WO2007033598A1 - Water soluble biodegradable material - Google Patents

Water soluble biodegradable material Download PDF

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Publication number
WO2007033598A1
WO2007033598A1 PCT/CN2006/002474 CN2006002474W WO2007033598A1 WO 2007033598 A1 WO2007033598 A1 WO 2007033598A1 CN 2006002474 W CN2006002474 W CN 2006002474W WO 2007033598 A1 WO2007033598 A1 WO 2007033598A1
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Prior art keywords
polyvinyl alcohol
water
weight
starch
mixture
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PCT/CN2006/002474
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English (en)
French (fr)
Inventor
Xiaolu Li
Original Assignee
Xiaolu Li
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Application filed by Xiaolu Li filed Critical Xiaolu Li
Priority to EP06791065.3A priority Critical patent/EP1942137B1/en
Publication of WO2007033598A1 publication Critical patent/WO2007033598A1/zh

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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • B29B7/82—Heating or cooling
    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • 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
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • 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
    • 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
    • B29B7/30—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
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2429/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • 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 and completely biodegradable plastic molding material which contains polyvinyl alcohol, glycerol, diethylene glycol, sorbitol, fiber, white carbon black. , ultra-fine calcium, modified starch.
  • CN1405230A also discloses a preparation method of the material: adding 1-30 parts of glycerin to a polyvinyl alcohol raw material, stirring at a high temperature, fully wetting, and then adding an appropriate amount of a plasticizer, a crosslinking agent, Reinforcing agent, modifier, filler, etc.; then, the reaction is blended at a temperature of 25-65 V for 5-50 minutes, and the obtained material is added to a single-screw or twin-screw extruder for granulation, and The film is blown and foamed in a temperature range of 150-250 Torr.
  • the inventors of the present invention have found that only a small portion of the material is in a molten state, and is heated. By 200 ° C, the material has begun to carbonize. This means that the material is not a thermoplastic material, and blown film formation or foam molding in a molten state cannot be achieved, and the cast film can be prepared only by a casting method without heating and melting ST.
  • CN1357563A discloses a preparation method of a starch-polyvinyl alcohol-polyester ternary system biodegradable film, wherein the weight percentage of the selected raw materials is: starch: 30-65%, polyvinyl alcohol: 15- 40%, polyester: 0-10%, plasticizer: 10-20%, reinforcing agent: ⁇ 0.4%, wet strength U: 0.5-1.5%, defoamer: ⁇ 0.4%.
  • the biodegradable film is prepared by first mixing polyvinyl alcohol with starch, and then mixing an aqueous solution in which a reinforcing agent, a wet strength agent and an antifoaming agent are dissolved.
  • the mixture of vinyl alcohol and starch is mixed 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 forming or foam forming in a molten state, and can only be melted without heating.
  • the casting method was used to prepare a cast film.
  • 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.
  • One of the main disadvantages of the casting method is that the casting method can only produce film products and cannot produce products such as injection, foaming and extruded sheets. Therefore, it is required to produce a foamed article by foam molding a material containing polyvinyl alcohol in a heated and molten state. Summary of the invention
  • the object of the present invention is to overcome the shortcomings of the existing biodegradable material containing polyvinyl alcohol, which is difficult to be foamed, and to provide a water-soluble biodegradable material capable of preparing a foamed product by foam molding and a preparation method thereof .
  • the inventors of the present invention conducted research on polyvinyl alcohol, and as a result, found that a large amount of hydroxyl groups exist in the polyvinyl alcohol molecule, and a strong relationship between the hydroxyl group and the hydroxyl group is formed.
  • the hydrogen bonding causes a large amount of hydrogen bonds between the polyvinyl alcohol molecules and within the molecules.
  • the polyvinyl alcohol molecules are flexible molecules, and the molecules are intertwined to form an intricate high-barrier molecular chain structure, and the interaction force between the polymer molecules is much larger than the van der Waals force between the general compound molecules. To overcome this 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 ° C).
  • 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 can react with components such as starch in a molten state to form a biodegradable state with a stable molten state.
  • 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 CN1357563A is to first mix polyvinyl alcohol with starch, and then add an aqueous solution.
  • the polyvinyl alcohol is flocculent, granular or powder at normal temperature, and since the water absorption of the starch is much larger than the water absorption of the polyvinyl alcohol, Most of the added water is quickly absorbed by the starch, and only a very small portion of the water is absorbed by the polyvinyl alcohol, and most of the polyvinyl alcohol remains in its 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.
  • 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 Appearance quality and physical properties of the product. 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 outlet gives a bulk material pellet which can reach a stable melting temperature and whose melting temperature is significantly lower than its decomposition temperature.
  • the bulk material pellet has a melting temperature of 130-190 ° C and a decomposition temperature of 250-400 ⁇ .
  • the thermoplastic (processability) is very good, and can be used for foam molding after being mixed with a foaming agent to form a foamed product.
  • the molecular weight of water is very small.
  • water When water is contacted with polyvinyl alcohol alone, water easily enters the molecular structure of polyvinyl alcohol, and the molecular chain of polyvinyl alcohol is opened to make the originally interwoven polyvinyl alcohol.
  • the molecular chain is fully stretched, so that the plasticizer can be more easily entered into the polyvinyl alcohol, and the polyvinyl alcohol can be plasticized and modified together, and the fully plasticized and modified polyvinyl alcohol can form a stable molten state.
  • the reaction product is obtained by reacting with starch and a plasticizer under molten conditions.
  • the reaction product not only has a stable melting temperature of 130 to 190 ° C, but also has a melting temperature significantly lower than its decomposition temperature of 250 to 400 ° C and also significantly lower than the decomposition temperature of polyvinyl alcohol of 200 ° C.
  • the above properties of the host material determine that the host material is a completely new thermoplastic material, making thermoplastic molding of biodegradable materials possible. Therefore, the water-soluble biodegradable material containing the host material and the foaming agent is also a completely new thermoplastic material which can be thermoformed in a molten state.
  • the present invention provides a water-soluble biodegradable material comprising a host material and a foaming agent, wherein the host material is a product formed by melting a mixture comprising starch, a polyol and an aqueous polymer Vinyl alcohol, the polyvinyl alcohol is a hydrophilic polyvinyl alcohol.
  • the water-soluble biodegradable material provided by the present invention contains a host material which is a product obtained by melting a mixture, the host material has a melting temperature of 130-190 ° C, a decomposition temperature of 250-400 ° C, and a melting temperature. It is far below the decomposition temperature, so it can reach the molten state. It has unparalleled thermoplastic processing properties with a simple physical mixing between ordinary polyvinyl alcohol, starch and polyol, enabling true extrusion granulation. And foam molding.
  • the water-soluble biodegradable material provided by the present invention can be obtained by foam molding to obtain various kinds of foamed articles, such as trays, lunch boxes, bowls, cups, foamed cloths, shockproof materials, and soundproof materials.
  • the foamed article obtained from the water-soluble biodegradable material provided by the present invention has good expansion ratio (greater than 45%), compressive strength (not less than 35 kPa), compression resilience and dimensional stability.
  • the biodegradation rate is extremely high, the biodegradation rate is more than 62% in 45 days, the biodegradation rate in 60 days is more than 76%, and the biodegradation rate in 99 days is more than 93%, which fully meets the requirements of ISO 14855 for biodegradable products (180 days)
  • the biodegradation rate is greater than 90%). Since the material is a water-soluble material, the foamed product can be completely dissolved in water within 15 minutes, so that 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.
  • the addition of an organic carboxylic acid during the preparation of the host material of the water-soluble biodegradable material can prevent the occurrence of blocking of the foamed article obtained from the water-soluble biodegradable material.
  • DSC differential scanning calorimetry
  • FIG. 2 is a thermogravimetric graph of a host material of a water-soluble biodegradable material prepared in Example 1 of the present invention
  • Figure 3 is a scanning electron micrograph of the original starch used in Example 1 of the present invention
  • Figure 4 is a scanning electron micrograph of a cross section of a host material of a water-soluble biodegradable material according to Example 1 of the present invention. detailed description
  • the water-soluble biodegradable material provided by the present invention comprises a host material and a foaming agent, wherein the host material is a product formed by melting a mixture, the mixture comprising starch, a polyol and an aqueous polyvinyl alcohol, Polyvinyl alcohol is a hydrophilic polyvinyl alcohol.
  • the content of the aqueous polyvinyl alcohol in the mixture is from 10 to 60% by weight, preferably from 15 to 50% by weight, based on the total weight of the mixture, of from 10 to 85% by weight, preferably from 20 to 80% by weight;
  • the content of the polyol is from 10 to 50% by weight, preferably from 15 to 40% by weight.
  • the host material contained in 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 content of each component in the mixture is different, and the melting temperature and decomposition temperature of the obtained host material are also slightly different.
  • Example 1 the composition of the mixture was 21% by weight aqueous polyvinyl alcohol, 15% by weight glycerin, 15% by weight sorbitol, 40% by weight starch, 3% by weight methyl cellulose, 2% by weight hard fat Zinc acid and 4% by weight of epoxidized soybean oil, the resulting host material has a melting temperature of 135-184 ° C and a decomposition temperature of 255-352.
  • 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 conventional hydrophilic polyvinyl alcohols, and the hydrophilic polyvinyl alcohol refers to polyvinyl alcohol which is soluble in water at 45 ° C or lower, and hydrophobic polyvinyl alcohol refers to It can only be dissolved in polyvinyl alcohol in water above 45 °C.
  • 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 hydrophilic polyvinyl alcohol has a median degree of polymerization of 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, polyacetic acid The olefin is reduced, and the degree of alcoholysis indicates the degree of reduction (alcoholysis). The higher the degree of alcoholysis, the higher the degree of reduction of polyvinyl acetate to polyvinyl alcohol.
  • the polyol may be selected from ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, polyethylene glycol or a low molecular weight condensate thereof (having a molecular weight of 400 or less), incomplete esterification of pentaerythritol and long-chain fatty acids.
  • One or more of the products e.g., glyceryl monostearate
  • the polyol can function 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 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 may be included in an amount of from 0 to 10% by weight, based on the total weight of the mixture, preferably from 2 to 6% by weight.
