CN111100245A - Modified thermoplastic starch and preparation method and application thereof - Google Patents
Modified thermoplastic starch and preparation method and application thereof Download PDFInfo
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- CN111100245A CN111100245A CN201811248739.9A CN201811248739A CN111100245A CN 111100245 A CN111100245 A CN 111100245A CN 201811248739 A CN201811248739 A CN 201811248739A CN 111100245 A CN111100245 A CN 111100245A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention relates to modified thermoplastic starch and a preparation method and application thereof, and mainly solves the technical problems that the continuity of the preparation process of the thermoplastic starch is poor, granules obtained by preparation are easy to adhere and agglomerate due to the precipitation of a plasticizer, the subsequent use is influenced, and the performance stability is poor in the prior art. The modified thermoplastic starch comprises the following components in parts by weight: (1) raw material starch: 55-85 parts; (2) plasticizer: 15-45 parts of a solvent; (3) reactive monomers: 1-20 parts; (4) initiator: 0.05-1 part; and/or the product generated by the reaction between the components, thereby better solving the problem and being applicable to the industrial production of the thermoplastic starch modified material.
Description
Technical Field
The invention relates to modified thermoplastic starch and a preparation method and application thereof.
Background
Starch is also a degradable natural polymer with high annual yield, widely exists in seeds and tubers of plants, about 15 percent of starch is contained in potatoes, about 60 percent of starch is contained in wheat and up to 75 percent of starch is contained in rice, and the starch is mainly used in glue, paste, paper making and textile industries besides being used as food and animal feed for human beings. The starch is a natural polymer which is obtained by converting carbon dioxide and water in the atmosphere into plants through photosynthesis, so that the carbon element in the starch belongs to recently fixed carbon and is different from carbon elements fixed before millions of years in fossil fuels such as petroleum or coal and petrochemical products thereof, and the carbon elements fixed at different periods can pass through14And C isotope calibration method. Due to the differences, the bio-based polymer material prepared based on the biomass raw material has the advantage of low carbon of the raw material compared with the petroleum-based polymer material, and the green low-carbon polymer material can be produced by adopting the production process with low energy consumption and low carbon emission. In view of such considerations, natural polymers including cellulose, hemicellulose, lignin, starch, chitin, and the like, and derivatives thereof have received wide attention in the world to develop high-quality green, low-carbon, and environmentally-friendly materials. The wide application of the green low-carbon material confirmed by Life Cycle Assessment (Life Cycle Assessment) is helpful for supporting green production and green Life style, and contributes to reducing the content of greenhouse effect gases (carbon dioxide and the like) in the atmosphere and relieving global climate change.
Although starch has the advantage of low carbon in raw materials, it is used in small quantities as a plastic because of the strong hydrogen bonding between molecules in starch, which makes it melt above its thermal decomposition temperature without thermoplasticity. In order to overcome the defects, researchers have successfully developed thermoplastic starch materials through efforts. The thermoplastic starch is thermoplastic natural macromolecule with lowest cost, and the starch thermal plastification mainly comprises adding micromolecular plasticizer into raw starch to reduce the flow temperature of the starch, thereby achieving the effect of thermal plastification.
The strength and extensibility of the thermoplastic starch are closely related to the amount of plasticizer used, with higher plasticizer contents providing lower strength and higher extensibility of the thermoplastic starch, and conversely lower plasticizer contents providing higher strength and lower extensibility of the thermoplastic starch. However, due to the problem that the plasticizer is easy to separate out after the content of the plasticizer in the thermoplastic starch is high, the content of the plasticizer in the common thermoplastic starch is in a certain proper range, and the thermoplastic starch generally belongs to a brittle material.
In combination with the above situation, the invention discloses a modified thermoplastic starch and a preparation method and application thereof. The modified thermoplastic starch is prepared by adding raw material starch, plasticizer, reactive monomer, initiator and auxiliary agent into a double-screw extruder according to the principle of solid-liquid separation, and performing mixing, plasticizing, reaction, extrusion, cooling and granulation. According to the modified thermoplastic starch prepared by the method, solid and liquid materials are fed separately, the steps are simplified, and the adjustable range of the plasticizer is enlarged; the hydrogen bonds among starch molecules are weakened after modification, the dosage of a plasticizing agent required by thermal plasticizing is reduced, and the possibility that the subsequent use is influenced by particle adhesion due to plasticizer precipitation is reduced; the whole process is continuous and stable, high-efficiency and high-yield, has good practicability and economy, and can be used for industrial production.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the continuity of the preparation process of the thermoplastic starch is poor, the prepared granules are easy to adhere and agglomerate due to the precipitation of the plasticizer, the subsequent use is affected and the performance stability is poor in the prior art, and the modified thermoplastic starch is provided, the hydrogen bonds among starch molecules after modification are weakened, the dosage of the plasticizer required by thermoplastic modification is reduced, and the possibility that the subsequent use is affected due to the particle adhesion caused by the precipitation of the plasticizer is reduced.
