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WO2007033596A1 - Materiau biodegradable aqueux - Google Patents

Materiau biodegradable aqueux Download PDF

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Publication number
WO2007033596A1
WO2007033596A1 PCT/CN2006/002472 CN2006002472W WO2007033596A1 WO 2007033596 A1 WO2007033596 A1 WO 2007033596A1 CN 2006002472 W CN2006002472 W CN 2006002472W WO 2007033596 A1 WO2007033596 A1 WO 2007033596A1
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WO
WIPO (PCT)
Prior art keywords
polyvinyl alcohol
weight
water
mixture
starch
Prior art date
Application number
PCT/CN2006/002472
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English (en)
Chinese (zh)
Inventor
Xiaolu Li
Original Assignee
Xiaolu Li
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of WO2007033596A1 publication Critical patent/WO2007033596A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/86—Component parts, details or accessories; Auxiliary operations for working at sub- or superatmospheric pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Definitions

  • This invention relates to a biodegradable material, and more particularly to a water soluble biodegradable material. Background technique
  • CN 1405230 A discloses a water-soluble, non-contaminating plastic molding material which is completely hydrolyzable and completely biodegradable in a short period of time, which material comprises polyvinyl alcohol, glycerol, diethylene glycol, sorbitol, fiber , white carbon black, ultra-fine calcium, modified starch.
  • CN 1405230A also discloses a preparation method of the material: adding 1-30 parts of glycerin to the polyvinyl alcohol raw material, stirring at a high temperature, sufficiently wetting, and then adding an appropriate amount of a plasticizer and a crosslinking agent.
  • the above materials can be blown and foamed in a temperature range of from 150 to 250 °C.
  • the material prepared by this method is subjected to thermoplastic extrusion under heating at 160 to 190 ° C according to the method of CN 1405230A, the inventors of the present invention have found that only a small part of the material is in a molten state, and is heated. By 200 ° C, the material has begun to carbonize. This indicates that the material is not a thermoplastic material, and blown film formation in a molten state cannot be achieved, and the cast film can be prepared only by a casting method which does not require heating and melting.
  • CN 1357563A discloses a preparation method of a starch-polyvinyl alcohol-polyester ternary system biodegradable film, the raw material of the biodegradable film containing: 30-65% starch, 15-40% poly Vinyl alcohol, 0-10% polyester, 10-20% plasticizer, 0.4% reinforcing agent, 0.5-1.5% wet strength agent and 0.4% antifoaming agent, wherein plasticizer by weight
  • the biodegradable film is prepared by first mixing polyvinyl alcohol with starch, and then Dissolve water dissolved in a reinforcing agent, a wet strength agent and an antifoaming agent The liquid is mixed with the above mixture of polyvinyl alcohol and starch, and finally mixed with a plasticizer and stirred and uniformly granulated and extruded.
  • the material prepared by this method cannot form a molten state, and the material is not a thermoplastic material, nor can it be blown film formed in a molten state, and can only be cast by a method which does not require heating and melting. A cast film was prepared.
  • the cast film is not easy to control the thickness during the preparation process, and the cast film prepared is generally thick and uneven.
  • the mechanical properties of the cast film such as tensile rupture strength, elongation at break and right angle tear strength are inferior to those of the thermoplastic formed blown film, and the general requirements for the mechanical properties of the film product cannot be satisfied.
  • the production efficiency of the cast film is very low, and the method and process for forming the cast film into a product are complicated. For example, when a bag is made of a cast film, it is necessary to fold a cast film in half, and then cast the folded film.
  • the object of the present invention is to overcome the shortcomings of the existing biodegradable materials containing polyvinyl alcohol which are not plastic, can not be used for preparing sheet-formed articles, and provide a plasticity which can be used for preparing sheet-formed articles. Water-soluble biodegradable material and preparation method thereof.
  • the inventors of the present invention conducted research on polyvinyl alcohol, and as a result, found that there is a large amount of hydroxyl groups in the molecule of polyvinyl alcohol, and between the hydroxyl group and the hydroxyl group. Strong hydrogen bonding is formed, so that a large number of hydrogen bonds exist between the molecules of the polyvinyl alcohol and in the molecule; in addition, since the polyvinyl alcohol molecules are flexible molecules, the molecules are intertwined to form an intricate high-barrier molecular chain structure.
  • the interaction force between the polymer molecules is much larger than the van der Waals force between the molecules of the general compound, thus causing to overcome this
  • the force requires a higher melting temperature.
  • the melting temperature of polyvinyl alcohol is as high as 220-240 ° C, which is higher than its decomposition temperature (about 200 )).
