CN108624020B - Seawater degradation material with adjustable use period and degradation period and preparation method thereof - Google Patents
Seawater degradation material with adjustable use period and degradation period and preparation method thereof Download PDFInfo
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a seawater degradation material with adjustable use period and degradation period and a preparation method thereof. The seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight: 8-90 parts of thermoplastic modified polyvinyl alcohol; 8-90 parts of polyester; 0-2 parts of a compatilizer. The preparation method of the seawater degradation material comprises the following steps: 1) thermoplastic modification of polyvinyl alcohol: uniformly mixing polyvinyl alcohol and a plasticizer, sealing and plasticizing, and extruding and granulating to obtain the polyvinyl alcohol-plasticizer composite material; 2) preparing a seawater degradation material: uniformly mixing the thermoplastic modified polyvinyl alcohol, polyester and compatilizer according to a proportion, extruding, granulating and injecting to obtain the seawater degradation material with adjustable use period and degradation period. The seawater degradation material is a PVA composite material which can be processed by melt blending, the process is simple and controllable, the energy consumption is low, and the problems of high cost and low efficiency of the traditional process based on PVA aqueous solution are effectively solved.
Description
Technical Field
The invention relates to the technical field of seawater purification. More particularly, relates to a seawater degradation material with adjustable use period and degradation period and a preparation method thereof.
Background
In recent years, plastics and their products have been used in the world at not less than 2.4 million tons per year, and it is conservatively estimated that 480 + 1270 ten thousand tons of plastic wastes are directly discarded or pass through river channels from land, wind power and finally enter the ocean, and they are widely present in the entire ocean ecosystem by ocean currents. The plastic garbage is subjected to solar radiation (such as photodegradation and embrittlement), weathering, wave mechanical force and biota, and finally forms tiny plastic fragments or particles, and the plastic fragments or particles are defined as 'micro plastic' when the diameter is less than 5 mm. From large-volume plastic products to micro-plastics, the plastic wastes which exist in a solid form and are difficult to degrade cause serious damage to the marine ecological environment, so that the development of the plastic which can automatically disappear and be rapidly degraded in a seawater environment has great significance for solving the problem of marine plastic pollution.
Many water-soluble polymer materials fully satisfy this condition in order to "disappear" as soon as possible after the material is discarded into seawater. However, in order not to pollute the marine environment, the materials should be degradable to produce small molecules that are not harmful to the environment. Based on the above consideration, polyvinyl alcohol (PVA) can meet the requirements, not only has water solubility which is adjustable along with the change of polymerization degree or alcoholysis degree, can be synthesized through a non-petrochemical route, but also can be completely biodegraded under the condition that bacteria exist in wet environments such as sewage sludge, river water and the like, so that the PVA is used as a main component of a seawater degradation material under the background that petroleum resources are increasingly exhausted and the pollution of land marine plastics is increasingly intensified, and has great application prospects. However, due to the characteristic of strong hydrogen bonds of the PVA polyhydroxy group, the decomposition temperature (200-250 ℃) is close to the melting point (230 ℃), and the thermoplastic processing is difficult, so that the processing of the PVA is mostly based on the aqueous solution of the PVA at present.
In order to realize the low-cost and high-efficiency melt processing of PVA, a plasticizer such as polyols and carboxylic acid substances is required to be added to form hydrogen bond composition with the PVA, so that the crystallization of the PVA is inhibited, the melting point is reduced, the processing interval is widened, and the purposes of prolonging the service cycle and the degradation cycle of the thermoplastic processing of the PVA are achieved. For example, CN 106589852a discloses a water degradable material with adjustable degradation period, however, the use of polyvinyl alcohol as hydrolysis promoter directly melt-extruding with aliphatic polyester and auxiliary agent is not desirable, because PVA without thermoplastic modification is not only difficult to thermoplastic process, easy to decompose, and has lost mechanical properties, but also has no good water solubility. It is also worth noting that while PVA is completely biodegradable, its degradation is more environmentally demanding, and in marine environments characterized by low temperature, high salt, high pressure, flow and dilute nutrients, where the number and variety of microorganisms is much smaller than in soil and river water, it is basically certain that PVA degrades relatively slowly, although its water solubility allows it to dissolve in seawater and thus promote biodegradation. Meanwhile, PVA has a drawback of poor water resistance when used as a material for products. The problem of poor water resistance of PVA in use can be overcome while ensuring the water solubility of PVA, which is a challenging technical problem.