The second technical problem to be solved by the invention is to provide a preparation method of modified thermoplastic starch corresponding to the first technical problem, the method comprises the steps of adding required amount of raw material starch, plasticizer, reactive monomer, initiator and auxiliary agent into a double-screw extruder by adopting the principle of solid-liquid separation, and mixing, plasticizing, reacting, extruding, cooling and granulating to obtain the modified thermoplastic starch.
The invention also provides an application method of the modified thermoplastic starch corresponding to the technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the modified thermoplastic starch comprises the following components in parts by weight:
(1) raw material starch: 55-85 parts;
(2) plasticizer: 15-45 parts of a solvent;
(3) reactive monomers: 1-20 parts;
(4) initiator: 0.05-1 part;
and/or a product of a reaction between the above components.
In the technical scheme, the raw material starch is preferably, but not limited to, one or a compound of more of corn starch, tapioca starch, sweet potato starch, mung bean starch, potato starch, wheat starch, water chestnut starch, lotus root starch, rice starch and the like.
In the above technical solution, the plasticizer is preferably but not limited to one or more of water, ethanol, glycerol, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, urea, formamide, and the like.
In the above technical solution, the reactive monomer is preferably at least one of compounds having a group such as a hydroxyl group, a carboxyl group, a carbonyl group, an ester group, an amino group, a mercapto group, a sulfonic acid group, an ether bond, a halogen, a peptide bond, an acid anhydride bond, etc., and further having an unsaturated carbon-carbon double bond; more preferably at least one of maleic anhydride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide and the like; further preferably at least one of maleic anhydride, acrylate and methacrylate compounds.
In the above technical solution, the initiator is a radical initiator, i.e. an organic compound capable of decomposing to generate radicals under a certain condition, preferably: at least one of acyl peroxide, alkyl peroxide, perester, alkyl hydroperoxide, ketone peroxide and azo compound; more preferably: at least one of benzoyl peroxide, azodicarbonic diisobutyronitrile, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, benzoic peroxide, 2, 5-dimethyl-2, 5-di-t-butyl peroxy hexane, and the like; further preferably: at least one of benzoyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide and the like.
In the above technical solution, the components preferably further comprise: (5) auxiliary agent: 0 to 20 parts of
In the above technical solution, the kind of the auxiliary agent includes, but is not limited to, at least one of a compatibility agent, a stabilizer, an antioxidant, a slipping agent, an adhesive, and the like.
In order to solve the second technical problem, the invention adopts the technical scheme that: adding raw material starch, plasticizer, reactive monomer, initiator and auxiliary agent with required amount into a double-screw extruder according to the principle of solid-liquid separation, and mixing, plasticizing, reacting, extruding, cooling and granulating to obtain the modified thermoplastic starch.
In the technical scheme, the solid-liquid separation principle is that solid and liquid with mass percent more than 2 percent of the total mass of all components are fed separately; solids having a mass percent of not more than 2% may be fed together with the liquid if they are uniformly and stably dispersed in the liquid, or may be fed separately from the liquid if they are not uniformly and stably dispersed in the liquid.
In the technical scheme, the solid-liquid separation principle is that different solids are fed optionally and respectively or fed after premixing; the different liquids which can be uniformly and stably dispersed are optionally fed separately or after premixing, and the different liquids which cannot be uniformly and stably dispersed are fed separately.
In the above technical solution, the processing temperature of the twin-screw extruder is preferably 100 ℃ to 400 ℃, more preferably 110 ℃ to 250 ℃, and still more preferably 120 ℃ to 180 ℃.
In the above technical solution, the screw rotation speed of the twin-screw extruder is preferably 20rpm to 1500rpm, more preferably 50rpm to 1000rpm, and even more preferably 100rpm to 300 rpm.
In order to solve the third technical problem, the invention adopts the technical scheme that: a method for applying a modified thermoplastic starch according to any one of the preceding technical solutions.
In the above technical solutions, the application method is not particularly limited, and those skilled in the art can use the method according to the prior art, for example, but not limited to, the method is used in the fields of film making, injection molding, spinning, plastic sucking, extrusion, and the like after being blended with other thermoplastic polymer materials.
In the above technical solution to solve the technical problem, the preferable solution is as follows:
1. thermoplastic starch
Starch is a natural polysaccharide with high annual yield and low price. The starch is in a solution or melt state, a plasticizer is added into the starch through a physical blending method, and the starch is mixed to reduce the interaction between starch molecules, so that the starch has thermoplasticity. The thermal plasticization process of starch in solution is roughly: dissolving starch and a proper amount of plasticizer in a solvent (usually water), heating and stirring to fully gelatinize the starch and completely disperse the starch and the plasticizer, and gradually evaporating the solvent to dryness to obtain the thermoplastic starch. The melt thermal plasticizing process of the starch comprises the following steps: starch and a proper amount of proper plasticizer are fully stirred and mixed in equipment such as an internal mixer, a single-screw extruder or a double-screw extruder in a melt state, and then the mixture is cooled and sliced to obtain the thermoplastic starch. Suitable temperatures for thermal plasticization of the starch melt include from about 80 ℃ to the starch thermal decomposition temperature.
