CN112480580A - Water-soluble biodegradable polymer alloy and preparation method thereof - Google Patents
Water-soluble biodegradable polymer alloy and preparation method thereof Download PDFInfo
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- CN112480580A CN112480580A CN202011374713.6A CN202011374713A CN112480580A CN 112480580 A CN112480580 A CN 112480580A CN 202011374713 A CN202011374713 A CN 202011374713A CN 112480580 A CN112480580 A CN 112480580A
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- polyvinyl alcohol
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- alcohol resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the technical field of polyvinyl alcohol compositions, in particular to a water-soluble biodegradable polymer alloy and a preparation method thereof, wherein the water-soluble biodegradable polymer alloy comprises polyvinyl alcohol resin, thermoplastic polyester and reactive functional group oligomer, and the weight ratio of the polyvinyl alcohol resin to the thermoplastic polyester is 80-99.9: 0.1-20, the weight ratio of the polyvinyl alcohol resin to the reactive functional group oligomer is 50-90: 50-10. The invention carries out blending modification on the thermoplastic processing of the polyvinyl alcohol resin, and the blending modified polyvinyl alcohol resin is obtained by selecting a small molecular compound or oligomer with a complementary structure with the polyvinyl alcohol resin for blending, plasticizing and modifying, is physical modification on the polyvinyl alcohol resin and does not change the molecular structure, so that the PVA resin after blending modification still has certain crystallinity, improves melt fluidity and expands the application of the PVA resin in many fields. Meanwhile, the preparation process is relatively simple, low in production cost, high in production efficiency and environment-friendly.
Description
Technical Field
The invention relates to the technical field of polyvinyl alcohol compositions, in particular to a water-soluble biodegradable polymer alloy and a preparation method thereof.
Background
Polyvinyl alcohol (PVA) is a water-soluble polymer material with excellent performance and wide application. Because of its good water solubility, film forming property, adhesion, emulsifying property and barrier property, it is widely used in the fields of fiber, film, adhesive, paper making auxiliary agent, etc. In recent years, research has proved that PVA is a synthetic polymer material which can be completely biodegraded, which further expands the application range. However, the melting temperature of PVA is 220-240 ℃ and is close to the decomposition temperature, which brings difficulty to the thermoplastic processing and molding of PVA. For this reason, the commonly used methods for forming PVA materials are all solution forming methods such as solution spinning, solution casting film formation, and the like. The solution processing and forming needs to go through the dissolving and drying processes, and has the defects of complex process, high cost, low yield and the like. Therefore, PVA formed by solution processing can only be used for preparing films, fibers and the like which are mostly used for low-end coatings, films and products or used as auxiliary and auxiliary materials. Compared with solution processing, the thermoplastic processing has the advantages of simple process, low energy consumption, high efficiency, low cost and the like. If the thermoplastic processing methods such as extrusion, injection molding and the like are used, a PVA three-dimensional product can be prepared, so that the application field of PVA is expanded. Therefore, it is important to realize thermoplastic processing of PVA, and in order to realize good thermoplastic processing of PVA, it is necessary to produce a thermoplastic polyvinyl alcohol water-soluble alloy having good melt flowability.
Disclosure of Invention
In order to solve the problems, the invention provides a water-soluble biodegradable polymer alloy and a preparation method for preparing the water-soluble biodegradable polymer alloy.
The invention is realized by adopting the following scheme:
a water-soluble biodegradable high-molecular alloy comprises polyvinyl alcohol resin, thermoplastic polyester and reactive functional group oligomer, wherein the weight ratio of the polyvinyl alcohol resin to the thermoplastic polyester is 80-99.9: 0.1-20, the weight ratio of the polyvinyl alcohol resin to the reactive functional group oligomer is 50-90: 50-10.
Further, the reactive functional group oligomer is an organic substance, an inorganic substance, a vegetable oil, a mineral oil or a composite substance with carboxyl, conjugated olefin, epoxy, acid anhydride, cyano, amide and hydroxyl.
Furthermore, the polyvinyl alcohol resin is water-soluble polyvinyl alcohol resin at normal temperature, the alcoholysis degree is 70-92mol/mol, and the polymerization degree is 300-2000-.