  • the starch may be various starches of the prior art, for example, natural starch or modified starch may be used.
  • the natural starch may be 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.
  • Examples of the modified starch include oxidized starch, esterified starch, and etherified starch.
  • the esterified starch may be selected from one or more of starch phosphate, starch sulfate, starch nitrate, starch acetate, and 'starch propionate.
  • the etherified starch may be selected from the group consisting of carboxyl starch, cyano starch, amide starch, hydroxyalkyl starch, mercapto starch, aryl starch, primary amine starch ether, secondary amine starch ether, tertiary amine starch ether, and key starch ether.
  • One or more of the cyanamide starch may be selected from the group consisting of carboxyl starch, cyano starch, amide starch, hydroxyalkyl starch, mercapto starch, aryl starch, primary amine starch ether, secondary amine starch ether, tertiary amine starch ether, and key starch ether.
  • cyanamide starch One or more of the cyanamide starch.
  • a product obtained from a composition of the above components such as a foamed article
  • the mixture may further contain an organic carboxylic acid, and the content of the organic carboxylic acid may be 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 .
  • a salt additive may optionally be included in the mixture.
  • the salt additive may be selected from the group consisting of alkyl sulfonates, organic acid iron salts, polyhydroxybutyrate, stearates such as calcium stearate, magnesium stearate, zinc stearate, barium stearate, stearic acid. Sour and stearic acid, calcium carbonate, calcium bicarbonate, light calcium carbonate, and shell powder. One or more of calcium stearate, zinc stearate and iron stearate are preferred.
  • 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 kinds, and it is preferred to use two or more of them in combination.
  • the content of the salt additive is 0 to 5% by weight, preferably 0.2 to 2% by weight.
  • the mixture may optionally further contain some auxiliary agents, and the auxiliary agent may be an antioxidant, a light/heat stabilizer, a photo oxidant, an antifogging agent, a flame retardant, an antistatic agent, a coupling agent, and a coloring agent.
  • the auxiliaries are well known to those skilled in the art, for example, the auxiliaries are present in an amount of from 0 to 5% by weight, preferably from 0.3 to 4% by weight, based on the total weight of the mixture.
  • a light/heat stabilizer may be added.
  • the antioxidant may be selected from tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (abbreviated as antioxidant 1010), distearyl thiodipropionate (abbreviation)
  • antioxidant 1010 tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester
  • distearyl thiodipropionate abbreviation
  • the light/heat stabilizer can be selected from UV-series light/ One or more of heat stabilizer, carbon black, organotin light/heat stabilizer, tridecyl phenyl phosphite (TNPP), epoxidized soybean oil.
  • UV-series light/ One or more of heat stabilizer, carbon black, organotin light/heat stabilizer, tridecyl phenyl phosphite (TNPP), epoxidized soybean oil epoxidized soybean oil.
  • the UV-series light/heat stabilizer may be ⁇ -hydroxy-4-n-octyloxybenzophenone (abbreviated as UV531); the organotin light/heat stabilizer may be selected from dibutyltin dilaurate, Dithioethanol isooctyl ester dimethyl ester ethylethylene tin (referred to as ester tin), ester tin tin RWS-784, bis(thioglycolate isooctyl) di-n-octyltin (referred to as Jingxi 8831), One or more of dibutyltin dimaleate and dibutyltin thioglycol isooctyl ester.
  • the above various adjuvants may be used singly or in combination of two or more.
  • the foaming agent contained in the water-soluble biodegradable material provided by the present invention may be water or a chemical foaming agent, preferably a chemical foaming agent.
  • the type of chemical blowing agent is well known to those skilled in the art, and may be, for example, one or more selected from the group consisting of a hydrazine-nitrous compound blowing agent, an azo compound blowing agent, and a hydrazide blowing agent.
  • hydrazine-nitrogen compound blowing agents examples include hydrazine, hydrazine-dinitrosopentamethylenetetramine (DPT), hydrazine, hydrazine-dimethyl-N,N-di-terephthalamide (NTA)
  • examples of the azo compound blowing agent include azodicarbonamide (AC), azobisisobutyronitrile, isopropyl azodicarboxylate, diethyl azodicarboxylate, diazoaminobenzene, and even
  • the hydrazide-based compound blowing agent examples include 4,4-disulfonyl quinone diphenyl ether (OBSH:), p-benzenesulfonyl hydrazide, 3,3-disulfonyl hydrazine diphenyl sulfone, 4 , 4-diphenyldisulfonyl hydrazide, 1,3-benzene disulfon
  • the content ratio of the host material to the foaming agent is from 10:1 to 1000:1, preferably from 15:1 to 100:1.
  • the water-soluble biodegradable material provided by the present invention can be obtained by heating and melting a mixture containing starch, a polyol and an aqueous polyvinyl alcohol, and then reacting and extruding the obtained melt to obtain a host material, and then The host material is mixed with a blowing agent.
  • 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 is 50. -650 rpm, contact time 30-60 minutes, contact temperature 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, a polyol, and an aqueous polyvinyl alcohol can be obtained by uniformly mixing the aqueous polyvinyl alcohol, the polyol, and the starch obtained above.
  • an aqueous polyvinyl alcohol, a polyol and a starch are mixed, it is also preferred to add an organic carboxylic acid.
  • 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, the polyol is added in an amount of 10 to 50% by weight, and the starch is added in an amount of 10 to 85% by weight, and the organic carboxyl group is used.
  • the acid is added in an amount of 0.5 to 10% by weight, the cellulose-based polymer is added in an amount of 0 to 10% by weight, the salt additive is added in an amount of 0 to 5% by weight, and the auxiliary agent is added in an amount of 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, and the vacuum section has a vacuum of 0.02 to 0.09 MPa.
  • the degree of vacuum here refers to the absolute value of the difference between absolute pressure and atmospheric pressure (absolute pressure is less than atmospheric pressure).
  • the intermeshing twin-screw pair is added to the twin-screw extruder.
  • the material has a strong friction and shearing action, and the heat generated by the friction and shearing causes the actual temperature of the material to be higher than the set temperature of each of the above sections.
  • the host material may be mixed with the foaming agent by various known methods.
  • a powdery chemical foaming agent may be blended into the host material and uniformly mixed.
  • the solvent is selected from any solvent which does not react with the blowing agent and the pellets and is easily removed. Commonly used are dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF).
  • DMSO dimethyl sulfoxide
  • DMF N,N-dimethylformamide
  • the concentration of the solution is at least 0.5% by weight, and the highest concentration may be the concentration at which the chemical blowing agent reaches saturation in the solvent.
  • the conditions of the impregnation are preferably immersed in an autoclave at a temperature of 20 to 105 ° C and a pressure of 0.15 to 15 MPa for 3 to 360 minutes. After the mixture is uniformly mixed, the solvent is removed, and the solvent is removed. The solvent is preferably removed under reduced pressure.
  • water used as the blowing agent, the host material can be wetted with water.
  • contacting polyvinyl alcohol with water and swelling sufficiently to obtain aqueous polyvinyl alcohol, followed by addition of starch, polyol, organic carboxylic acid, and optionally cellulose-based polymer, salt additive and/or auxiliary The above materials were mixed to obtain a mixture.
  • the polyvinyl alcohol is contacted with water for 30-60 minutes, and the stirring speed is 50-650 rpm;
  • the aqueous polyvinyl alcohol is polymerized with starch, polyol, organic carboxylic acid, and optionally cellulose-based polymer.
  • the stirring and blending time of the substance, the salt additive and/or the auxiliary agent may be 5 to 60 minutes, and the stirring and blending rotation speed is 50-650 rpm, preferably firstly stirring at a low speed and then stirring at a high speed;
  • the temperature of each section is set to 90-150 ° C, 95-155 ° C, 100-160 ° C, 115-165 ° C, 12 (M75 ° C, 125-175 ° C, 130-185 ° C, 135-185 ° C, 110-180 ° C, 115-
  • the mixture obtained above is melt-extruded and granulated at 175 ° C, 120-185 ° C, 130-180 ° C, and the vacuum degree of the vacuum section is 0.02 to 0.09 MPa to obtain the host material;
  • the mixing may be performed by immersing the host material in a chemical blowing agent solution at a temperature of 20-105 ° C, a pressure of 0.1-15 MPa, and an immersion time of 3-360 minutes.
  • the solvent is removed after immersion, and the solvent is removed.
  • the solvent is preferably removed under reduced pressure.
  • water is used as the blowing agent, the host material is wetted with water.
  • the water-soluble biodegradable material provided by the present invention can be produced into a foam-like product by a foam molding method.
  • the steps and conditions of the foam molding are well known to those skilled in the art.
  • the foam molding method includes, but is not limited to, the following two types:
  • Method 1 The water-soluble biodegradable material obtained above is put into a feeder of a single-stage single-screw extruder, and the single-screw extruder is generally divided into six zones from the feeding end to the discharging end. Section, from the feed end to the discharge end, the temperature of each section is set to 100-155 ° C, 105-165 ° C:, 110-175 ° C, 120-185 ° C, 130-195 ° C, Under the process condition of screw rotation speed of 50-300 rpm, the water-soluble biodegradable material is melted and extruded into a foaming material through an annular die, and then the foaming material is vacuum-applied on the molding machine. After molding, after punching, the foamed product can be obtained; or the foam can be directly formed by extrusion through a single hole and/or a porous die, and the foam is cut into individual foams by means of die face hot cutting. Body product
  • Method 2 The water-soluble biodegradable material obtained above is put into a feeder of a first-stage single-screw extruder of a two-stage single-screw extruder, and the first-stage single-screw extruder is advanced.
  • the material end to the discharge end is generally divided into 6 sections. From the feeding end to the discharge end, the temperature of each section is set to 100°C-155°C, 105°C-165°C, 110°C. -175.
  • This embodiment is intended to illustrate the water-soluble biodegradable material provided by the present invention and a method for preparing the same.
  • This embodiment is intended to illustrate the water-soluble biodegradable material provided by the present invention and a method for preparing the same.