Suitable classes of starches for preparing the thermoplastic starch of the present invention include: corn starch, cassava starch, sweet potato starch, mung bean starch, potato starch, wheat starch, water caltrop starch, lotus root starch, rice starch and the like. Suitable plasticizers for preparing the thermoplastic starch of the present invention are: water, ethanol, glycerol, sorbitol, ethylene glycol, urea, formamide, etc. The mass ratio of the plasticizer to the entire thermoplastic starch is 5% to 50%, and in order to achieve a sufficient plasticizing effect and prevent precipitation of the plasticizer, it is more preferably 15% to 40%, and still more preferably 20% to 35%.
One thermoplastic starch suitable for use in the present invention is thermoplastic corn starch obtained by melt plasticization with glycerol or glycerol and other non-glycerol compounds as plasticizers, the mass content of plasticizer in the thermoplastic starch being from about 10% to about 35%. The plasticizing process is carried out in a twin screw extruder, the temperature of the plasticizing zone is from about 80 ℃ to about 180 ℃, more preferably the temperature of the plasticizing zone is from about 100 ℃ to about 160 ℃, and the thermoplastic starch is air cooled, sliced, sealed and stored for later use.
2. Reactive monomer
The reactive monomer in the present invention is a vinyl compound, and the compound preferably includes, but is not limited to, the following groups in the molecule: hydroxyl, carboxyl, carbonyl, ester, amino, mercapto, sulfonic acid, ether bond, halogen, peptide bond, acid anhydride bond, etc. The reactive monomer can react with other components (mainly starch) in the blend under certain conditions, and then is grafted to other components through covalent bonds to play a role in modification.
The reactive monomer in the present invention is preferably at least one of maleic anhydride, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, acrylamide, methacrylamide and the like. More preferred reactive monomers are methacrylates, such as at least one of hydroxyethyl methacrylate (HEMA), Glycidyl Methacrylate (GMA), and the like.
In addition, the polarity of the reactive monomer can be selected as desired, for example, where high polarity is desired, a reactive monomer with a terminal hydroxyl group can be selected, such as hydroxyethyl methacrylate (HEMA); on the other hand, when the polarity is not required to be too high, monomers such as n-butyl (meth) acrylate and n-octyl (meth) acrylate can be selected.
3. Initiator
The initiator described in the present invention is a free radical initiator which under certain conditions can decompose an organic compound which generates free radicals, including but not limited to: acyl peroxides, such as Benzoyl Peroxide (BPO); alkyl (dialkyl) peroxides such as di-t-butylperoxide, di-cumylperoxide, 3, 5-trimethylcyclohexane-1, 1-diperoxy-t-butyl, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, and the like; peresters such as t-butyl peroxypivalate, t-butyl per-2-ethylhexanoate, t-butyl perbenzoate, peroxydodecanoic acid, etc.; alkyl hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, etc.; ketone peroxides, such as methyl ethyl ketone peroxide; azo compounds, such as Azobisisobutyronitrile (AIBN).
The initiator suitable for use in the present invention is preferably at least one of benzoyl peroxide, azobisisobutyronitrile, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, benzoic acid peroxide, 2, 5-dimethyl-2, 5-di-t-butyl-peroxy-hexane, and the like. More preferred initiators are at least one of benzoyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane.
4. Twin-screw extrusion processing of polymer materials
The double screw extruder is one of the most widely applied processing devices in the industry, has the characteristics of high shearing rate, strong mixing capability and the like, is mainly used in the fields of addition agent addition, melt chain extension and the like of high polymer materials, and can also be applied to some polymer forming fields by replacing different dies. The twin-screw extruder of the invention mainly provides heat and strong shearing action, thereby providing conditions for mixing and reacting raw material starch, plasticizer, reactive monomer, initiator and auxiliary agent.
The following two methods for preparing modified thermoplastic starch by continuous melt extrusion are suitable for the present invention: firstly, according to the raw material proportion, raw material starch and a plasticizer are mixed, extruded, cooled and granulated in a double-screw extruder to prepare thermoplastic starch, then the thermoplastic starch is mixed with a reactive monomer and an initiator, preferably an auxiliary agent, and the mixture is melted, reacted, extruded, cooled and granulated in the double-screw extruder to obtain modified thermoplastic starch; secondly, the preparation and modification processes of the thermoplastic starch are carried out in the same step, namely, all the components are added into a double-screw extruder together, and the modified thermoplastic starch is prepared by a one-step method through mixing, plasticizing, reacting, extruding, cooling and granulating.
Twin screw extruders suitable for use in the present invention include, but are not limited to: a Micro27 twin screw extruder manufactured by Leistritz, Germany, which has a switchable co/counter-rotating function; a co-rotating twin screw extruder model PolyLab, EuroLab, etc. manufactured by Thermo Fisher Scientific, USA; ZKMcc 18 co-rotating parallel twin screw extruder manufactured by Coperion, Germany, and the like. The processing temperature of the twin-screw extruder is preferably 100 ℃ to 400 ℃, more preferably 110 ℃ to 250 ℃, and still more preferably 120 ℃ to 180 ℃. The screw rotation speed of the twin-screw extruder is preferably 20rpm to 1500rpm, more preferably 50rpm to 1000rpm, and still more preferably 100rpm to 300 rpm.