Further, the thermoplastic polyester is polyester formed by aliphatic ester of poly phthalic acid and at least one of ethylene glycol, butanediol, pentanediol or aromatic diol.
Further, the thermoplastic polyester is a polyester formed by aromatic ester and at least one of ethylene glycol, butanediol, pentanediol or aromatic diol.
Further, the plasticizer comprises at least one of glycerol, polyethylene glycol, water or starch.
A preparation method of a water-soluble biodegradable polymer alloy comprises the following steps:
step 1, placing polyvinyl alcohol resin, reactive functional group oligomer and plasticizer into a closed reaction kettle with a reflux device;
step 2, mixing, crushing and stirring for 0.5-2 hours at room temperature to 60 ℃;
step 3, stirring the mixture in the step 2 in another cooling mixer for 2-6 hours at room temperature for later use;
step 4, uniformly mixing the mixture stirred at room temperature in the step 3 with thermoplastic polyester, a stabilizer and a lubricant;
step 5, extruding the mixture in the step 4 at the temperature of 120-190 ℃ by using a double-screw extruder;
and 6, cooling the extrudate to 20-40 ℃, and then cutting and packaging.
Further, the reactive functional group oligomer in the step 1 is ethylene oxide, and the thermoplastic polyester in the step 4 is polybutylene succinate.
Further, the thermoplastic polyester in the step 4 is a poly aliphatic or aromatic phthalate.
Further, in the step 4, the stabilizer is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] ester, and the lubricant is pentaerythritol distearate.
Compared with the prior art, the invention has the following beneficial effects:
the water-soluble biodegradable high molecular alloy provided by the invention is prepared from components such as polyvinyl alcohol resin, thermoplastic polyester, reactive functional group oligomer and the like, the polyvinyl alcohol resin is subjected to blending modification by thermoplastic processing, and the blending modified polyvinyl alcohol resin is subjected to physical modification on the polyvinyl alcohol resin without changing the molecular structure because small molecular compounds or oligomers with complementary structures with the polyvinyl alcohol resin are selected for blending, plasticizing and modifying, so that the PVA resin after blending modification still has certain crystallinity, the melt flowability is improved, and the application of the PVA resin in many fields is expanded. Meanwhile, the preparation process is relatively simple, low in production cost, high in production efficiency and environment-friendly.
Detailed Description
The present invention will be described in further detail below with reference to specific examples in order to facilitate understanding of the invention by those skilled in the art.
The invention provides a water-soluble biodegradable polymer alloy, which comprises polyvinyl alcohol resin (PVA), thermoplastic polyester and reactive functional group oligomer, wherein the weight ratio of the polyvinyl alcohol resin to the thermoplastic polyester is 80-99.9: 0.1-20, the weight ratio of the polyvinyl alcohol resin to the reactive functional group oligomer is 50-90: 50-10. Also comprises a plasticizer, wherein the plasticizer comprises at least one of glycerol, polyethylene glycol, water or starch.
The reactive functional group oligomer is organic matter, inorganic matter, vegetable oil, mineral oil or composite with carboxyl, conjugated olefin, epoxy group, acid anhydride, cyano group, amide group and hydroxyl.
The polyvinyl alcohol resin is water-soluble polyvinyl alcohol resin at normal temperature, the alcoholysis degree is 70-92mol/mol, and the polymerization degree is 300-2000-one-year-old.
The thermoplastic polyester is formed by the aliphatic ester of the poly phthalic acid and at least one of ethylene glycol, butanediol, pentanediol or aromatic diol, and the thermoplastic polyester can also be formed by the aromatic ester and at least one of ethylene glycol, butanediol, pentanediol or aromatic diol. For example, polybutylene succinate (PBS) can be used.