  • the host material pellet Z2 was obtained from the mixture M2 in the same manner as in the step (2) of Example 1.
  • This embodiment is intended to illustrate the water-soluble biodegradable material provided by the present invention and a method for preparing the same.
  • This embodiment is intended to illustrate the water-soluble biodegradable material provided by the present invention and a method for preparing the same.
  • Water was added to 3 times by weight of polyvinyl alcohol (degree of alcoholysis of 88, average degree of polymerization of 1500) at a stirring speed of 150 rpm, and after stirring at 25 ° C for 40 minutes, water was obtained.
  • Polyvinyl alcohol in the obtained aqueous polyvinyl alcohol, the weight ratio of polyvinyl alcohol to water was 4.2. 48 parts by weight of the aqueous polyvinyl alcohol obtained above and 30 parts by weight of starch were mixed in a mixer. The mixer was first stirred at 100 rpm for about ⁇ minutes, and then stirred at 200 rpm for 8 minutes. Then, 12 parts by weight of glycerin, 10 parts by weight of sorbitol, and uniformly mixed to obtain a mixture M4 were added.
  • This embodiment is intended to illustrate the water-soluble biodegradable material provided by the present invention and a method for preparing the same.
  • aqueous polyvinyl alcohol 42 parts by weight of the above obtained aqueous polyvinyl alcohol was mixed with 10 parts by weight of glycerin and 25 parts by weight of pentaerythritol in a blender, and the stirrer was first stirred at 200 rpm for about 15 minutes, and then stirred at 300 rpm for 10 minutes; Further, 3 parts by weight of acetic acid and 20 parts by weight of starch were added and mixed to obtain a mixture M5.
  • the water-soluble biodegradable material BSR-07V-FS5 provided by the present invention was obtained from the host material pellet Z5 in the same manner as in the step (3) of Example 1.
  • This embodiment is intended to illustrate the water-soluble biodegradable material provided by the present invention and a method for preparing the same.
  • Water was added to 3 times by weight of polyvinyl alcohol (degree of alcoholysis of 86, median polymerization degree of 1750) at a stirring speed of 200 rpm, and after stirring at 30 ° C for 40 minutes, Aqueous polyvinyl alcohol. Among them, in the obtained aqueous polyvinyl alcohol, the weight ratio of polyvinyl alcohol to water was 4.1.
  • aqueous polyvinyl alcohol 40 parts by weight of the above obtained aqueous polyvinyl alcohol was mixed with 10 parts by weight of sorbitol and 15 parts by weight of pentaerythritol in a blender, and the stirrer was first stirred at 200 rpm for about 15 minutes, and then stirred at 400 rpm for 5 minutes; Then, 25 parts by weight of starch, 4 parts by weight of acetic acid, 2 parts by weight of succinic acid, 2 parts by weight of epoxidized soybean oil, 1 part by weight of calcium stearate, and 1 part by weight of zinc stearate were added and mixed to obtain a mixture M6.
  • the water-soluble biodegradable materials BSR-07V-FS1 to BSR-07V-FS6 obtained in Examples 1-6 were respectively put into the feeder of the first-stage single-screw extruder of the two-stage single-screw extruder. From the feed end to the discharge end, the temperature of each section of the first-stage single-screw extruder is set to 120 ° C, 140 ° C, 145 ° C, 160 ° C, 180 ° C, and the screw speed is 200.
  • the material is melt extruded, and the molten material is conveyed by a screw connection device to a second stage single screw extruder, and in the fifth and sixth stages of the first stage single screw extruder Between the sections, liquid butadiene is injected as a physical co-blowing agent; the pressure in the second-stage single-screw extruder is maintained at 100 kg/cm 2 , and the molten material is extruded through a ring die to become a foamed material.
  • the foamed sheet is formed by slitting, and then the foamed sheet is subjected to vacuum forming and punching on a molding machine to obtain desired foamed products FS1 to FS6.
  • the above foaming products were subjected to various performance tests by the following methods, and the measurement results are shown in Table 1.
  • the relative density of the water-soluble biodegradable materials BSR-07V-FS1 to BSR-07V-FS6 and the foamed products FS1 to FS6 were determined according to the plastic density and relative density test methods specified in GB1033-1986, and the foaming was calculated by the following formula. Magnification: Density of water-soluble biodegradable material
  • the density of the water-soluble biodegradable material is determined according to the IS01856 standard, and the compressive strength, compression rebound rate, and dimensional stability of the product are determined; wherein the compressive strength is represented by the compressive stress when the product is relatively deformed by 10% by volume; Rate refers to the percentage of the volume of the product to the original volume after compressing the product to 50% by volume and maintaining for 72 hours; dimensional stability is to place the article at a temperature of 105 ⁇ 3 ° C for 7 days, the deformation rate of the product Indicates the dimensional stability of the product, and the smaller the deformation rate, the better the dimensional stability;
  • the biodegradation rate of the product was determined according to the method specified in ISO 14855-99; Water solubility test: First, the above foamed products FS1 to FS6 were broken into small pieces having a size of less than 10 mm x 10 mm x 5 mm, and then 20 g of the above were weighed. The chips were soaked in 100 g of water at 25 ° C, filtered through a filter paper having a pore size of 80-120 ⁇ m after 5 minutes, 10 minutes and 15 minutes, and the obtained solid was dried at 100 ° C for 1 hour, weighed, and weighed before and after soaking. The ratio of the difference to the weight before soaking is the solubility of the articles FS1 to FS6 in water at 25 ° C at different time points.
  • the foamed articles PF1 to PF6 made of the water-soluble biodegradable material pellets BSR-07V-FS1 to BSR-07V-FS6 of Examples 1-6 had good hair growth.
  • Bubble ratio greater than 45%
  • compressive strength ⁇ 35 MPa
  • compression rebound rate and dimensional stability
  • high biodegradation rate, biodegradability of 45 days is greater than 62%
  • biodegradation rate of 60 days is greater than 76 %, 99 days of biodegradation rate greater than 93%, fully in line with ISO 14855 requirements for biodegradable products (biodegradation rate greater than 90% in 180 days).
  • the foamed products FS1 to FS6 can be completely dissolved in water within 15 minutes, so that when the product is used, it is dissolved in water under natural conditions to accelerate degradation, and does not pollute the environment. .
  • This example is intended to illustrate the melting and thermal decomposition properties of the host material of the water-soluble biodegradable material provided in Example 1 of the present invention.
  • the melting and thermal decomposition properties of the host material Z1 of the water-soluble biodegradable material provided in Example 1 were determined by the following method.
  • the DSC curve of the sample has an endothermic peak in the temperature range of 135 ⁇ -184 ⁇ , 255°C and 270°C; as can be seen from Fig. 2, it is 255°C-352°.
  • the sample loses weight quickly, and the weight of the sample is substantially not lost in the temperature range of 135 °C - 184 °C.
  • the results of Figure 1 and Figure 2 show that the endothermic peak at 135 °C-184 °C in the DSC curve of the sample is the endothermic peak caused by the melting endothermic of the sample, and the absorption near 255 °C and 270 °C.
  • the heat peak decomposes at this temperature due to the rapid weight loss accompanying the sample. Therefore, the endothermic peak is an endothermic peak caused by sample decomposition.
  • the pellets are subjected to thermoplastic processing. As shown in Table 2, the water-soluble biodegradable material of Example 1 was melted and foamed. The foaming ratio, compressive strength and compression resilience of the foamed product are excellent.
  • 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 which is much lower than its own decomposition temperature and is also low. Among them are the decomposition temperatures of any of polyvinyl alcohol and starch.
  • This example is intended to illustrate the properties of the water-soluble biodegradable material of the present invention.
  • FIG 3 and 4 are cross-sectional scanning electron micrographs of the original starch used in Example 1 and the host material Z1 of the water-soluble biodegradable material obtained in Example 1, respectively, at a magnification of 2000 times. .
  • the scanning electron micrograph was obtained using a scanning electron microscope (Japan Electronics Co., Ltd.) of the model JSM5600LV.
  • the starch granules are spherical granules, and the presence of starch granules is no longer visible in Figure 4.
  • the water-soluble biodegradable material provided by the present invention contains a host material which is completely different from a simple mixture containing polyvinyl alcohol, starch and a plasticizer, and is a completely new material.
  • the data in Table 2 shows that the foamed product, the compressive strength and the compression rebound rate of the foamed product which is melted and foamed by the water-soluble biodegradable material of Example 1 provided by the present invention is excellent, and is superior to An article made from any single component of the material.
  • the host material contained in the water-soluble biodegradable material provided by the present invention is a completely new reaction product which is completely different from the existing simple mixture.