  • the melting temperature of polyvinyl alcohol is higher than its decomposition temperature so that polyvinyl alcohol generally begins to decompose and carbonize before melting, and it is almost impossible for polyvinyl alcohol to reach a stable molten state.
  • polyvinyl alcohol must react with starch and other components in a molten state to form a biodegradable material having a stable molten state.
  • the polyvinyl alcohol under the above process conditions fails to destroy the original hydrogen bond.
  • the action is not possible to achieve a stable molten state, so that the existing polyvinyl alcohol-containing biodegradable material cannot achieve the molten state and its thermoplastic processing.
  • the inventors of the present invention have speculated that although the method disclosed in CN 1405230A uses plasticizer glycerin to plasticize polyvinyl alcohol, the plasticizer glycerol cannot destroy the interweaving between polyvinyl alcohol molecules and cannot enter. In the case of polyvinyl alcohol molecules, the mixing between the plasticizer and the polyvinyl alcohol is only a simple physical blend. The polyvinyl alcohol in the mixture is still the original polyvinyl alcohol, and the plasticizer cannot truly be used for the polyvinyl alcohol.
  • the preparation method disclosed in CN 1357563A is to first mix polyvinyl alcohol with starch, and then add an aqueous solution in which a reinforcing agent, a wet strength agent and an antifoaming agent are dissolved, and the polyvinyl alcohol is flocculent, granular or powder at normal temperature. Since the water absorption of starch is much greater than the water absorption of polyvinyl alcohol, most of the water added is quickly absorbed by the starch, and only a very small part of the water is absorbed by the polyvinyl alcohol, and most of the polyvinyl alcohol remains in the original physical state.
  • the polyvinyl alcohol is coated in the starch due to the expansion gelation of the starch after absorbing moisture, which prevents the contact of the polyvinyl alcohol with the water, so that even if a large amount of water is added, it cannot be contacted with the polyvinyl alcohol, and most of the polyethylene is
  • the alcohol is still in the original state of polyvinyl alcohol, and such polyvinyl alcohol still cannot reach the molten state.
  • the added plasticizer still cannot be plasticized into polyvinyl alcohol and can only be absorbed by the starch, so the above mixture is a simple mixture of the aqueous starch and polyvinyl alcohol, plasticizer and auxiliary components. The molten state is still not achieved.
  • prior art granulation and subsequent extrusion molding thereof, etc. The process is carried out by heating and melting the mixture in a single-screw or twin-screw extruder in a molten state with a certain fluidity. Only such molten material can be used in a single-screw or twin-screw extruder. Extrusion granulation and extrusion molding in a subsequent process.
  • the materials disclosed in the existing polyvinyl alcohol-containing materials such as CN 1405230A and CN 1357563A, are a simple mixture. Since polyvinyl alcohol is not substantially plasticized, most of the polyvinyl alcohol The original state exists.
  • thermoplastic materials Under normal circumstances, water is a taboo in the processing of thermoplastic materials, because there is no compatibility between the free state water and the thermoplastic material, so that the thermoplastic material will have a large number of bubbles or even cracks during the processing, thus seriously affecting the product. Appearance quality and physical properties. Therefore, in the preparation of thermoplastic materials, it is necessary to strictly control the content of water in the raw materials and the amount of water present during the processing.
  • the inventors of the present invention have unexpectedly discovered that water and polyvinyl alcohol are first mixed, and after the polyvinyl alcohol is sufficiently swollen by water to form an aqueous polyvinyl alcohol, the mixture obtained by adding the polyol and the starch and mixing them uniformly can be squeezed.
  • Extrusion granulation in a molten state in the machine to obtain pellets of water-soluble biodegradable material the pellet can reach a stable melting temperature, and its melting temperature is significantly lower than its decomposition temperature.
  • the pellets have a melting temperature of 130-190 ° C and a decomposition temperature of 250-400 ° C.
  • the thermoplastic processing properties are very good and can be used for extrusion molding into sheet-formed articles.
  • the reaction product is not only stable
  • the melting temperature of 130-190 Torr, and the melting temperature is significantly lower than its decomposition temperature of 250-400 ° C, and also significantly lower than the decomposition temperature of polyvinyl alcohol of 200 ° C.
  • the above properties of the material determine that the material is a completely new thermoplastic material that makes thermoplastic molding of biodegradable materials possible.
  • the present invention provides a water-soluble biodegradable material, wherein the material is a product formed by melting a mixture comprising starch, a polyol, and an aqueous polyvinyl alcohol, the polyvinyl alcohol being a pro
  • the aqueous polyvinyl alcohol is contained in an amount of from 10% by weight to less than 19% by weight based on the total mass of the mixture.