The raw material starch, plasticizer and initiator used in the present invention have no carbonyl group, and only the reactive monomer contains a carbonyl group. In the Fourier transform Infrared (FT-IR) test, the carbonyl was at about 1725cm-1There is a significant absorption signal at wavenumber and therefore it is possible to pass the FTIR test on the modified starch after purification if it is at 1725cm-1And an absorption peak is formed near the wave number, which indicates that the reactive monomer is successfully grafted in the modified starch.
By adopting the technical scheme of the invention, according to the principle of solid-liquid separation, the modified thermoplastic starch prepared by continuous melt extrusion in a double-screw extruder is successfully grafted with the reactive monomer onto the thermoplastic starch molecules, and the thermoplastic starch is stored for 30 days without adhesion and agglomeration among granules, the preparation process is continuous and stable, the high efficiency and the high yield are realized, the practicability and the economical efficiency are good, and the better technical effect is obtained.
Drawings
Figure 1 is a FT-IR spectrum of modified TPS and purified modified TPS.
Figure 2 schematic diagram of modified TPS structure.
The invention carries out performance measurement according to the following method:
fourier transform Infrared (FT-IR) test: the test was performed on FT-IRSpectrometry Frontier series from PerkinElmer, USA, in reflectance mode, using a Universal ATR Sampling Access Accessory. The processing software is Perkinelmer Spectrum, and the range of the test wave number is 4000-650 cm-1Each test is scanned 4 times with a resolution of 2cm-1. The FT-IR test samples in the invention are basically all powder, and the common sample preparation method comprises the following steps: the powder is ground by using a grinding bowl as much as possible, and then kept for 1min under 10MPa in a Specac hydraulic press to obtain compact sample pieces with the diameter of about 10mm and the thickness of 1-2 mm for the FT-IR test.
Film tensile test: the measurement was carried out according to ISO 527-3 using a model 3344 materials tester from INSTRON with the processing software Bluehill version 2.31. The film was cut into type 5 according to ISO 527-3 standard, the film direction was Machine Direction (MD), and the film was left in a Bluepard BPS-100CB constant temperature and humidity cabinet (temperature 23 ℃ C., relative humidity 50%) of Shanghai-Hengsciences instruments Ltd for 24 hours. During testing, the initial clamp spacing was 75mm, the test pull rate was 10mm/min, and each sample was tested at least 5 times, and the average was taken.
The invention is further illustrated by the following specific examples, without restricting the inventive content to the scope shown by the examples.
Detailed Description
The present invention is specifically described by the following examples. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
Comparative example 1
The starch used in the invention is edible corn starch produced by Jilin company of Chinese food, and the glycerol is analytically pure glycerol of chemical reagents of national drug group. The two raw materials were uniformly melt-mixed, plasticized and granulated by means of a Micro27 co-rotating twin-screw extruder (screw diameter 27mm, length-diameter ratio 40) from Leistritz, Germany to give a thermoplastic Starch (TPS). The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 60 ℃,80 ℃,100 ℃,120 ℃,120 ℃,120 ℃,120 ℃,120 ℃,120 ℃ and 120 ℃, and the screw rotation speed is set at 150 rpm. Corn starch is fed to the 1 st section of a double-screw extruder by a K-CL-24-KT20 type weight loss feeder of the Switzerland K-Tron company, wherein the feeding speed is as follows: 7600 g/hr. The glycerol is injected into a double-screw extrusion section 2 by an HLB-1008 type constant flow plunger pump produced by a Yanshan instrument general factory in east Taiwan city through a liquid charging opening, and the flow rate is as follows: 2400 g/hr. After the operation has stabilized, the twin-screw extrusion pressure is 47-56bar and the torque is about 49%. The bush that this extruder was furnished with has two diameters to be 4 mm's circular export, and spline stretchability is relatively poor, extrudes the back from the bush, behind about 3 m's air-cooled conveyer belt, cuts into the cylindrical particle that length is about 5mm with the pelleter, collects the encapsulation and uses for use. It was found that 30 minutes after pelletizing, the pellets had significantly agglomerated.