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Description

水溶性可生物降解材料 技术领域
本发明是关于一种可生物降解材料，尤其是关于一种水溶性可生物降解 材料。 背景技术
CN 1405230A公开了一种水溶性、无污染且短期内即可完全生物降解的 塑料成型材料， 该材料含有聚乙烯醇、 丙三醇、 二缩二乙二醇、 山梨醇、 纤 维、 白炭黑、超细钙、改性淀粉。 CN1405230A还公开了该材料的制备方法： 在聚乙烯醇原料中加入 1-30份的丙三醇， 在高温下搅拌， 使其充分润湿后 再加入适量的助增塑剂、交联剂、补强剂、改性剂、填料等；然后，在 25-65 V 的温度下共混反应 5-50分钟， 再将所得物料加入到单螺杆或双螺杆挤出机 中进行造粒， 并且可在 150-250Ό的温度范围内吹膜、 发泡成型。 但是， 当 按照 CN 1405230A的方法， 用该方法制备的材料在 160-190°C加热条件下进 行热塑挤出时， 本发明的发明人发现， 该材料只有很少一部分呈熔融状态， 在加热到 200°C时， 该材料已经开始碳化。 这说明， 该材料不是一种热塑性 材料， 不能实现在熔融状态下吹膜成型或发泡成型， 只能通过无需加热熔 ST 的流延法制备流延膜。
CN1357563A公开了一种淀粉-聚乙烯醇-聚酯类三元体系生物降解膜的 制备方法， 该方法所选择的原料的重量百分含量为： 淀粉： 30-65 % , 聚乙 烯醇： 15-40% , 聚酯类： 0-10% , 增塑剂： 10-20% , 补强剂： ≤0.4%， 湿强 齐 U: 0.5-1.5%, 消泡剂： ≤0.4%。其中增塑剂按重量比为乙二醇： 甘油： 聚酯 多元醇 = 1-3 : 9-15： 3-6三元复合体系及水。 该生物降解膜的制备方法为先 将聚乙烯醇与淀粉混合， 再将溶解有补强剂、湿强剂和消泡剂的水溶液与聚 乙烯醇和淀粉的所述混合物混合， 最后与增塑剂混合并搅拌均匀造粒挤出。 与 CN 1405230A公开的材料一样， 用该方法制备的材料也不能形成熔融状 态， 该材料也不是一种热塑性材料， 也不能实现在熔融状态下吹膜成型或发 泡成型， 只能通过无需加热熔融的流延法制备流延膜。
而众所周知， 流延膜在制备过程中不容易控制厚度， 制备出来的流延膜 一般厚度较大而且不均匀。此外， 与热塑成型的吹塑薄膜相比， 流延膜的力 学性能如拉伸断裂强度、 断裂延伸率和直角撕裂强度比较差， 无法满足对薄 膜制品力学性能的一般要求。流延法更主要的一个缺点是， 流延法只能生产 薄膜类产品， 不能够生产注射类、 发泡类以及挤出片材类的产品。 因此， 需 要使含有聚乙烯醇的材料能够在加热熔融状态下发泡成型制备发泡类制品。 发明内容
本发明的目的是克服现有的含有聚乙烯醇的可生物降解材料难以进行 发泡成型的缺点，提供一种能够通过发泡成型制备发泡类制品的水溶性可生 物降解材料及其制备方法。
为了能够使含有聚乙烯醇的可生物降解材料实现熔融状态，本发明的发 明人对聚乙烯醇进行了研究， 结果发现， 聚乙烯醇分子中存在大量的羟基， 羟基与羟基之间形成较强的氢键作用，使得聚乙烯醇分子间和分子内有大量 的氢键存在。另外聚乙烯醇分子为柔性分子， 分子相互交织在一起形成错综 复杂的高阻隔性分子链结构，并且这种聚合物分子之间的相互作用力比一般 化合物分子之间的范德华力大得多，要想克服这种作用力需要较高的熔融温 度， 事实上， 聚乙烯醇的熔融温度高达 220-240°C， 高于其分解温度（200°C 左右）。 聚乙烯醇的熔融温度高于其分解温度使得聚乙烯醇一般在熔融之前 就开始分解碳化了， 聚乙烯醇几乎不可能达到稳定的熔融状态。而聚乙烯醇 在熔融状态下才能与淀粉等组分反应，生成具有稳定的熔融状态的可生物降 解材料， 因此， 正是由于上述工艺条件下的聚乙烯醇未能破坏原有的氢键作 用而不可能达到稳定的熔融状态，才使得现有的含聚乙烯醇的可生物降解材 料不能实现熔融状态及其热塑加工。
据本发明的发明人推测， 虽然 CN 1405230A公开的方法使用增塑剂丙 三醇对聚乙烯醇进行增塑，但增塑剂丙三醇不能破坏聚乙烯醇分子之间的交 织作用， 无法进入到聚乙烯醇分子中， 增塑剂与聚乙烯醇之间的混合只是一 种简单的物理共混， 混合物中聚乙烯醇仍然是原始状态的聚乙烯醇， 增塑剂 无法真正对聚乙烯醇起到增塑和改性的作用， 因而不能降低聚乙烯醇的熔融 温度， 仍然不能实现聚乙烯醇的熔融状态， 聚乙烯醇与增塑剂和淀粉等的混 合物同样也不能实现熔融状态。
CN1357563A公开的制备方法为先将聚乙烯醇与淀粉混合， 再加入水溶 液， 聚乙烯醇在常温下为絮状、 颗粒状或粉状， 由于淀粉的吸水性远大于聚 乙烯醇的吸水性， 因而加入的水大部分迅速被淀粉吸收， 只有非常少部分的 水分被聚乙烯醇吸收， 绝大部分聚乙烯醇仍为原始物理状态。 由于吸收水分 后的淀粉膨胀胶化而将聚乙烯醇包覆在淀粉内， 阻止了聚乙烯醇与水分的接 触， 因而即便加入再大量的水也无法与聚乙烯醇接触， 绝大部分聚乙烯醇仍 然为原始状态的聚乙烯醇， 这样的聚乙烯醇仍然不能达到熔融状态。而且加 入的增塑剂仍然不能进入聚乙烯醇中对其进行增塑， 只能被淀粉吸收， 因而 上述混合物是含水的淀粉与聚乙烯醇、 增塑剂及助剂等组分的简单混合物， 仍然不能实现熔融状态。
而本领域技术人员公知的是，现有技术中的造粒及其后续的发泡成型等 工艺均是在单螺杆或双螺杆挤出机中将混合物加热熔融使其处于熔融态， 同 时物料还需要具有一定的流动性， 这样的熔融态的物料才能进行发泡成型。 但是， 现有的含聚乙烯醇的材料， 如 CN 1405230A和 CN1357563A中公开 的材料都是一种简单的混合物， 由于聚乙烯醇实质上并没有被增塑， 绝大部 分聚乙烯醇以其原始的状态存在， 在对这些简单的混合物进行加热时， 如果 加热温度高于聚乙烯醇的熔融温度，至少部分聚乙烯醇未经熔融就已经被分 解碳化了， 而如果温度低于熔融温度， 聚乙烯醇不能熔融， 也就不能使其在 熔融态下与增塑剂和淀粉实现真正意义上的混合并反应，形成具有稳定的熔 融状态的反应产物， 也就根本无法实现发泡成型。
一般情况下， 水是热塑性材料的加工过程中的大忌， 因为自由状态的水 与热塑性材料之间没有相容性， 因而会使热塑性材料在加工过程中出现大量 的气泡甚至破裂， 从而严重影响制品外观质量和物理性能。 因此在热塑性材 料的制备过程中， 需要严格控制原料中水的含量及加工过程中水的存在量。
本发明的发明人意外地发现， 先将水与聚乙烯醇进行混合， 待聚乙烯醇 被水充分溶胀形成含水的聚乙烯醇后，再加入多元醇和淀粉并混合均匀后得 到的混合物可以在挤出机中在熔融状态下挤出造粒， 得到一种主体材料粒 料，该粒料可以达到稳定的熔融温度，并且其熔融温度明显低于其分解温度。 该主体材料粒料的熔融温度为 130-190°C、分解温度为 250-400Ό，·热塑性 (加 工性能)非常好， 可以与发泡剂混合后用于发泡成型制成发泡类制品。 这可 能是因为， 水的分子量很小， 将水与聚乙烯醇单独接触时， 水很容易进入到 聚乙烯醇分子结构内部， 打开聚乙烯醇的分子链， 使原本交织在一起的聚乙 烯醇分子链充分舒展， 使增塑剂更容易进入到聚乙烯醇中， 共同对聚乙烯醇 起到增塑和改性作用， 充分增塑并改性后的聚乙烯醇可以形成稳定的熔融状 态， 在熔融条件下与淀粉和增塑剂反应得到反应产物。 该反应产物不仅具有 稳定的 130-190°C的熔融温度， 而且该熔融温度明显低于其分解温度 250-400 °C , 也明显低于聚乙烯醇的分解温度 200°C。该主体材料的上述性质 决定了该主体材料是一种全新的热塑性材料，使可生物降解材料热塑成型成 为可能。 因此， 含有该主体材料和发泡剂的水溶性可生物降解材料也是一种 全新的热塑性材料， 可以在熔融状态下热塑成型。 本发明提供了一种水溶性可生物降解材料，该材料含有主体材料和发泡 剂， 其中， 该主体材料为一种混合物经熔融而形成的产物， 所述混合物含有 淀粉、 多元醇和含水的聚乙烯醇， 所述聚乙烯醇为亲水性聚乙烯醇。
由于本发明提供的水溶性可生物降解材料所含有的主体材料为一种混 合物经熔融而形成的产物， 主体材料的熔融温度为 130-190°C， 分解温度为 250-400 °C , 熔融温度远低于分解温度， 因而可以达到熔融态， 具有普通聚 乙烯醇、淀粉及多元醇之间简单物理混合得到的混合物材料无可比拟的热塑 加工性， 能够实现真正意义上的挤出造粒和发泡成型。