  • the resulting material is extremely soluble in water. Moreover, since the material does not contain any synthetic resin that is difficult to biodegrade under natural environmental conditions, the materials and articles thereof provided by the present invention are fully biodegradable (ISO 14855, biodegradation rate greater than 90% in 180 days). Most importantly, since the water-soluble biodegradable material provided by the present invention is a product formed by melting a mixture, the melting temperature of the material is 130-190 ° C, the decomposition temperature is 250-400 ° C, and the melting temperature is far.
  • the water-soluble biodegradable material provided by the invention can be obtained by extrusion molding to obtain a sheet-formed product, and the obtained product has good impact strength and tensile yield strength of the simply supported beam, and the biodegradation rate is extremely high, 45 days.
  • the biodegradation rate is greater than 60%, the 60-day biodegradation rate is greater than 75%, and the 99-day biodegradation rate is greater than 92%. It fully meets the requirements of ISO 14855 for biodegradable products (the biodegradation rate is greater than 90% in 180 days).
  • the sheet-like shaped article can be completely dissolved in water within 15 minutes, so that when the product is used, it is dissolved in water under conventional waste treatment conditions or under natural conditions to accelerate degradation. It will not pollute the environment.
  • an organic carboxylic acid during the preparation of the water-soluble biodegradable material can avoid the phenomenon of oily small liquid beads oozing out from the surface of the product prepared from the material and the phenomenon of adhesion between the products. Step to improve the usability of the product
  • Example 1 is a differential scanning calorimetry (DSC) curve of a water-soluble biodegradable material prepared in Example 1 of the present invention
  • FIG. 2 is a thermogravimetric curve of a water-soluble biodegradable material prepared in Example 1 of the present invention
  • FIG. 3 is a scanning electron micrograph of the original starch used in Example 1 of the present invention
  • Fig. 4 is a scanning electron micrograph of the surface of a sheet-like molded article obtained from the water-soluble biodegradable material of Example 1 of the present invention. detailed description .
  • the present invention provides a water-soluble biodegradable material, wherein the material is a product formed by melting a mixture comprising starch, a polyol, and an aqueous polyvinyl alcohol, the polyvinyl alcohol being a pro
  • the aqueous polyvinyl alcohol has a content of the polyol of 10% by weight or less, based on the total weight of the mixture, of less than 19% by weight.
  • the content of starch in the mixture is from 25 to 75% by weight, preferably from 35 to 70% by weight, based on the total weight of the mixture; the content of aqueous polyvinyl alcohol is from 10 to 60% by weight, preferably from 15 to 50% by weight The content of the polyol is from 10% by weight to less than 19% by weight, preferably from 10 to 1% by weight.
  • the water-soluble biodegradable material provided by the present invention has a melting temperature of 130 to 190 ° C, preferably 140 to 190 ° C, and a decomposition temperature of 250 to 400 ° C.
  • the mixture contains 15% by weight of aqueous polyvinyl alcohol, 70% by weight of starch, 13% by weight of glycerin, 5.0% by weight of sorbitol, 5.0% by weight of glycerol, 0.5% by weight Pentaerythritol, 1.0% by weight of carboxymethylcellulose, 2.0% by weight of zinc stearate, 1.5% by weight of epoxidized soybean oil, the resulting material has a melting temperature of 155-190 ° (, decomposition temperature of 252-355 ° C. The content of each component in the mixture is different, The melting temperature and decomposition temperature of the resulting material are also slightly different.
  • the weight ratio of polyvinyl alcohol to water is from 0.75 to 10, preferably from 1 to 6.
  • the polyvinyl alcohol may be various hydrophilic polyvinyl alcohols in the prior art.
  • the hydrophilic polyvinyl alcohol refers to a polyvinyl alcohol which is soluble in water at 45 ° C or lower.
  • the polyvinyl alcohol has the formula -(CH 2 CHOH) n -, which is white or yellowish flocculent, granular or powdery solid at normal temperature.
  • the degree of alcoholysis of the hydrophilic polyvinyl alcohol is from 80 to 95%, preferably from 85 to 90%; and the degree of polymerization of the hydrophilic polyvinyl alcohol is from 500 to 2,000, preferably from 1,000 to 2,000.
  • Polyvinyl alcohol is mainly obtained by the alcoholysis of polyvinyl acetate, that is, the reduction of polyvinyl acetate, the degree of alcoholysis indicates the degree of reduction (alcoholysis), and the higher the degree of alcoholysis, the reduction of polyvinyl acetate to polyethylene. The higher the degree of alcohol.
  • the polyol may be selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol or a low molecular weight condensate thereof (having a molecular weight of 400 or less), incomplete esterification products of pentaerythritol and long-chain fatty acids (such as single hard).
  • the polyol acts to plasticize the polyvinyl alcohol.
  • the polyols may be used singly or in combination of two or more kinds, and are preferably used in combination.
