind of preparation method of nanometer of rice starch |
| CN111554930B (en) * | 2020-05-08 | 2021-08-27 | 珠海冠宇电池股份有限公司 | Binder and lithium ion battery containing same |
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