本发明提供的水溶性可生物降解材料可以通过发泡成型得到各种不同 种类的发泡类制品， 例如托盘、 餐盒、 碗、 杯、 发泡布、 防震材料、 隔音材 料。 由本发明提供的水溶性可生物降解材料得到的发泡类制品具有良好的发 泡倍率 （大于 45 % )、 压縮强度 （不低于 35千帕）、 压縮回弹率和尺寸稳定 性， 生物降解率极高， 45天的生物降解率大于 62%， 60天的生物降解率大 于 76%， 99天的生物降解率大于 93 %， 完全符合 ISO 14855对可生物降解 制品的要求（180天内生物分解率大于 90% )。 由于所述材料为水溶性材料， 发泡类制品在 15分钟内可以完全溶于水中， 因此当所述制品使用完后在废 弃物处理条件下或自然条件下溶于水中而加速降解， 不会对环境造成污染。 在水溶性可生物降解材料的主体材料的制备过程中加入有机羧酸，可以避免 由所述水溶性可生物降解材料制得的发泡类制品出现粘连的现象。 附图说明
图 1为本发明实施例 1制备的水溶性可生物降解材料的主体材料的差示 扫描量热 （DSC) 曲线图；
图 2为本发明实施例 1制备的水溶性可生物降解材料的主体材料的热重 曲线图； 图 3为本发明实施例 1所使用的原淀粉的扫描电子显微照片；
图 4为本发明实施例 1的水溶性可生物降解材料的主体材料的横截面的 扫描电子显微照片。 具体实施方式
本发明提供的水溶性可生物降解材料含有主体材料和发泡剂， 其中， 该 主体材料为一种混合物经熔融而形成的产物， 所述混合物含有淀粉、 多元醇 和含水的聚乙烯醇， 所述聚乙烯醇为亲水性聚乙烯醇。
以混合物的总重量为基准， 所述混合物中含水的聚乙烯醇的含量为 10-60重量％， 优选为 15-50重量 淀粉的含量为 10-85重量％， 优选为 20-80重量％; 多元醇的含量为 10-50重量％, 优选为 15-40重量％。
本发明提供的水溶性可生物降解材料中所含有的主体材料的熔融温度 为 130-190°C， 优选为 140-190°C， 分解温度为 250-400 °C。 混合物中各组分 的含量不同， 所得主体材料的熔融温度和分解温度也略有不同。 例如， 在实 施例 1中， 混合物的组成为 21重量％含水聚乙烯醇、 15重量％甘油、 15重 量％山梨糖醇、 40重量％淀粉、 3重量％甲基纤维素、 2重量％硬脂酸锌与 4重量％环氧大豆油， 所得主体材料的熔融温度为 135-184°C， 分解温度为 255-352 。
所述含水的聚乙烯醇中，聚乙烯醇与水的重量比为 0.75-10，优选为 1-6。 所述聚乙烯醇可以是现有的各种亲水性聚乙烯醇，亲水性聚乙烯醇指可溶于 45°C或 45°C以下的水中的聚乙烯醇， 疏水性聚乙烯醇指只能溶于 45°C以上 的水中的聚乙烯醇。所述聚乙烯醇的结构式为 -(CH2CHOH)n -,常温下为白色 或微黄色絮状、颗粒状或粉末状固体。亲水性聚乙烯醇的醇解度为 80-95 % , 优选为 85-90 % ; 亲水性聚乙烯醇的中值聚合度为 500-2000， 优选为 1000-2000。 聚乙烯醇主要是由聚醋酸乙烯醇解得到的， 也就是将聚醋酸乙 烯进行还原， 醇解度表示还原 （醇解） 的程度， 醇解度越高， 则表示聚醋酸 乙烯还原成聚乙烯醇的程度越高。
所述多元醇可以选自乙二醇、 二甘醇、 丙二醇、 甘油、 山梨糖醇、 聚乙 二醇或其低分子量縮合物（分子量小于等于 400)、季戊四醇和长链脂肪酸的 不完全酯化产物（如单硬脂酸甘油酯） 中的一种或几种， 优选为甘油、 山梨 糖醇和季戊四醇中的一种或几种。多元醇可以起到对聚乙烯醇进行增塑的作 用。 所述多元醇可单独使用或者两种或两种以上配合使用， 优选配合使用。
此外， 所述的混合物中还可以含有纤维素基聚合物， 该纤维素基聚合物 同样可以起到对聚乙烯醇进行增塑的作用。所述纤维素基聚合物选自羧甲基 纤维素 （CMC)、 甲基纤维素、 乙基纤维素、 羟丙基甲基纤维素 （HPMC)、 羟丙基乙基纤维素中的一种或几种。 以混合物的总重量为基准， 纤维素基聚 合物的含量可以为 0-10重量％， 优选为 2-6重量％。
所述淀粉可以是现有技术中的各种淀粉，例如可以使用天然淀粉或者改 性淀粉。 天然淀粉可以选自玉米淀粉、 马铃薯淀粉、 红薯淀粉、 木薯淀粉、 麦类淀粉和豆类淀粉中的一种或几种，可以是支链淀粉和 /或直链淀粉。所述 改性淀粉的例子包括氧化淀粉、酯化淀粉和醚化淀粉。所述酯化淀粉可以选 自淀粉磷酸酯、 淀粉硫酸酯、 淀粉硝酸酯、 淀粉醋酸酯、 '淀粉丙酸酯中的一 种或几种。 所述醚化淀粉可以选自羧基淀粉、 氰基淀粉、 酰胺淀粉、 羟烷基 淀粉、 垸基淀粉、 芳基淀粉、 伯胺淀粉醚、 仲胺淀粉醚、 叔胺淀粉醚、 鑰类 淀粉醚、 氨腈淀粉中的一种或几种。
此外， 本发明的发明人发现， 由上述组分的组合物制得的制品如发泡类 制品在温度大于 23 V、相对湿度大于 60%的环境下会发生表面发粘的现象， 因此多个制品之间容易粘连在一起或者与其它物品粘连在一起，给制品的使 用带来不便。 为了解决这个问题， 所述混合物还可以含有有机羧酸， 以混合 物的总重量为基准， 有机羧酸的含量可以为 0.5-10重量％， 优选为 2-7重量 %。
所述有机羧酸可以为碳原子数为 1-20 的有机羧酸中的一种或几种， 优 选为碳原子数为 1-12 的有机羧酸中的一种或几种。 所述有机羧酸可以为一 元有机羧酸， 也可以为多元有机羧酸。所述有机羧酸的例子包括但不限于甲 酸、 乙酸、 丙酸、 丁酸及其异构体、 戊酸及其异构体、 己酸及其异构体、 庚 酸及其异构体、 辛酸及其异构体、 壬酸及其异构体、 癸酸及其异构体， 丙二 酸、 丁二酸及其异构体、 戊二酸及其异构体、 己二酸及其异构体、庚二酸及 其异构体、 辛二酸及其异构体、 壬二酸及其异构体、 癸二酸及其异构体、 柠 檬酸、 酒石酸、 月桂酸、 苯甲酸。
所述混合物中可以选择性地含有盐类添加剂。盐类添加剂可以选自烷基 磺酸盐， 有机酸铁盐， 聚羟基丁酸盐， 硬脂酸盐如硬脂酸钙、 硬脂酸镁、 硬 脂酸锌、 硬脂酸钡、 硬脂酸铈及硬脂酸铁， 碳酸钙， 碳酸氢钙， 轻质碳酸钙, 和贝壳粉。优选为硬脂酸钙、 硬脂酸锌和硬脂酸铁中的一种或几种。 这类添 加剂可以作为润滑剂降低材料各组分之间、以及材料与加工设备之间的摩擦 力。所述添加剂可单独使用或者两种或两种以上配合使用， 优选为两种或两 种以上配合使用。 盐类添加剂的含量为 0-5重量％， 优选为 0.2-2重量％。
所述混合物中还可以选择性地含有一些助剂， 所述助剂可以为抗氧剂、 光 /热稳定剂、光氧化剂、 防雾剂、 阻燃剂、 抗静电剂、 偶联剂、 着色剂、 润 滑剂中的一种或几种。助剂的用量和种类已为本领域技术人员所公知，例如， 以混合物的总重量为基准， 助剂的含量为 0-5重量％， 优选为 0.3-4重量％。 例如为了防止和抑制淀粉在加工过程中或使用过程中， 由于光、 热、 氧、 微 生物或菌等因素引起过早降解， 可以加入抗氧剂、光 /热稳定剂。抗氧化剂可 以选自四 [β-(3，5-二叔丁基 -4-羟基苯基)丙酸]季戊四醇酯（简称抗氧剂 1010)、 硫代二丙酸二硬脂醇酯（简称抗氧剂 DSTP)、含硫酯类、亚磷酸酯类、 复合 抗氧剂 PKY、 双酚 Α中的一种或几种。 光 /热稳定剂可以选自 UV-系列光 / 热稳定剂、 炭黑、有机锡类光 /热稳定剂、 亚磷酸三壬基苯酯（TNPP)、 环氧 大豆油中的一种或几种。其中， UV-系列光 /热稳定剂可以为 α-羟基 -4-正辛氧 基二苯甲酮（简称 UV531 ); 所述有机锡类光 /热稳定剂可以选自二月桂酸二 丁基锡、 二硫代乙醇异辛酯二甲酯基亚乙基锡 （简称酯基锡）、 酯基锡 RWS-784, 双 （硫代甘醇酸异辛酯） 二正辛基锡 （简称京锡 8831 )、 二马来 酸二丁基锡、硫代甘醇异辛酯二丁基锡中的一种或几种。 上述各种助剂可以 单独使用， 也可以两种或两种以上配合使用。
本发明提供的水溶性可生物降解材料中含有的发泡剂可以为水或化学 发泡剂，优选为化学发泡剂。化学发泡剂的种类已为本领域技术人员所公知， 例如可以选自 Ν-亚硝化合物发泡剂、 偶氮化合物发泡剂、 酰肼类化合物发 泡剂中的一种或几种。 Ν-亚硝化合物发泡剂的例子包括 Ν,Ν-二亚硝基五次 甲基四胺 (DPT)、 Ν,Ν-二甲基 -N，N-二亚对苯二甲酰胺 (NTA); 偶氮化合物发 泡剂的例子包括偶氮二甲酰胺 (AC)、 偶氮二异丁腈、 偶氮二甲酸异丙酯、 偶 氮二甲酸二乙酯、 二偶氮氨基苯、 偶氮二甲酸钡； 酰肼类化合物发泡剂的例 子包括 4,4-二磺酰肼二苯醚 (OBSH：)、对苯磺酰肼、 3,3-二磺酰胼二苯砜、 4，4- 二苯二磺酰肼、 1,3-苯二磺酰肼、 1,4-苯二磺酰肼。优选使用 AC发泡剂、 DPT 发泡剂或 DBSH发泡剂。在所述水溶性可生物降解材料中， 所述主体材料与 所述发泡剂的含量重量比为 10: 1至 1000: 1， 优选为 15: 1至 100: 1。
本发明提供的水溶性可生物降解材料可以通过以下步骤制得：将含有淀 粉、 多元醇和含水的聚乙烯醇的混合物加热熔融， 然后将所得熔融物反应、 挤出造粒得到主体材料， 之后将主体材料与发泡剂混合。