  • the mixture of the present invention may further contain a cellulose-based polymer which also functions to plasticize polyvinyl alcohol.
  • the cellulose-based polymer is selected from the group consisting of carboxymethyl cellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose (HPMC), and hydroxypropyl ethyl cellulose. Or several.
  • the cellulose-based polymer is contained in an amount of from 0 to 10% by weight, based on the total weight of the mixture, preferably from 1 to 6% by weight.
  • the starch may be various starches of the prior art, for example, natural starch or modified starch such as oxidized starch, esterified starch or etherified starch may be used.
  • the natural starch is selected from one or more of corn starch, potato starch, sweet potato starch, tapioca starch, wheat starch, and legume starch, and may be amylopectin and/or amylose.
  • the starch of the present invention is preferably an amylopectin in the above natural starch.
  • the esterified starch may be selected from the group consisting of starch phosphate, starch sulfate, starch nitrate, starch acetate, One or more of starch propionates.
  • the etherified starch may be selected from the group consisting of carboxyl starch, cyano starch, amide starch, hydroxymethyl starch, sulfhydryl starch, aryl starch, primary amine starch ether, secondary amine starch ether, tertiary amine starch ether, terpenoid starch ether, ammonia One or more of nitrile starch.
  • a product obtained from a composition containing the above components such as a sheet-formed article, may have a lot of oily surface on the surface of the product at a temperature of more than 23 ° C and a relative humidity of more than 60%.
  • the inventors of the present invention have found that the above problems can be effectively avoided by adding an organic carboxylic acid to the above mixture.
  • the mixture of the present invention may further contain an organic carboxylic acid in an amount of from 0.5 to 10% by weight, preferably from 2 to 7% by weight, based on the total weight of the mixture.
  • the organic carboxylic acid may be one or more of organic carboxylic acids having 1 to 20 carbon atoms, preferably one or more of organic carboxylic acids having 1 to 12 carbon atoms.
  • the organic carboxylic acid may be a monobasic organic carboxylic acid or a polybasic organic carboxylic acid.
  • organic carboxylic acid examples include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid and isomers thereof, valeric acid and isomers thereof, hexanoic acid and isomers thereof, heptanoic acid and isomers thereof, Octanoic acid and its isomers, citric acid and its isomers, citric acid and its isomers, malonic acid, succinic acid and its isomers, glutaric acid and its isomers, adipic acid and Isomers, pimelic acid and its isomers, suberic acid and its isomers, sebacic acid and its isomers, sebacic acid and its isomers, citric acid, tartaric acid, lauric acid, benzoic acid One or several of them.
  • the mixture may also optionally contain a salt additive.
  • the salt additive may be selected from one or more of an alkyl sulfonate, an organic acid iron salt, a polyhydroxybutyrate, a stearate, a calcium carbonate, a calcium hydrogencarbonate, a light calcium carbonate, and a shell powder.
  • the stearates include stearates of Ca, Mg, Zn, Ba, Ce, and Fe.
  • Such additives can act as lubricants to reduce friction between components of the material and between the material and the processing equipment. These additives may be used singly or in combination of two or more, and it is preferred to use them in combination.
  • the content of the salt additive is from 0 to 5% by weight, preferably from 0.2 to 5% by weight, based on the total amount of the mixture.
  • some commonly used auxiliary agents may be added as needed, and the auxiliary agents include an antioxidant, a light/heat stabilizer, a photo oxidizing agent, an antifogging agent, a flame retardant, an antistatic agent, and a coupling agent.
  • an antifoaming agent, a coloring agent, and a lubricant are commonly used.
  • the amount of the adjuvant is from 0 to 5% by weight, preferably from 0.3 to 4% by weight, based on the total amount of the mixture.
  • an antioxidant in order to prevent and inhibit starch from being prematurely degraded by factors such as light, heat, oxygen, microorganisms or bacteria during processing or during use, an antioxidant, a light/heat stabilizer may be added.
  • the antioxidant may be selected from tetrakis(3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid) pentaerythritol ester (referred to as antioxidant 1010), thiodipropionate distearyl
  • One or more of an acid ester referred to as antioxidant DSTP
  • a phosphite a composite antioxidant PKY
  • a bisphenol oxime a bisphenol oxime.
  • the light/heat stabilizer may be selected from one or more of UV-series light/heat stabilizers, carbon black, organotin light/heat stabilizers, tridecyl phenyl phosphite (TNPP), epoxidized soybean oil.
  • TNPP tridecyl phenyl phosphite
  • the UV-series light/heat stabilizer may be ct-hydroxy-4-n-octyloxybenzophenone (abbreviated as UV-531).