[ example 1 ]
The reactive monomer used in the present invention, hydroxyethyl methacrylate (HEMA), is an analytically pure product of tokyo chemical corporation (TCI), the initiator, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane (bis-dipenta), is an analytically pure product of bailingwei science and technology ltd, and bis-dipenta is dispersed in HEMA to prepare a solution with a volume fraction of 5%. A Micro27 type co-rotating double screw extruder (screw diameter is 27mm, length-diameter ratio is 40) of Leistritz company in Germany is selected to mix raw material starch, glycerol and a solution of HEMA of dipenta, plasticization, reaction and extrusion to prepare the grafted modified thermoplastic starch (mTPS). The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 80 ℃,100 ℃,120 ℃,140 ℃,160 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and 180 ℃, the screw speed being set at 100 rpm. Corn starch is fed to the 1 st section of a double-screw extruder by a K-CL-24-KT20 type weight-loss feeder of the Switzerland K-Tron company, wherein the feeding speed is as follows: 3600g/hr, injecting glycerin into a double-screw extrusion section 2 from an HLB-1008 constant flow plunger pump produced by a Yanshan instrument general factory of Tokyo city through a liquid charging port, wherein the flow rate is as follows: 1200 g/hr. The twenty-five HEMA solution was injected into the 4 th section of the twin screw extruder using an Optos Pump 2LMP metering Pump from Eldex Laboratories, USA, at a flow rate of: about 231 mL/hr. After running stabilization, the twin-screw extrusion pressure is 60-65bar and the torque is about 27%. The bush that this extruder was furnished with has two diameters to be 4 mm's circular export, and the spline has better stretchability, extrudes the back from the bush, behind the forced air cooling conveyer belt of about 3m, cuts into the cylindrical particle that length is about 5mm with the pelleter, collects the encapsulation and reserve. The pellets were found to be slightly darker in color than in comparative example 1, and substantially no agglomeration of the pellets occurred.
[ example 2 ]
The above-mentioned HEMA and hydroxyethyl methacrylate (HEMA), which is a reactive monomer used in the present invention, was an analytically pure product of tokyo chemical corporation (TCI), and the initiator, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane (bis-penta), was an analytically pure product of bainwei technologies ltd, and the bis-penta was dispersed in HEMA to prepare a solution with a volume fraction of 8%. A Micro27 type co-rotating double screw extruder (screw diameter 27mm, length-diameter ratio 40) of Leistritz company in Germany is selected to mix, plasticize, react and extrude raw material starch, glycerol and a solution of HEMA of Bidao-Wu to prepare the graft modified thermoplastic starch. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 is used for feeding only and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 80 ℃,100 ℃,120 ℃,140 ℃,160 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and 180 ℃, the screw speed being set at 100 rpm. Corn starch is fed to the 1 st section of a double-screw extruder by a K-CL-24-KT20 type weight-loss feeder of the Switzerland K-Tron company, wherein the feeding speed is as follows: 3600g/hr, injecting glycerin into a double-screw extrusion section 2 from an HLB-1008 constant flow plunger pump produced by Yanshan instrument general works of Tokyo city through a liquid charging port, wherein the flow rate is as follows: 1200 g/hr. The twenty-five HEMA solution was injected into the 4 th section of the twin screw extruder using an Optos Pump 2LMP metering Pump from Eldex Laboratories, USA, at a flow rate of: about 460 mL/hr. After the operation is stabilized, the twin-screw extrusion pressure is 55-60bar and the torque is about 25%. The bush that this extruder was furnished with has two diameters to be 4 mm's circular export, and the spline has better stretchability, extrudes the back from the bush, behind about 3 m's air-cooled conveyer belt, cuts into the cylindrical particle that length is about 5mm with the pelleter, collects the encapsulation and reserve. It was found that the pellet color was similar to that of example 1, and substantially no agglomeration of the pellets occurred.
[ example 3 ]
The initiator used in the invention, Benzoyl Peroxide (BPO), is a 98% pure product of Bailingwei science and technology Limited. BPO was dispersed in HEMA as described above to make a 5% volume fraction solution. The graft modified thermoplastic starch was prepared by mixing, plasticizing, reacting, extruding the above mentioned HEMA (5% volume fraction) of corn starch, glycerol and BPO directly in a co-rotating twin screw extruder (screw diameter 27mm, length to diameter ratio 40) of type Micro27 from Leistritz, germany. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 60 ℃,80 ℃,120 ℃,140 ℃,140 ℃,140 ℃,140 ℃,140 ℃,140 ℃ and 140 ℃, the screw speed is set at 100 rpm. Corn starch is fed to the 1 st section of a double-screw extruder by a K-CL-24-KT20 type weight-loss feeder of the Switzerland K-Tron company, wherein the feeding speed is as follows: 3600g/hr, injecting glycerin into a double-screw extrusion section 2 from an HLB-1008 constant flow plunger pump produced by a Yanshan instrument general factory of Tokyo city through a liquid charging port, wherein the flow rate is as follows: 1200 g/hr. The HEMA solution of BPO was injected into the 4 th section of the twin screw extruder using an Optos Pump 2LMP metering Pump from Eldex Laboratories, USA, at a flow rate of: about 231 mL/hr. After the operation is stabilized, the twin-screw extrusion pressure is 40-45bar and the torque is about 12%. The bush that this extruder was furnished with has two diameter to be 4 mm's circular export, and the spline has better stretchability, extrudes the back from the bush, behind the forced air cooling conveyer belt of about 3m, cuts into the cylindrical particle that length is about 5mm with the pelleter, collects the encapsulation and reserve. The pellet color was found to be close to that of comparative example 1, and substantially no agglomeration of the pellets occurred.