所述含水的聚乙烯醇可以通过将水与聚乙烯醇接触而得到，接触的条件 以及聚乙烯醇和水的用量足以使聚乙烯醇充分溶胀。聚乙烯醇充分溶胀是指 溶胀的聚乙烯醇即含水的聚乙烯醇中聚乙烯醇与水的重量比为 0.75-10， 优 选为 1-6。 将水与聚乙烯醇接触的原因是水的分子量小，将水与聚乙烯醇单独接触 时， 水非常容易进入到聚乙烯醇分子结构内部， 破坏聚乙烯醇分子间和分子 内的氢键， 将错综复杂交织在一起的聚乙烯醇分子链最大程度地展开， 为多 元醇类增塑剂最大程度地进入到聚乙烯醇分子结构内部奠定了基础，从而最 终降低聚乙烯醇熔融温度， 使含有聚乙烯醇的混合物能够实现熔融状态。为 了使聚乙烯醇充分溶胀， 优选聚乙烯醇与水的用量重量比为 0.5-5， 优选为 1-4。当聚乙烯醇与水的用量重量比远小于 0.5时， 聚乙烯醇被溶解在水中形 成溶液状态而不是本发明所需的溶胀状态； 当聚乙烯醇与水的加料重量比远 大于 5时， 聚乙烯醇不能全部被充分溶胀， 达不到降低聚乙烯醇熔融温度的 目的。
所述接触的条件只要满足能够使聚乙烯醇充分溶胀即可。例如， 可以使 水与聚乙烯醇在静置状态下接触足够长的时间， 直至聚乙烯醇被充分溶胀， 采用这种方式虽然可以使聚乙烯醇充分溶胀， 但是需要的接触时间会比较 长， 生产效率比较低， 因此， 为了使聚乙烯醇在较短的时间内即可充分溶胀 从而提高生产效率，所述接触的条件优选包括所述聚乙烯醇与水在搅拌下接 触,搅拌速度为 50-650转 /分钟，接触时间为 30-60分钟，接触温度为 20-99 °C。 由于水与聚乙烯醇的混合物粘度较大， 搅拌的阻力较大， 因而搅拌过程中会 产生大量的热， 这种热会使加入的部分水蒸发掉， 并且搅拌时间越长， 产生 的热量也越高， 蒸发掉的水也越多； 搅拌速度越快， 产生的热量也越高， 蒸 发掉的水也越多， 因此在上述聚乙烯醇与水的用量重量比和接触条件下， 得 到的含水的聚乙烯醇中聚乙烯醇与水的重量比略大于聚乙烯醇与水的用量 重量比，而且当搅拌速度较快和 /搅拌时间较长时，可以适当地增加水的用量， 以使含水的聚乙烯醇中聚乙烯醇与水的重量比在 0.75-10的范围内。
所述含有淀粉、多元醇和含水的聚乙烯醇的混合物可以通过将上述得到 的含水的聚乙烯醇、 多元醇和淀粉混合均匀而得到。 在将含水的聚乙烯醇、 多元醇和淀粉混合时， 还优选加入有机羧酸。 在将含水的聚乙烯醇、 多元醇和淀粉混合时， 还可以加入纤维素基聚合 物、 盐类添加剂和助剂中的一种或几种并混合均匀。
所述混合优选在搅拌下进行， 搅拌的速度可以为 50-650转 /分钟。
该混合物中各种成分的混合顺序可以是任意的， 例如， 可以将含水的聚 乙烯醇与淀粉先混合均匀后再加入多元醇并混合均匀；可以将淀粉与多元醇 混合均匀后再加入含水的聚乙烯醇并混合均匀；可以将含水的聚乙烯醇与多 元醇先混合均匀后再加入淀粉并混合均匀； 也可以将含水的聚乙烯醇、 多元 醇、 淀粉一起混合均匀。优选情况下， 为了使多元醇更好地起到对含水的聚 乙烯醇的增塑作用，先将含水的聚乙烯醇与多元醇混合均匀后再加入淀粉并 混合均匀。
其中， 以混合物的总量为基准， 含水的聚乙烯醇的加入量为 10-60重量 % , 多元醇的加入量为 10-50重量％， 淀粉的加入量为 10-85重量％， 有机 羧酸的加入量为 0.5-10重量％， 纤维素基聚合物的加入量为 0-10重量％， 盐类添加剂的加入量为 0-5重量％， 助剂的加入量为 0-5重量％。
将该混合物加热熔融， 然后将所得熔融物挤出造粒的方法、条件已为本 领域技术人员所公知。例如， 可以采用双螺杆挤出机在下述条件下将所得熔 融物挤出造粒，双螺杆挤出机的长径比为 20-64，螺杆转速 50-1500转 /分钟。 所述双螺杆挤出机从进料端到出料端一般分为 12个区段， 从进料端到出料 端，各区段温度分别依次设定为 90-150°C、 95-155°C、 100-160 °C , 115-165°C、 120-175°C、 125-175°C、 130-185Ό、 135-185°C、 110-180°C、 115-75°C、 120-185°C、 130-180°C , 第 4和 10个区段为真空段， 真空段的真空度为 0.02 至 0.09兆帕。此处的真空度是指绝对压力与大气压力的差值的绝对值（绝对 压力小于大气压力）。 双螺杆挤出机的双螺杆相互啮合， 当螺杆的转速较高 时如大于等于 500转 /分钟，相互啮合的双螺杆对加入到双螺杆挤出机中的物 料有很强的摩擦和剪切作用，摩檫和剪切作用产生的热量使物料的实际温度 高于上述各区段的设定温度。
可以通过已知的各种方法将主体材料与发泡剂混合， 例如， 可以将粉末 状的化学发泡剂掺配到主体材料中并混合均匀。为了使化学发泡剂与主体材 料均匀混合， 优选情况下， 将化学发泡剂溶于溶剂中形成溶液， 用该溶液浸 渍主体材料。 所述溶剂选自任何不与发泡剂和粒料反应并且容易除去的溶 剂， 常用的有二甲基亚砜（DMSO)、 N，N-二甲基甲酰胺（DMF)。 所述溶液 的浓度最低为 0.5重量％， 最高浓度可以是化学发泡剂在溶剂中达到饱和时 的浓度。 浸渍的条件优选为在温度为 20-105°C、 压力为 0.15-15兆帕的条件 下在高压釜中浸渍 3-360分钟。 混合均匀后除去溶剂， 除去溶剂的方法优选 为减压除去溶剂。 当使用水作为发泡剂时， 可以用水浸润所述主体材料。
按照本发明， 用于制备本发明材料的方法的具体步骤如下：
( 1 ) 将聚乙烯醇与水接触并充分溶胀， 得到含水的聚乙烯醇， 之后加 入淀粉、 多元醇、有机羧酸以及选择性含有的纤维素基聚合物、 盐类添加剂 和 /或助剂，将上述物料混合均匀得到混合物。其中，聚乙烯醇与水接触的时 间为 30-60分钟， 搅拌的速度为 50-650转 /分钟； 含水的聚乙烯醇与淀粉、 多元醇、有机羧酸、选择性含有的纤维素基聚合物、盐类添加剂和 /或助剂的 搅拌共混的时间可以是 5-60分钟， 搅拌共混的转速为 50-650转 /分钟， 优选 先以低速搅拌再以高速搅拌；
(2)采用双螺杆挤出机，在长径比为 20-64，螺杆转速 50-1200转 /分钟， 从进料端到出料端，各区段温度依次设定为 90-150°C、 95-155°C、 100-160 °C、 115-165°C、 12(M75°C、 125-175°C、 130-185°C、 135-185°C、 110-180°C、 115-175°C、 120-185°C、 130-180°C， 真空段的真空度为 0.02至 0.09兆帕的 条件下将上述得到的混合物熔融挤出造粒， 得到所述主体材料；
(3 ) 将主体材料与发泡剂混合， 得到本发明提供的水溶性可生物降解 材料粒子。 其中， 混合的方式可以是将主体材料浸渍于化学发泡剂溶液中， 浸渍的温度为 20-105°C、 压力为 0.1-15兆帕、浸渍时间为 3-360分钟。浸渍 后除去溶剂，除去溶剂的方法优选为减压除去溶剂。当使用水作为发泡剂时， 用水浸润所述主体材料。
本发明提供的水溶性可生物降解材料可以通过发泡成型的方法制成发 泡类制品。 所述发泡成型的步骤和条件已为本领域技术人员所公知， 例如， 所述发泡成型方法包括但不限于以下两种：
方法一：将上述得到的水溶性可生物降解材料投入到单段式单螺杆挤出 机的喂料器中， 所述单螺杆挤出机从进料端到出料端一般分为 6个区段， 从 进料端到出料端， 各区段的温度依次设定为 100-155°C、 105-165°C：、 110-175°C、 120-185°C、 130-195 °C , 在螺杆转速为 50-300转 /分的工艺条件 下， 将水溶性可生物降解材料熔融， 再经环形模头挤出后成为发泡材料， 然 '后在成型机上对发泡材料进行真空吸塑成型、冲切后，即可得到发泡类制品； 或经单孔和 /或多孔模头挤出直接形成发泡体，同时采用模面热切的方式将发 泡体切成单独的发泡体产品；
方法二：将上述得到的水溶性可生物降解材料投入到双段式单螺杆挤出 机的第一段单螺杆挤出机的喂料器中，所述第一段单螺杆挤出机从进料端到 出料端一般分为 6个区段， 从进料端到出料端， 各区段的温度依次设定为 100°C-155°C、 105°C-165°C、 110°C-175。C、 120°C-185°C、 130°C-195°C， 在 第一段单螺杆挤出机的螺杆转速为 50-300转 /分的工艺条件下， 将水溶性可 生物降解材料熔融并通过螺杆连接装置将熔融物料输送至第二段单螺杆挤 出机中，并在第一段单螺杆挤出机的第五和第六区段之间注入液态氟利昂或 丁烷作为物理助发泡剂； 第二段单螺杆挤出机中保持 20-280千克 /平方厘米 的压力， 熔融物料经环形模头挤出后成为发泡材料， 然后在成型机上对发泡 材料进行真空吸塑成型、冲切后， 即可得到发泡类制品；或经单孔和 /或多孔 模头挤出直接形成发泡体， 同时采用模面热切的方式将发泡体切成单独的发 泡体产品。
以下通过实施例对本发明进行详细说明。 实施例 1
该实施例用于说明本发明提供的水溶性可生物降解材料及其制备方法。