  • the organotin light/heat stabilizer may be selected from the group consisting of dibutyltin dilaurate, isooctyl dimethyl thiomethacrylate (hereinafter referred to as ester tin), ester tin RWS-784, and double ( Isooctyl thioglycolate)
  • ester tin isooctyl dimethyl thiomethacrylate
  • ester tin RWS-784 ester tin RWS-784
  • double Isooctyl thioglycolate
  • Jingxi 8831 di-n-octyltin
  • dibutyltin dimaleate dibutyltin thioglycol isooctyl ester.
  • the lubricant may be various lubricants conventionally used, such as liquid paraffin and/or petroleum ether. Lubricants are used to reduce the friction between the pellets and the article and the injection machine, which facilitates demolding of the article.
  • the above various adjuvants may be used singly or in combination of two or more.
  • the water-soluble biodegradable material provided by the present invention can be obtained by heat-melting a mixture containing starch, a polyol and a water-containing polyvinyl alcohol, and then reacting, extruding, and granulating the obtained melt.
  • the aqueous polyvinyl alcohol can be obtained by contacting water with polyvinyl alcohol, and the conditions of contact as well as the amount of polyvinyl alcohol and water are sufficient to sufficiently swell the polyvinyl alcohol.
  • the sufficient swelling of the polyvinyl alcohol means that the weight ratio of the polyvinyl alcohol to water in the swollen polyvinyl alcohol, that is, the aqueous polyvinyl alcohol is from 0.75 to 10, preferably from 1 to 6.
  • the reason for the contact of water with polyvinyl alcohol is that the molecular weight of water is small. When water is contacted with polyvinyl alcohol alone, water easily enters the molecular structure of the polyvinyl alcohol, and the hydrogen bonds between the molecules of the polyvinyl alcohol and the molecules are destroyed.
  • the mixture of vinyl alcohol is capable of achieving a molten state.
  • the weight ratio of the polyvinyl alcohol to water is from 0.5 to 5, preferably from 1 to 4.
  • the polyvinyl alcohol When the weight ratio of polyvinyl alcohol to water is much less than 0.5, the polyvinyl alcohol is dissolved in water to form a solution state instead of the swelling state required by the present invention; when the weight ratio of polyvinyl alcohol to water is much greater than 5, The polyvinyl alcohol cannot be fully swelled, and the purpose of lowering the melting temperature of the polyvinyl alcohol is not achieved.
  • the conditions of the contact may be sufficient to sufficiently swell the polyvinyl alcohol.
  • the water may be contacted with the polyvinyl alcohol in a standing state for a sufficient period of time until the polyvinyl alcohol is sufficiently swollen.
  • the contact time required may be long.
  • the production efficiency is relatively low. Therefore, in order to sufficiently swell the polyvinyl alcohol in a short period of time to improve the production efficiency, the contact conditions preferably include the polyvinyl alcohol being contacted with water under stirring, and the stirring speed may be 50-650 rpm, the contact time can be 30-60 minutes, and the contact temperature can be 20-99 °C.
  • the weight ratio of polyvinyl alcohol to water in the aqueous polyvinyl alcohol is slightly larger than the weight ratio of polyvinyl alcohol to water, and when the stirring speed is faster and the stirring time is longer, the amount of water can be appropriately increased, so that The weight ratio of polyvinyl alcohol to water in the aqueous polyvinyl alcohol is in the range of 0.75-10.
  • the mixture containing starch, polyol and aqueous polyvinyl alcohol can be obtained by the above The aqueous polyvinyl alcohol, polyol and starch are uniformly mixed.
  • an aqueous polyvinyl alcohol, a polyol and a starch are mixed, it is also preferred to add an organic carboxylic acid.
  • an organic carboxylic acid When the aqueous polyvinyl alcohol, the polyol, and the starch are mixed, one or more of a cellulose-based polymer, a salt additive, and an auxiliary agent may be added and uniformly mixed.
  • the mixing is preferably carried out under agitation, and the stirring speed may be from 50 to 650 rpm.
  • the mixing order of the various components in the mixture may be any.
  • the aqueous polyvinyl alcohol may be mixed with the starch first, and then the polyol may be added and uniformly mixed; the starch and the polyol may be uniformly mixed and then added to the aqueous solution.
  • the polyvinyl alcohol is uniformly mixed; the aqueous polyvinyl alcohol and the polyol may be first mixed uniformly, then the starch is added and uniformly mixed; and the aqueous polyvinyl alcohol, the polyol and the starch may be uniformly mixed together.
  • the aqueous polyvinyl alcohol and the polyol are uniformly mixed, and then the starch is added and uniformly mixed.