The melt index of the water-soluble biodegradable polymer alloy is 8-35 g/10min, the melting temperature is 120-280 ℃, the water-soluble temperature is 20-80 ℃, and the water-soluble biodegradable polymer alloy has low crystallinity and good melt flowability. The invention carries out blending modification on the thermoplastic processing of the polyvinyl alcohol resin, and the blending modified polyvinyl alcohol resin is obtained by selecting a small molecular compound or oligomer with a complementary structure with the polyvinyl alcohol resin to carry out blending plasticizing modification, is physical modification on PVA and does not change the molecular structure, so that the PVA resin after blending modification still has certain crystallinity, improves melt fluidity and expands the application of the PVA resin in many fields.
The invention also provides a preparation method of the water-soluble biodegradable polymer alloy, which is used for preparing the water-soluble biodegradable polymer alloy and comprises the following steps:
step 1, placing polyvinyl alcohol resin, reactive functional group oligomer and plasticizer into a closed reaction kettle with a reflux device;
step 2, mixing, crushing and stirring for 0.5-2 hours at room temperature to 60 ℃;
step 3, stirring the mixture in the step 2 in another cooling mixer for 2-6 hours at room temperature for later use;
step 4, uniformly mixing the mixture stirred at room temperature in the step 3 with thermoplastic polyester, a stabilizer and a lubricant;
step 5, extruding the mixture in the step 4 at the temperature of 120-190 ℃ by using a double-screw extruder;
and 6, cooling the extrudate to 20-40 ℃, and then cutting and packaging.
The reactive functional group oligomer in the step 1 is ethylene oxide, and the thermoplastic polyester in the step 4 is polybutylene succinate (PBS).
In addition, the thermoplastic polyester in the step 4 can also adopt poly phthalic acid aliphatic ester or aromatic ester.
In the step 4, the stabilizer is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the lubricant is pentaerythrityl distearate.
The present invention is described in detail below by referring to various examples, and it should be noted that the following examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and that the skilled person in the art may make some insubstantial modifications and adaptations of the present invention based on the above descriptions and still fall within the scope of the present invention.
Example 1
In the embodiment, 6 parts of polyvinyl alcohol resin, 2 parts of polybutylene succinate, 0.2 part of ethylene oxide oligomer, and 1 part of a mixture of water and glycerol (in a weight ratio of 1: 1) are adopted according to the parts by weight.
Under the condition of the mixture ratio, the prepared water-soluble biodegradable polymer alloy has the initial melting point of 176 ℃, the tensile strength of 36 MPa, the elongation of 400 percent and the bending strength of 490 MPa.
Example 2
In the embodiment, 6 parts of polyvinyl alcohol resin, 2 parts of polybutylene succinate, 0.4 part of ethylene oxide oligomer and 0.8 part of a mixture of water and glycerol (the weight ratio is 1: 1) are adopted according to the parts by weight.
Under the condition of the proportioning, the prepared water-soluble biodegradable polymer alloy has the initial melting point of 166 ℃, the tensile strength of 46 MPa, the elongation of 450 percent and the bending strength of 801 MPa.
Example 3
In the embodiment, 6 parts of polyvinyl alcohol resin, 2 parts of polybutylene succinate, 0.6 part of ethylene oxide oligomer and 0.6 part of a mixture of water and glycerol (the weight ratio is 1: 1) are adopted according to the parts by weight.
Under the condition of the proportioning, the prepared water-soluble biodegradable polymer alloy has the initial melting point of 157 ℃, the tensile strength of 55 MPa, the elongation of 513 percent and the bending strength of 802 MPa.
Example 4
In the embodiment, 6 parts of polyvinyl alcohol resin, 2 parts of polybutylene succinate, 0.8 part of ethylene oxide oligomer and 0.4 part of a mixture of water and glycerol (the weight ratio is 1: 1) are adopted according to the parts by weight.
Under the condition of the proportioning, the prepared water-soluble biodegradable polymer alloy has the initial melting point of 153 ℃, the tensile strength of 31 MPa, the elongation of 455 percent and the bending strength of 612 MPa.
Example 5
In the embodiment, 6 parts of polyvinyl alcohol resin, 2 parts of polybutylene succinate, 1 part of ethylene oxide oligomer, and 0.2 part of a mixture of water and glycerol (in a weight ratio of 1: 1) are adopted according to the parts by weight.