( 1 )在 500转 /分钟的搅拌速度下将水加入到 1.5倍重量的聚乙烯醇（醇 解度为 86， 平均聚合度为 1750)中， 在 65°C下搅拌 35分钟之后， 得到含水 的聚乙烯醇。 其中在得到的含水的聚乙烯醇中， 聚乙烯醇与水的重量比为 2.3。 将 21重量份上述得到的含水聚乙烯醇与 15重量份甘油、 15重量份山 梨糖醇在搅拌机混合，搅拌机先以 100转 /分钟搅拌约 20分钟，然后再以 200 转 /分钟搅拌 30分钟； 然后再加入 40重量份淀粉、 3重量份甲基纤维素、 2 重量份硬脂酸锌、 4重量份环氧大豆油并混合均匀得到混合物 Ml。
(2)将上述得到的混合物送入双螺杆挤出机的进料口中， 挤出机的长 径比 L:D=48:1， 螺杆直径为 Φ58毫米。调整螺杆的转速至 900转 /分钟， 从 进料端到出料端，各区段温度分别设定为 130°C、135°C、140°C、150°C、160°C、 165°C、 165°C、 170°C、 175°C、 170°C、 180°C和 170°C ; 真空段的真空度保 持在 -0.02至 -0.09兆帕；在挤出机的出料口得到直径为 3毫米的条状挤出物， 将条状挤出切粒， 得到长度为 2毫米的主体材料粒料 Z1。
( 3 )将 2.5重量份 AC发泡剂溶于 25重量份 DMSO中形成溶液，在 25 °C、 1兆帕的条件下在高压釜中用该溶液浸渍 100重量份上述得到的粒料 10分 钟， 然后减压除去 DMSO, 最终得到本发明提供的水溶性可生物降解材料 BSR-07V-FSl o 对比例 1 该对比例用于说明现有的含聚乙烯醇的可生物降解材料及其制备方法。
( 1 )将 15重量份聚乙烯醇 （醇解度为 86， 中值聚合度为 1750) 与 40 重量份淀粉混合均匀， 然后与 10重量份水、 15重量份甘油、 15重量份山梨 糖醇、 3重量份甲基纤维素、 2重量份硬脂酸锌和 4重量份环氧大豆油一起 加入到搅拌机中混合，搅拌机先以 100转 /分钟搅拌约 20分钟，然后再以 200 转 /分钟搅拌 30分钟， 得到混合物 CM1；
(2)用与实施例 1步骤（2)相同的方法将上述混合物 CM1挤出造粒， 结果得到没有任何可塑性的粉末状碳化物。这可能是因为双螺杆挤出机的双 螺杆相互啮合，螺杆的转速高达 900转 /分钟，相互啮合的双螺杆对加入到双 螺杆挤出机中的物料有强烈的摩擦和剪切作用，而聚乙烯醇为未增塑的聚乙 烯醇， 在聚乙烯醇融化并与其它组分反应前， 强烈的摩擦和剪切作用产生的 热量就使温度达到聚乙烯醇分解温度，聚乙烯醇碳化造成了聚乙烯醇与其它 组分不能反应生成具有稳定熔融状态的反应产物， 因此生成了没有任何可塑 性的粉末状碳化物。 实施例 2
该实施例用于说明本发明提供的水溶性可生物降解材料及其制备方法。
( 1 )在 400转 /分钟的搅拌速度下将水加入到 2.5倍重量的聚乙烯醇（醇 解度为 90， 平均聚合度为 1750)中， 在 30Ό搅拌 55分钟之后， 得到含水的 聚乙烯醇。其中在得到的含水的聚乙烯醇中， 聚乙烯醇与水的重量比为 3.1。 将 27重量份上述得到的含水聚乙烯醇、 50重量份淀粉与 20重量份甘油、 3 重量份环氧大豆油在搅拌机中混合， 搅拌机先以 100转 /分钟搅拌约 7分钟， 然后再以 200转 /分钟搅拌 8分钟， 搅拌均匀得到混合物 M2。
(2)按照与实施例 1的步骤（2)相同的方法由混合物 M2制得主体材 料粒料 Z2。 (3 )将 4重量份 AC发泡剂溶于 50重量份 DMSO中形成溶液，在 55°C、 12兆帕的条件下在高压釜中用该溶液浸渍 100重量份上述得到的粒料 100 分钟，然后减压除去 DMSO,最终制得本发明提供的水溶性可生物降解材料
Figure imgf000017_0001
实施例 3
该实施例用于说明本发明提供的水溶性可生物降解材料及其制备方法。
( 1 )在 100转 /分钟的搅拌速度下将水加入到 3.6倍重量的聚乙烯醇（醇 解度为 88， 平均聚合度为 1500)中， 在 50°C下搅拌 60分钟之后， 得到含水 的聚乙烯醇。 其中在得到的含水的聚乙烯醇中， 聚乙烯醇与水的重量比为 5.2。 将 70重量份淀粉与 12重量份山梨糖醇在搅拌机中混合， 搅拌机先以 100转 /分钟搅拌约 7分钟， 然后再以 200转 /分钟搅拌 8分钟； 然后再加入 18重量份上述得到的含水聚乙烯醇并混合均匀得到混合物 M3。
(2)按照与实施例 1的步骤（2)相同的方法由混合物 M3制得主体材 料粒料 Z3。
(3)将 5重量份 AC发泡剂溶于 50重量份 DMSO中形成溶液，在 65 °C、 10兆帕的条件下在高压釜中用该溶液浸渍 100重量份上述得到的粒料 200 分钟，然后减压除去 DMSO,最终制得本发明提供的水溶性可生物降解材料
Figure imgf000017_0002
实施例 4
该实施例用于说明本发明提供的水溶性可生物降解材料及其制备方法。 ( 1 )在 150转 /分钟的搅拌速度下将水加入到 3倍重量的聚乙烯醇 （醇 解度为 88, 平均聚合度为 1500)中， 在 25 °C下搅拌 40分钟之后， 得到含水 的聚乙烯醇。 其中在得到的含水的聚乙烯醇中， 聚乙烯醇与水的重量比为 4.2。将 48重量份上述得到的含水聚乙烯醇与 30重量份淀粉在搅拌机中混合， 搅拌机先以 100转 /分钟搅拌约 Ί分钟， 然后再以 200转 /分钟搅拌 8分钟； . 然后再加入 12重量份甘油、 10重量份山梨糖醇并混合均匀得到混合物 M4。
(2)按照与实施例 1的步骤（2)相同的方法由混合物 M4制得主体材 料粒料 Z4。
(3 )将 6重量份 AC发泡剂溶于 40重量份 DMSO中形成溶液，在 55°C、 5兆帕的条件下在高压釜中用该溶液浸渍 100重量份上述得到的粒料 10分 钟， 然后减压除去 DMSO， 最终制得本发明提供的水溶性可生物降解材料 BSR-07V-FS4。 实施例 5
该实施例用于说明本发明提供的水溶性可生物降解材料及其制备方法。
( 1 )在 200转 /分钟的搅拌速度下将水加入到 3倍重量的聚乙烯醇 （醇 解度为 86， 中值聚合度为 1950)中， 在 30°C下搅拌 40分钟之后， 得到含水 的聚乙烯醇。 其中在得到的含水的聚乙烯醇中， 聚乙烯醇与水的重量比为 4.1。 将 42重量份上述得到的含水聚乙烯醇与 10重量份甘油和 25重量份季 戊四醇在搅拌机中混合， 搅拌机先以 200转 /分钟搅拌约 15分钟， 然后再以 300转 /分钟搅拌 10分钟；然后再加入 3重量份乙酸和 20重量份淀粉并混合 均匀得到混合物 M5。
(2)按照与实施例 1的步骤（2)相同的方法由混合物 M5制得主体材 料粒料 Z5。
(3 )按照与实施例 1的步骤（3 )相同的方法由主体材料粒料 Z5制得 本发明提供的水溶性可生物降解材料 BSR-07V-FS5。
该实施例用于说明本发明提供的水溶性可生物降解材料及其制备方法。 ( 1 )在 200转 /分钟的搅拌速度下将水加入到 3倍重量的聚乙烯醇 （醇 解度为 86， 中值聚合度为 1750)中， 在 30°C下搅拌 40分钟之后， 得到含水 的聚乙烯醇。 其中在得到的含水的聚乙烯醇中， 聚乙烯醇与水的重量比为 4.1。 将 40重量份上述得到的含水聚乙烯醇与 10重量份山梨糖醇和 15重量 份季戊四醇在搅拌机中混合， 搅拌机先以 200转 /分钟搅拌约 15分钟， 然后 再以 400转 /分钟搅拌 5分钟； 然后再加入 25重量份淀粉、 4重量份乙酸、 2 重量份丁二酸、 2重量份环氧大豆油、 1重量份硬脂酸钙和 1重量份硬脂酸 锌并混合均匀得到混合物 M6。
(2)按照与实施例 1的步骤（2)相同的方法由混合物 M6制得主体材 料粒料 Z6。
(3 ) 按照与实施例 1的步骤 （3 ) 相同的方法由主体材料粒料 Z6制得 本发明提供的水溶性可生物降解材料 BSR-07V-FS6。 实施例 7-12
下面的实施例说明本发明提供的水溶性可生物降解材料的性能。
分别将实施例 1-6 得到的水溶性可生物降解材料 BSR-07V-FS1 至 BSR-07V-FS6投入到双段式单螺杆挤出机的第一段单螺杆挤出机的喂料器 当中， 从进料端到出料端， 第一段单螺杆挤出机各区段的温度依次设定为 120°C、 140°C、 145°C、 160°C、 180°C， 螺杆转速为 200转 /分， 将所述材料 熔融挤出， 并通过螺杆连接装置将熔融物料输送至第二段单螺杆挤出机中， 并在第一段单螺杆挤出机的第五区段和第六区段之间，注入液态丁垸作为物 理助发泡剂；第二段单螺杆挤出机中的压力保持在 100千克 /平方厘米，熔融 物料经环形模头挤出后成为发泡材料， 经分切延展开形成发泡片材， 然后在 成型机上对发泡片材进行真空吸塑成型、冲切后， 即可得到所要求的的发泡 制品 FS1至 FS6。 采用如下方法对上述发泡类制品进行各项性能测试，测定结果如表 1所
按照 GB1033-1986 中规定的塑料密度和相对密度试验方法分别测定水 溶性可生物降解材料 BSR-07V-FS1至 BSR-07V-FS6和发泡制品 FS1至 FS6 的相对密度， 利用下式计算发泡倍率： 水溶性可生物降解材料的密度一制品的密度