  • the aqueous polyvinyl alcohol is added in an amount of 10 to 60% by weight, preferably 15 to 50% by weight, based on the total weight of the mixture; the polyol is added in an amount of 10% by weight to less than 19% by weight, preferably 10%. 18.9 wt% ; starch is added in an amount of 25 to 75% by weight, preferably 35 to 70% by weight, and the organic carboxylic acid is added in an amount of 0 to 10% by weight, preferably 0.5 to 10% by weight, based on the cellulose-based polymer
  • the amount added is 0 to 10% by weight
  • the amount of the salt additive is 0 to 5% by weight
  • the amount of the auxiliary agent is 0 to 5% by weight.
  • the method and conditions for extruding the mixture by heating and then extruding the resulting melt are well known to those skilled in the art.
  • the obtained melt may be subjected to extrusion granulation using a twin-screw extruder under the following conditions, and the twin-screw extruder has an aspect ratio of 20 to 64 and a screw rotation speed of 50 to 1,500 rpm.
  • the twin-screw extruder is generally divided into 12 sections from the feeding end to the discharging end. The temperature of each section is set to 90-150 ° C and 95-155 ° respectively from the feeding end to the discharging end.
  • the 4th and 10th sections are vacuum sections, the vacuum is 0.02-0.09 trillion Pa.
  • the degree of vacuum means the absolute value of the difference between the absolute pressure and the atmospheric pressure (absolute pressure is less than atmospheric pressure).
  • the intermeshing twin-screw has strong friction and shear on the material added to the twin-screw extruder.
  • the heat generated by the action, friction and shear causes the actual temperature of the material to be higher than the set temperature of each of the above sections.
  • the obtained mixture is melted, extruded and granulated.
  • the granulation can be, for example, a twin-screw extruder having a length to diameter ratio of 20-64, a screw rotation speed of 50-1200 rpm, and 12 sections from the feed end to the discharge end.
  • the temperature of each zone is set to 90-150 ° C, 95-155 ° C, 100-160 ° C, 115-165 ° C, 120-175 ° C, 125-175 ° C, 130-185 ° C, 135.
  • the 4th and 10th sections are vacuum sections, the vacuum degree of the vacuum section is 0.02-0.09
  • the mixture obtained above was melt-extruded and granulated under conditions of MPa.
  • the water-soluble biodegradable material of the present invention can be used for preparing a sheet-like shaped article, and the method for preparing a sheet-like shaped article from the water-soluble degradable material can employ, for example, first extruding the mixture of the present invention through a twin-screw extruder The granulation is used to obtain the raw material, and then the raw material is put into a single-screw extruder with a screw diameter of 120 mm, and is generally divided into six sections from the feeding end to the discharging end, and the temperature of each section is set to 140 ° C in this order.
  • the temperature of the T-die is set to 185 ° C, 175 ° C, 185 ° C, respectively, so that the molten material passes through the T-die After extrusion, it is rolled by three rolls and wound into a semi-finished sheet; then at a temperature of 160-185 ° C in a molding machine The above-mentioned sheet semi-finished product is molded in the mold and finally formed into a sheet-like molded product.
  • This embodiment is for explaining the water-soluble biodegradable material provided by the present invention and a preparation method thereof.
  • sorbitol 5.0 parts by weight of sorbitol, 5.0 parts by weight of glycerin, and 0.5 part by weight of pentaerythritol were added to 15.0 parts by weight of the aqueous polyvinyl alcohol obtained above, and the mixer was first mixed at a low speed of 100 rpm for about 5 minutes, and then Then, the mixture was mixed at a high speed of 200 rpm for a minute, and after standing at room temperature for 24 hours, 70.0 parts by weight (dry basis weight) of ordinary corn starch having a number average molecular weight of 150,000, 1.0 part by weight of carboxymethylcellulose, and 2.0 parts by weight.
  • Zinc stearate and 1.5 parts by weight of epoxidized soybean oil were added to the above mixture and stirred at 150 rpm to obtain a mixture M1 containing a starch, a polyol and an aqueous polyvinyl alcohol.
  • the composition of M1 is shown in Table 1 below. ;
  • a strip-shaped extrudate having a diameter of 3 mm was obtained at the discharge port of the extruder, and the strip-like extrudate was pelletized to obtain a water-soluble biodegradable material for preparing a sheet-like shaped article having a length of 2 mm.
  • This comparative example is used to illustrate the existing biodegradable material containing polyvinyl alcohol and a preparation method thereof.
  • This embodiment is for explaining the water-soluble biodegradable material provided by the present invention and a preparation method thereof.
  • An aqueous polyvinyl alcohol was obtained in which the weight ratio of polyvinyl alcohol to water was 8.25:1.
  • 5.0 parts by weight of sorbitol and 5.0 parts by weight of glycerin were added to 22.0 parts by weight of the aqueous polyvinyl alcohol obtained above, and the mixer was first mixed at a low speed of 100 rpm for about 5 minutes, and then at a high speed of 200 rpm.