[ example 4 ]
The reactive monomer used in the invention, n-butyl methacrylate (nBMA), is an analytically pure product of a national pharmacy test. The solution with volume fraction of 5% was prepared by dispersing the bis-di-penta in nBMA. A Micro27 type co-rotating double screw extruder (screw diameter 27mm, length-diameter ratio 40) of Leistritz company in Germany is selected to mix, plasticize, react and extrude raw materials of starch, glycerol and a solution of nBMA of dipenta to prepare the graft modified thermoplastic starch. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 80 ℃,100 ℃,120 ℃,140 ℃,160 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and 180 ℃, the screw speed being set at 100 rpm. Feeding corn starch to the 1 st section of a double-screw extruder by using a K-CL-24-KT20 type weight-loss feeding machine of K-Tron company of Switzerland at the feeding speed of: 3600g/hr, injecting glycerin into a double-screw extrusion section 2 from an HLB-1008 constant flow plunger pump produced by a Yanshan instrument general factory of Tokyo city through a liquid charging port, wherein the flow rate is as follows: 1200 g/hr. The HEMA solution of duyiwu was injected into the 4 th section of the twin-screw extruder using the Optos Pump 2LMP metering Pump of Eldex Laboratories, usa at the flow rate: about 231 mL/hr. After the operation is stabilized, the twin-screw extrusion pressure is 58-63bar and the torque is about 28%. The die matched with the extruder is provided with two circular outlets with the diameters of 4mm, the sample strips have better stretchability, and after being extruded from the die and passing through an air-cooled conveyor belt with the diameter of about 3m, the sample strips are cut into cylindrical particles with the length of about 5mm by a granulator and are collected and packaged for later use. It was found that the pellet color was similar to that of example 1, and substantially no agglomeration of the pellets occurred.
Comparative example 2
The corn starch, glycerin, HEMA and dipenta described above were mixed as 36: 12: 2.3: 1, and then the mixture is mixed, plasticized, reacted and extruded in a Micro27 type co-rotating twin-screw extruder (screw diameter 27mm, length-diameter ratio 40) of Leistritz company of Germany to prepare the graft modified thermoplastic starch (mTPS). The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 80 ℃,100 ℃,120 ℃,140 ℃,160 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and 180 ℃, the screw speed being set at 100 rpm. Feeding the 1 st section of the double-screw extruder by using a K-CL-24-KT20 model weight loss type feeding machine of Switzerland K-Tron company at the following feeding speed: 8000 g/hr. The liquid wetting trace is found on the wall of the charging barrel, the bridging accumulation risk exists in the materials in the charging barrel (the condition is particularly obvious in a single-screw conveying feeder), the bridging accumulation is easy to occur when the materials enter a feeding port, the normal operation is influenced, and the condition is particularly obvious when the content of the plasticizing agent is higher. The pellet color was similar to that of example 1, and substantially no pellet agglomeration occurred.
Comparative example 3
The pellets of comparative example 1 and examples 1 to 4 described above were each subjected to the following treatments: firstly, placing the mixture in a plastic bag, sealing the bag after vacuumizing, and placing the bag for 3 days; secondly, placing the mixture in a plastic bag, sealing the plastic bag at normal pressure, and placing the plastic bag for 30 days. It was observed that the pellets of comparative example 1 were significantly agglomerated after storage by both methods, making it difficult to separate the pellets one by one, whereas the pellets of examples 1-4 were substantially free of agglomeration. Analysis of the above reasons is that the plasticizer is more easily separated out from the particles of comparative example 1, resulting in the granules having surfaces that are wet and sticky, whereas the granules of examples 1 to 4 have less tendency to aggregate with each other and repel the plasticizer because the starch is modified and the intermolecular hydrogen bonds thereof are weakened, and thus the particles are not significantly adhered to each other.
[ example 5 ]
The polybutylene succinate (PBS) used in the invention is produced by showa electrician and has the brand number of
Product of MD 1001. The PBS and the particles of example 1 were extruded through a twin-screw extruder in the same direction from Micro27, Leistritz, GermanyThe PBS/mTPS mixed particles can be obtained by melting, mixing, extruding, cooling and granulating the raw materials (the diameter of a screw is 27mm, the length-diameter ratio is 40) by a machine. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 is used for feeding only and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 60 ℃,80 ℃,100 ℃,120 ℃,140 ℃,150 ℃,150 ℃,150 ℃ and 140 ℃, and the screw rotation speed is set at 150 rpm. Two particle-type weight-loss feeders of K-Tron corporation were used to feed PBS particles and the particles of example 1 to the twin-screw extruder at stage 1, respectively, at PBS: 4000g/hr, example 1 particles: 3000 g/hr. After running stably, the pressure of the twin-screw extrusion is 60-66bar, and the torque is 50-54% of the maximum value. The mouth mold matched with the extruder is provided with two circular outlets with the diameters of 4mm, the sample strips are extruded from the mouth mold and are cut into cylindrical particles with the length of about 5mm by a granulator after passing through an air-cooled conveyor belt with the length of 5m, and the cylindrical particles are collected, dried and packaged for later use.