发泡倍率=
水溶性可生物降解材料的密度 按照 IS01856标准， 测定制品的压缩强度、 压縮回弹率、 尺寸稳定性； 其中压缩强度由制品相对变形 10体积％时的压縮应力来表示； 压縮回弹率 是指将制品压縮至 50体积％并维持 72小时后，制品的体积与最初体积的百 分比； 尺寸稳定性是将制品在 105±3°C的温度下放置 7天， 用制品的变形率 表示制品的尺寸稳定性， 变形率越小表示尺寸稳定性越好；
分别按照 ISO 14855-99中规定的方法测定制品的生物降解率； 水溶性测试： 首先将上述发泡制品 FS1至 FS6破碎成尺寸小于 10毫米 xlO毫米 x5毫米的小碎片， 然后称取 20克上述碎片浸泡到 100克 25°C的水 中， 5分钟、 10分钟和 15分钟后用孔径为 80-120微米的滤纸过滤， 将所得 固体在 100°C下干燥 1小时， 称重， 浸泡前后的重量差与浸泡前的重量之比 即为制品 FS1至 FS6在不同的时间点在 25°C水中的溶解度。
发泡类制品表面粘性的测试： 从发泡制品 FS1-FS6分别裁切出 20个尺 寸为 10厘米 xlO厘米 x3厘米的发泡片材，将 20个发泡片材分成 10组（每 组两个）， 将每组的两个发泡片材叠放在一起 （10厘米 xlO厘米的表面相接 触）， 然后在温度为 30°C、 相对湿度为 70%的环境中放置 48小时后以 1000 帕的压力按压每组的两个发泡片材 5秒钟，然后观察每组的两个发泡片材是 否粘在一起， 并记录粘在一起的发泡片材的组数。 表 1
Figure imgf000021_0001
从表 1所示的结果可以看出， 由实施例 1-6的水溶性可生物降解材料粒 料 BSR-07V-FS1至 BSR-07V-FS6制成的发泡制品 PF1至 PF6具有良好的发 泡倍率（大于 45% )、 压缩强度（≥35兆帕）、 压缩回弹率和尺寸稳定性； 生 物降解率极高， 45天的生物降解率大于 62% , 60天的生物降解率大于 76%， 99天的生物降解率大于 93 %， 完全符合 ISO 14855对可生物降解制品的要 求（180天内生物分解率大于 90% )。 由于所述材料为水溶性材料， 发泡制 品 FS1至 FS6在 15分钟内可以完全溶于水中， 因此当所述制品使用完后在 自然条件下溶于水中而加速降解， 不会对环境造成污染。
实施例 5 和 6 在制备水溶性可生物降解材料 BSR-07V-FS5 和 BSR-07V-FS6时加入了有机羧酸， 由 BSR-07V-FS5和 BSR-07V-FS6制得的 发泡制品 FS5和 FS6在表面粘性测试中没有出现粘连的现象，因此，与由实 施例 1-4的水溶性可生物降解材料粒料 BSR-07V-FS1至 BSR-07V-FS4制成 的发泡制品 FS1至 FS4相比， 由 BSR-07V-FS5和 BSR-07V-FS6制得的发泡 制品 FS5和 FS6的表面粘性显著降低，在使用过程中不会出现多个发泡制品 之间以及发泡制品与其它物品之间粘连的问题。 实施例 13
该实施例用于说明本发明实施例 1提供的水溶性可生物降解材料的主体 材料的熔融和热分解性质。
通过下面的方法测定实施例 1提供的水溶性可生物降解材料的主体材料 Z1的熔融和热分解性质。
准确称取约 4.7毫克实施例 1制得的主体材料 Zl，置于 NETZSCH DSC 204F1型示差扫描量热分析仪的样品池中， 在流速为 60毫升 /分钟的氮气保 护下， 以 1(TC/分钟的升温速率将样品由 25°C加热至 180°C，在 180°C下保持 2分钟， 然后以 10°C/分钟的升温速率继续加热至 300°C， 得到的如图 1所示 的 DSC曲线。
准确称取约 4.7毫克实施例 1制得的主体材料 Z1，置于型号为 TG209F1 的热重分析仪 （德国耐驰仪器制造有限公司） 的样品池中， 在流速为 60毫 升 /分钟的氮气保护下，以 10°C/分钟的升温速率将样品由 25°C加热至 180°C， 在 180°C下保持 2分钟， 然后以 10°C/分钟的升温速率继续加热至 600°C， 得 如图 2所示的热重测试曲线。
从图 1可以看出， 样品的 DSC曲线上在 135Ό-184Ό的温度范围内、 255°C和 270°C附近各有一个吸热峰； 从图 2可以看出， 在 255°C-352°C的温 度范围内， 样品快速失重， 而在 135°C-184°C的温度范围内样品的重量基本 上没有损失。 结合图 1 和图 2 的结果表明， 样品的 DSC 曲线中的在 135°C-184°C的吸热峰为样品熔融吸热造成的吸热峰， 在 255°C和 270°C附近 的吸热峰由于伴随着样品的快速失重， 说明样品在此温度下分解， 因此， 该 吸热峰为样品分解造成的吸热峰。 这说明实施例 1 得到的主体材料在 135 C-184°C的较宽的温度范围内可以实现稳定的熔融状态， 该熔融温度大 大低于其自身的分解温度， 可以在该较宽的温度范围内对粒料进行热塑加 工。如表 2所示， 由实施例 1的水溶性可生物降解材料熔融、 发泡成型的发 泡制品的发泡倍率、压缩强度和压縮回弹率非常优异。这进一步说明本发明 提供的材料完全不同于含有聚乙烯醇、淀粉和增塑剂的简单混合物， 是一种 全新的热塑性材料， 该材料的熔融温度大大低于其本身的分解温度， 也远低 于其中的有聚乙烯醇、 淀粉中任何一个的分解温度。 实施例 14
该实施例用于说明由本发明的水溶性可生物降解材料的性质。
图 3和图 4分别给出了实施例 1中所使用的原淀粉和实施例 1制得的水 溶性可生物降解材料的主体材料 Z1的横截面扫描电子显微照片， 放大倍数 均为 2000倍。该扫描电子显微照片采用型号为 JSM5600LV的扫描电子显微 镜 （日本电子株式会社） 得到。
在图 3中可以清晰地看到淀粉颗粒为球形颗粒，而在图 4中已经看不到 淀粉颗粒的存在。这说明在实施例 1制备所述粒料的过程中， 在双螺杆挤出 机的双螺杆的剪切作用下， 淀粉颗粒被充分细化， 而且淀粉与其它组分之间 不仅仅是发生了简单的物理混合， 而是形成了一种单一的均匀的产物。这进 一步说明本发明提供的水溶性可生物降解材料中所含的主体材料完全不同 于含有聚乙烯醇、 淀粉和增塑剂的简单混合物， 是一种全新的材料。
此外， 表 2中的数据表明， 本发明提供的由实施例 1的水溶性可生物降 解材料熔融、发泡成型的发泡制品的发泡倍率、压缩强度和压缩回弹率非常 优异， 优于由所述材料中的任意单一组分制成的制品。这也说明本发明提供 的水溶性可生物降解材料中所含的主体材料是一种完全不同于现有简单混 合物的全新的反应产物。

Claims

权利要求书
1、 一种水溶性可生物降解材料， 该材料含有主体材料和发泡剂， 其特 征在于， 该主体材料为一种混合物经熔融而形成的产物， 所述混合物含有淀 粉、 多元醇和含水的聚乙烯醇， 所述聚乙烯醇为亲水性聚乙烯醇。
2、 根据权利要求 1 所述的材料， 其中， 所述主体材料的熔融温度为 130-190 °C， 分解温度为 250-400 °C。
3、 根据权利要求 1所述的材料， 其中， 以混合物的总重量为基准， 所 述混合物中含水的聚乙烯醇的含量为 10-60重量％， 淀粉的含量为 10-85重 量％， 多元醇的含量为 5-40重量％。
4、 根据权利要求 1所述的材料， 其中， 所述含水的聚乙烯醇通过将聚 乙烯醇与水接触而得到，接触的条件及聚乙烯醇和水的用量足以使所述含水 的聚乙烯醇中聚乙烯醇与水的重量比为 0.75-10。
5、 根据权利要求 4所述的材料， 其中， 聚乙烯醇和水的用量重量比为 0.5-5
6、 根据权利要求 4所述的材料， 其中， 所述接触的条件包括所述聚乙 烯醇与水在搅拌下接触， 接触时间为 30-60分钟。
7、根据权利要求 1所述的材料， 其中， 所述聚乙烯醇的醇解度为 80-95 %； 聚乙烯醇的中值聚合度为 500-2000。
8、 根据权利要求 1所述的材料， 其中， 所述多元醇选自甘油、 山梨糖 醇和季戊四醇中的一种或几种。
9、 根据权利要求 1所述的材料， 其中， 所述混合物中还含有有机羧酸， 该有机羧酸的碳原子数为 1-20， 以所述混合物的总重量为基准， 该有机羧酸 的含量为 0.5-10重量％。
10、 根据权利要求 1所述的材料， 其中， 所述主体材料与所述发泡剂的 含量重量比为 10: 1至 1000: 1； 所述发泡剂为水或化学发泡剂。
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EP1942137A1 (en) 2008-07-09
CN1935881B (zh) 2012-05-09
CN1935881A (zh) 2007-03-28
EP1942137A4 (en) 2008-12-03

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