  • This embodiment is for explaining the water-soluble biodegradable material provided by the present invention and a preparation method thereof.
  • This embodiment is for explaining the water-soluble biodegradable material provided by the present invention and a preparation method thereof.
  • This embodiment is intended to illustrate the water-soluble biodegradable material provided by the present invention and a method for preparing the same.
  • (1) 15.0 parts by weight of purified water was added to 37.5 parts by weight of polyvinyl alcohol having a degree of alcoholysis of 90% and a median polymerization degree of 1500 under stirring at 500 rpm, and stirred at 60 ° C for 40 minutes.
  • An aqueous polyvinyl alcohol was obtained in which the weight ratio of polyvinyl alcohol to water was 3.15:1.
  • sorbitol 1.0 part by weight of sorbitol, 5.0 parts by weight of glycerin and 10.0 parts by weight of pentaerythritol were added to 18.0 parts by weight of the aqueous polyvinyl alcohol obtained above, and the mixer was first mixed at a low speed of 100 rpm for about 6 minutes.
  • This embodiment is intended to illustrate the water-soluble biodegradable material provided by the present invention and a method for preparing the same.
  • (1) 15.0 parts by weight of purified water was added to 37.5 parts by weight of polyvinyl alcohol having a degree of alcoholysis of 90% and a median polymerization degree of 1500 under stirring at 500 rpm, and stirred at 60 ° C for 40 minutes.
  • An aqueous polyvinyl alcohol was obtained in which the weight ratio of polyvinyl alcohol to water was 3.15:1.
  • sorbitol 1.0 part by weight of sorbitol, 5.0 parts by weight of glycerin and 10.0 parts by weight of pentaerythritol were added to 18.0 parts by weight of the aqueous polyvinyl alcohol obtained above, and the mixer was first mixed at a low speed of 100 rpm for about 6 minutes, and then Mixing at 200 rpm for 8 minutes at high speed, and then adding 50.0 parts by weight (dry basis weight) of ordinary potato starch having a number average molecular weight of 200,000 to the above mixture and stirring uniformly, and then 1.0 part by weight of carboxymethyl cellulose.
  • the above pellet products BSR-07V-HS1 to BSR-07V-HS6 were added to the feed port of the ⁇ 90 extruder manufactured by Guangdong Shantou Jinmeng Packaging Machinery Factory, and divided into 6 zones from the feeding end to the discharge end.
  • the temperature of each section is set to 140 °C, 150 °C, 160 °C, 170 °C, 175 V, 170 °C, and the temperature of the T-die is set to 185 °C, 175 °C, respectively.
  • the impact strength of the simply supported beam of the product is determined by the GB/T1043-93 hard plastic simply supported beam impact test method
  • the biodegradation rate of the above product was measured in accordance with the method specified in IS014855-99.
  • Water-soluble test method First, the above products HS1-HS6 were broken into small pieces having a size of less than 10 mm (length) X 10 mm (width), and then 20 g of the above pieces were weighed and soaked in 100 g of water at 25 ° C for 5 minutes. After 10 minutes and 15 minutes, it is filtered with a filter paper having a pore size of 80-120 ⁇ m, and the obtained solid is dried at 100 ° C for 1 hour, weighed, and the ratio of the weight difference before and after the immersion to the weight before the immersion is the product HS1- The solubility of HS6 in water at 25 ° C at different time points.
  • Test for surface tackiness of the product Cut the above products HS1-HS6 into 20 samples of 100 mm (length) X 100 mm (width) X 0.8 mm (thickness), and divide the 20 samples into 10 groups (each Two groups), two samples of each group are stacked together, the contact surface is 100 mm (length) X 100 mm (width) surface, and then in an environment with a temperature of 30 ° C and a relative humidity of 70% RH After standing for 48 hours, press each of the stacked samples in a direction perpendicular to the contact surface at a pressure of 1000 Pa, and then observe whether the samples of each group are stuck together, and record the number of sets of the samples stuck together. At the same time, it was observed whether or not oily small liquid beads appeared on each surface of the sample, and the results were recorded in Table 2 below. Table 2
  • the film products HS1 to HS6 made of the water-soluble biodegradable material pellets BSR-07V-HS1 to BSR-07V-HS6 of Examples 1-6 have a good simplicity. Beam strength and tensile yield strength; High biodegradation rate, 45 days biodegradation rate greater than 60%, 60 days biodegradation rate greater than 75%, 99 days biodegradation rate greater than 92%, fully in line with ISO 14855 Requirements for biodegradable products (biodegradation rate greater than 90% in 180 days).