Under the condition of the mixture ratio, the prepared water-soluble biodegradable polymer alloy has the initial melting point of 144 ℃, the tensile strength of 33 MPa, the elongation of 445 percent and the bending strength of 689 MPa.
In the description of the present invention, it is to be understood that the indicated orientations or positional relationships are only for convenience in describing the present invention and for simplicity in description, and are not intended to indicate or imply that the indicated devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be construed as limiting the present invention.
Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "connected," "secured," and the like are to be construed broadly, e.g., as meaning permanently attached, removably attached, or integral to one another; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
While the invention has been described in conjunction with the specific embodiments set forth above, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations that fall within the scope of the included claims.
Claims (10)
1. The water-soluble biodegradable polymer alloy is characterized by comprising polyvinyl alcohol resin, thermoplastic polyester and reactive functional group oligomer, wherein the weight ratio of the polyvinyl alcohol resin to the thermoplastic polyester is 80-99.9: 0.1-20, the weight ratio of the polyvinyl alcohol resin to the reactive functional group oligomer is 50-90: 50-10.
2. The water-soluble biodegradable polymer alloy according to claim 1, wherein the reactive functional group oligomer is an organic substance, an inorganic substance, a vegetable oil, a mineral oil or a synthetic substance having a carboxyl group, a conjugated olefin, an epoxy group, an acid anhydride, a cyano group, an amide group, a hydroxyl group.
3. The water-soluble biodegradable polymer alloy according to claim 1, wherein the polyvinyl alcohol resin is a water-soluble polyvinyl alcohol resin at room temperature, the alcoholysis degree is 70-92mol/mol, and the polymerization degree is 300-2000-.
4. The water-soluble biodegradable polymer alloy according to claim 1, wherein said thermoplastic polyester is a polyester of aliphatic ester of poly (phthalic acid) and at least one of ethylene glycol, butanediol, pentanediol, or aromatic diol.
5. The water-soluble biodegradable polymer alloy according to claim 1, wherein said thermoplastic polyester is a polyester of an aromatic ester and at least one of ethylene glycol, butylene glycol, pentylene glycol, or an aromatic diol.
6. The water-soluble biodegradable polymer alloy according to claim 1, further comprising a plasticizer, wherein said plasticizer comprises at least one of glycerol, polyethylene glycol, water, or starch.
7. A method for preparing a water-soluble biodegradable polymer alloy, which comprises the steps of:
step 1, placing polyvinyl alcohol resin, reactive functional group oligomer and plasticizer into a closed reaction kettle with a reflux device;
step 2, mixing, crushing and stirring for 0.5-2 hours at room temperature to 60 ℃;
step 3, stirring the mixture in the step 2 in another cooling mixer for 2-6 hours at room temperature for later use;
step 4, uniformly mixing the mixture stirred at room temperature in the step 3 with thermoplastic polyester, a stabilizer and a lubricant;
step 5, extruding the mixture in the step 4 at the temperature of 120-190 ℃ by using a double-screw extruder;
and 6, cooling the extrudate to 20-40 ℃, and then cutting and packaging.
8. The method for preparing water-soluble biodegradable polymer alloy according to claim 7, wherein the reactive functional group oligomer in step 1 is ethylene oxide, and the thermoplastic polyester in step 4 is polybutylene succinate.
9. The method according to claim 7, wherein the thermoplastic polyester in step 4 is a poly aliphatic or aromatic phthalate.
10. The method for preparing a water-soluble biodegradable polymer alloy according to claim 7, wherein the stabilizer in step 4 is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and the lubricant is pentaerythritol distearate.
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| CN202011374713.6A CN112480580A (en) | 2020-11-30 | 2020-11-30 | Water-soluble biodegradable polymer alloy and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115785595A (en) * | 2022-11-28 | 2023-03-14 | 河源市普立隆新材料科技有限公司 | Polyvinyl alcohol melt blown film based on anhydrous plasticization and preparation method thereof |
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2020
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115785595A (en) * | 2022-11-28 | 2023-03-14 | 河源市普立隆新材料科技有限公司 | Polyvinyl alcohol melt blown film based on anhydrous plasticization and preparation method thereof |
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