Comparative example 4
The PBS particles and the particles of comparative example 1 are melted, mixed, extruded, cooled and granulated in a Micro27 co-rotating twin-screw extruder (screw diameter 27mm, length-diameter ratio 40) of Leistritz company, Germany, to obtain PBS/TPS mixed particles. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 is used for feeding only and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 60 ℃,80 ℃,100 ℃,120 ℃,140 ℃,150 ℃,150 ℃,150 ℃ and 140 ℃, and the screw rotation speed is set at 150 rpm. Two particle type weight loss feeders of K-Tron company were used to feed PBS particles and particles of comparative example 1 to the 1 st stage of the twin screw extruder, respectively, at a feed rate of PBS: 4000g/hr, comparative example 1 particles: 3000g/hr (due to the severe agglomeration of particles, although it has been manually sieved, there are some large particles, thus affecting the feeding accuracy). After the operation is stable, the pressure of the twin-screw extrusion is 60-64bar, and the torque is 46-52% of the maximum value. The mouth mold matched with the extruder is provided with two circular outlets with the diameters of 4mm, the sample strips are extruded from the mouth mold and are cut into cylindrical particles with the length of about 5mm by a granulator after passing through an air-cooled conveyor belt with the length of 5m, and the cylindrical particles are collected, dried and packaged for later use.
[ example 6 ]
HAAKE manufactured by Thermo Fisher Scientific Inc. of USA is applied to two kinds of particles of example 5 and comparative example 4TMCast films were prepared on a Rheomex OS single screw extruder having a screw diameter of 19mm and a length to diameter ratio of 25 equipped with a 3:1 standard metering screw, made from HAAKETMPolyLabTMOS torque rheometer platform control. The extruder is provided with three heating sections, the numbers of the heating sections from a feed inlet to an outlet are respectively 1-3, a casting mouth die with the width of 150mm and the opening height of 0.6mm is configured, and the set temperatures of the single-screw extruder and the mouth die are respectively as follows: the film is prepared by drawing and stretching at 150 ℃,160 ℃,160 ℃ and 160 ℃ through three subsequent guide rollers at 20 ℃. By adjusting the rotation speed of the roller, the two kinds of particles can be made into a uniform film with the thickness of 30-50 mu m.
The elongation at break and the strength at break of the film of example 5 were found to be respectively: (430. + -.30)% and 20. + -.2 MPa, while comparative example 4 corresponds to a film having elongation at break and strength at break respectively: (410. + -. 70)% and 19. + -. 5 MPa. The above results show that, although the films corresponding to example 5 and comparative example 4 do not differ much in average value, the error in the test data of the film corresponding to example 5 is significantly lower than that of the film corresponding to comparative example 4, indicating that the properties of the film corresponding to example 5 are more uniform and stable and that the properties of the pellets of example 5 are also more uniform and stable in side reaction.
[ example 7 ]
The five total particles of comparative example 1 and examples 1-4 above were subjected to the FT-IR test described above. Samples of the modified thermoplastic starch samples, examples 1-4, were previously purified to try to remove ungrafted monomer and homopolymer formed by the self-polymerization of the monomer. The purification method of examples 1-3 was as follows: dispersing 1g of modified thermoplastic starch particles in 100mL of deionized water solution, fully stirring to form a uniform solution basically, adding 100mL of absolute ethyl alcohol, fully stirring, centrifuging to remove supernatant, dispersing lower-layer solids by using 100mL of 50% ethanol aqueous solution, fully stirring, centrifuging to remove supernatant, repeating the processes for more than 3 times, collecting centrifuged lower-layer solids, drying, and measuring FT-IR. The purification method of example 4 is as follows: dispersing 1g of modified thermoplastic starch particles in 100mL of deionized water solution, fully stirring to form a substantially uniform solution, adding 100mL of Tetrahydrofuran (THF), fully stirring, centrifuging to remove supernatant, pre-dispersing lower-layer solid with about 5mL of deionized water, adding 100mL of THF in a stirring state, fully stirring and dispersing, centrifuging to remove supernatant, repeating the above processes for at least 3 times, collecting centrifuged lower-layer solid, drying, and measuring FT-IR.
The raw material starch, plasticizer and initiator used in the present invention have no carbonyl group, and only the reactive monomer contains a carbonyl group. In the Fourier transform Infrared (FT-IR) test, the carbonyl was at about 1725cm-1There is a significant absorption signal at the wavenumber, and therefore it is possible to pass the FT-IR test on the modified starch after purification, if it is at 1725cm-1An absorption peak is present near the wave number, indicating that the modified starch is successfully grafted with the reactive monomer, and the stronger the signal, the larger the grafting amount of the reactive monomer.
The FT-IR test results for comparative example 1 and examples 1-4 are shown in FIG. 1. As can be seen from the figure, 1725cm of the purified modified thermoplastic starch granules (examples 1 to 4)-1The characteristic absorption peaks of the left and right carbonyl groups (shown by the dotted line) were also present, but were not present in the unmodified thermoplastic starch (comparative example 1), indicating that the modified thermoplastic starch of the above-mentioned method was successful. The method provides a good way for expanding the application of the starch plastic, has good technical effect and great application potential.