  • the material is a water-soluble material
  • the products HS1 to HS6 can be completely dissolved in water within 15 minutes, so when the product is used, it is dissolved in water under waste treatment conditions or under natural conditions to accelerate degradation, and will not Pollution to the environment.
  • This example is intended to illustrate the melting and thermal decomposition properties of the water-soluble biodegradable material provided in Example 1 of the present invention.
  • the melting and thermal decomposition properties of the water-soluble biodegradable material pellets BSR-07V-HS1 obtained in Example 1 were measured by the following methods.
  • the DSC curve of the sample has an endothermic peak in the temperature range of 155-190 ° C, 252 ° C and 270 ° C; as can be seen from Figure 2, at 252-355 ⁇ In the temperature range, the sample loses weight quickly, and the weight of the sample is substantially not lost in the temperature range of 150-185 °C.
  • the results of Figure 1 and Figure 2 show that the endothermic peak at 155-190 °C in the DSC curve of the sample is the endothermic peak caused by the melting endothermic of the sample, and the endothermic peak near 252 ° C and 270 ° C.
  • the sample Due to the rapid weight loss of the sample, the sample is decomposed at this temperature, and therefore, the endothermic peak is an endothermic peak caused by decomposition of the sample.
  • the pellet obtained in Example 1 can achieve a stable molten state in a wide temperature range of 155-190 ° C, which is much lower than its own decomposition temperature, and can be in the wide temperature range.
  • the pellets are subjected to thermoplastic processing. As shown in Table 2, the simply supported beam impact strength and tensile yield strength of the product obtained by melting and extruding the pellet of Example 1 were excellent. Far higher than the average cast film.
  • the material provided by the present invention is completely different from a simple mixture containing polyvinyl alcohol, starch and a plasticizer, and is a completely new thermoplastic material which has a melting temperature much lower than its own decomposition temperature and is also low.
  • This example is intended to illustrate the properties of articles made from the water-soluble biodegradable materials of the present invention.
  • FIG 3 and 4 show scanning electron microscopy of the original starch used in Example 1 and the cross-section of the water-soluble biodegradable material pellet BSR-07V-HS1 of Example 1 at a magnification of 2000 times, respectively. photo.
  • the scanning electron micrograph was obtained using a scanning electron microscope (Japan Electronics Co., Ltd.) of the model JSM5600LV.
  • the data in Table 2 indicates that the mechanical properties of the articles made of the water-soluble biodegradable material provided by the present invention, such as the simply supported beam impact strength and the tensile yield strength, are significantly improved, and are superior to any single one of the materials.

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Abstract

Matériau biodégradable aqueux issu de la fusion d'un mélange d'amidon, de polyol et d'alcool de polyvinyle qui contient de l'eau, ledit alcool étant du type hydrophile. La teneur en polyol est comprise entre 10 % et moins de 19 %, en poids, par rapport au poids total du mélange. Le matériau a une température de fusion comprise entre 130 et 190° C, une température de décomposition comprise entre 250 et 400° C, la première étant largement inférieure à la seconde. On peut ainsi utiliser le matériau pour la fabrication d'articles formés du type feuille, lesquels présentent, comme suit, de bonnes propriétés : résistance au choc en résilience Charpy, résistance à la traction, solubilité dans l'eau et biodégradabilité.
PCT/CN2006/002472 2005-09-21 2006-09-21 Materiau biodegradable aqueux WO2007033596A1 (fr)

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CN102173006A (zh) * 2011-03-14 2011-09-07 镇国广 超净无尘无静电聚乙烯绝缘料的生产方法
CN102161779A (zh) * 2011-06-01 2011-08-24 刘立文 一种硫酸钙玉米淀粉聚乙烯醇复合材料及其制备方法
CN102776597B (zh) * 2012-03-22 2014-01-29 上海罗洋新材料科技有限公司 一种高强高模聚乙烯醇纤维及其熔融纺丝方法
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CN103012856A (zh) * 2012-12-06 2013-04-03 湖南工业大学 一种基于微晶纤维素和聚乙烯醇增强的淀粉基全生物降解共混材料及其制备方法
CN103122083A (zh) * 2013-03-11 2013-05-29 太仓协乐高分子材料有限公司 一种土豆淀粉类生物降解塑料的制备方法
CN103122082A (zh) * 2013-03-11 2013-05-29 太仓协乐高分子材料有限公司 一种生物降解塑料的生产方法
CN105001569B (zh) * 2015-07-07 2017-06-27 四川大学 一种聚乙烯醇/贝壳粉生物质复合材料及其制备方法
CN113861515B (zh) * 2021-09-16 2023-04-21 无锡学院 一种可水溶性淀粉基包装缓冲填充物及其制备方法

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