Claims (10)
1. The modified thermoplastic starch comprises the following components in parts by weight:
(1) raw material starch: 55-85 parts;
(2) plasticizer: 15-45 parts of a solvent;
(3) reactive monomers: 1-20 parts;
(4) initiator: 0.05-1 part;
and/or a product of a reaction between the above components.
2. The modified thermoplastic starch as claimed in claim 1, wherein the raw starch is selected from one or more of corn starch, tapioca starch, sweet potato starch, mung bean starch, potato starch, wheat starch, water chestnut starch, lotus root starch, rice starch, etc.; the plasticizer is one or a compound of water, ethanol, glycerol, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, urea, formamide and the like.
3. The modified thermoplastic starch according to claim 1, wherein said reactive monomer is at least one of a compound having a hydroxyl group, a carboxyl group, a carbonyl group, an ester group, an amino group, a mercapto group, a sulfonic acid group, an ether bond, a halogen, a peptide bond, an acid anhydride bond group, and further having an unsaturated carbon-carbon double bond; more preferably at least one of maleic anhydride, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, acrylamide, methacrylamide and the like; further preferably at least one of maleic anhydride, acrylate and methacrylate compounds.
4. The modified thermoplastic starch of claim 1, wherein said initiator is a free radical initiator.
5. Modified thermoplastic starch according to claim 1, characterised in that the modified thermoplastic starch further comprises
(5) Auxiliary agent: 0 to 20 parts.
6. Modified thermoplastic starch according to claim 5, characterised in that the auxiliary agent is at least one of a compatibiliser, a stabiliser, an antioxidant, a slip agent, a binder.
7. A method for preparing a modified thermoplastic starch according to any one of claims 1 to 6, comprising the steps of:
adding raw material starch, plasticizer, reactive monomer, initiator and auxiliary agent with required amount into a double-screw extruder according to the principle of solid-liquid separation, and mixing, plasticizing, reacting, extruding, cooling and granulating to obtain the modified thermoplastic starch.
8. The process for preparing modified thermoplastic starch according to claim 7, wherein the solid-liquid separation principle is that solid and liquid are separately fed in a mass percentage of more than 2% of the total mass of all components; solids having a mass percentage of not more than 2% may be fed together with the liquid if they are uniformly and stably dispersed in the liquid, or may be fed separately from the liquid if they are not uniformly and stably dispersed in the liquid.
9. The method for preparing modified thermoplastic starch according to claim 7, wherein the solid-liquid separation principle is that different solids are optionally fed separately or fed after premixing; the different liquids which can be uniformly and stably dispersed are optionally fed separately or after premixing, and the different liquids which cannot be uniformly and stably dispersed are fed separately.
10. Use of a modified thermoplastic starch according to any one of claims 1 to 6.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358657A (en) * | 2020-11-26 | 2021-02-12 | 重庆和泰润佳股份有限公司 | Non-air-permeable biodegradable film and preparation method thereof |
| WO2023224593A1 (en) * | 2022-05-17 | 2023-11-23 | Общество С Ограниченной Ответствнностью "Биоинком" | Method for producing oligosaccharide copolymers |
| CN117143379A (en) * | 2023-10-27 | 2023-12-01 | 台州黄岩泽钰新材料科技有限公司 | Antibacterial starch degradable composite material and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060107945A1 (en) * | 2004-11-19 | 2006-05-25 | Board Of Trustees Of Michigan State University | Chemically modified plasticized starch compositions by extrusion processing |
| CN101412826A (en) * | 2008-11-28 | 2009-04-22 | 华南理工大学 | Rubber / modified starch composite material and preparation thereof |
| CN101792509A (en) * | 2010-03-30 | 2010-08-04 | 奇瑞汽车股份有限公司 | Thermoplastic modified starch materials and preparation method thereof |
| CN104892862A (en) * | 2015-06-26 | 2015-09-09 | 江南大学 | Starch based thermoplastic material and preparation method thereof |
-
2018
- 2018-10-25 CN CN201811248739.9A patent/CN111100245A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060107945A1 (en) * | 2004-11-19 | 2006-05-25 | Board Of Trustees Of Michigan State University | Chemically modified plasticized starch compositions by extrusion processing |
| CN101412826A (en) * | 2008-11-28 | 2009-04-22 | 华南理工大学 | Rubber / modified starch composite material and preparation thereof |
| CN101792509A (en) * | 2010-03-30 | 2010-08-04 | 奇瑞汽车股份有限公司 | Thermoplastic modified starch materials and preparation method thereof |
| CN104892862A (en) * | 2015-06-26 | 2015-09-09 | 江南大学 | Starch based thermoplastic material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358657A (en) * | 2020-11-26 | 2021-02-12 | 重庆和泰润佳股份有限公司 | Non-air-permeable biodegradable film and preparation method thereof |
| WO2023224593A1 (en) * | 2022-05-17 | 2023-11-23 | Общество С Ограниченной Ответствнностью "Биоинком" | Method for producing oligosaccharide copolymers |
| CN117143379A (en) * | 2023-10-27 | 2023-12-01 | 台州黄岩泽钰新材料科技有限公司 | Antibacterial starch degradable composite material and preparation process thereof |
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