Therefore, the invention provides a seawater degradation material with adjustable use period and degradation period and a preparation method thereof, and at least solves one of the problems.
Disclosure of Invention
The invention aims to provide a seawater degradation material with adjustable use period and degradation period.
The invention also aims to provide a preparation method of the seawater degradation material with adjustable use period and degradation period.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
8-90 parts of thermoplastic modified polyvinyl alcohol;
8-90 parts of polyester;
0-2 parts of a compatilizer.
Preferably, the thermoplastic modified polyvinyl alcohol is prepared by uniformly mixing polyvinyl alcohol and a plasticizer, sealing and plasticizing, extruding and granulating; wherein the mass ratio of the polyvinyl alcohol to the plasticizer is 80:20-90: 10.
Preferably, the temperature of the plasticization is room temperature-60 ℃; further, in some embodiments of the present invention, for example, the plasticizing temperature is from room temperature to 30 ℃, from room temperature to 40 ℃, from room temperature to 50 ℃, from 30 to 40 ℃, from 30 to 50 ℃, from 30 to 60 ℃, from 40 to 50 ℃, from 40 to 60 ℃, from 50 to 60 ℃, and the like.
Preferably, the plasticizing time is 3-6 h; further, in certain embodiments of the present invention, for example, the time of plasticization ranges from 3-4 hours, 3-5 hours, 4-6 hours, 5-6 hours, and the like.
Preferably, the temperature of the extrusion granulation is 160-200 ℃; further, in certain embodiments of the present invention, for example, the temperature of the extrusion granulation is 160-.
Preferably, the degree of polymerization of the polyvinyl alcohol is 300-2600, and the degree of alcoholysis of the polyvinyl alcohol is 88-99%.
Preferably, the polyvinyl alcohol is of type 0388, 0488, 0499, 0588, 0599, 1099, 1399, 1599, 1788, 1792, 1795, 1797, 1799, 2088, 2099, 2488, 2499, 2699.
Preferably, the plasticizer is selected from one or more of sorbitol, 1, 4-butanediol, glycerol, ethylene glycol, and citric acid.
Preferably, the polyester is a polyester with a weight loss of more than 30 wt% of a standard sample bar in seawater within one year.
Preferably, the polyester is polycaprolactone and/or polyhydroxyalkanoate.
Preferably, the compatibilizer is selected from one or more of ADR-4380, ADR-4370S, KH-560, KH-570, MDI and HDI.
Preferably, the seawater degradation material is an alloy material or a material with a skin-core structure.
Preferably, in the seawater degradation material with the skin-core structure, the skin layer material is polyester, and the core layer material is thermoplastic modified polyvinyl alcohol.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of the seawater degradation material with adjustable use period and degradation period comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol:
uniformly mixing polyvinyl alcohol and a plasticizer, sealing and plasticizing, and extruding and granulating to obtain the polyvinyl alcohol-plasticizer composite material;
2) preparing a seawater degradation material: uniformly mixing the thermoplastic modified polyvinyl alcohol, polyester and compatilizer according to a proportion, extruding, granulating and injecting to obtain the seawater degradation material with adjustable use period and degradation period.
Preferably, the temperature for plasticizing in step 1) is room temperature-60 ℃; further, in some embodiments of the present invention, for example, the temperature for plasticizing in step 1) is room temperature-30 ℃, room temperature-40 ℃, room temperature-50 ℃, 30-40 ℃, 30-50 ℃, 30-60 ℃, 40-50 ℃, 40-60 ℃, 50-60 ℃ and the like.
Preferably, the plasticizing time in the step 1) is 3-6 h; further, in certain embodiments of the present invention, for example, the time for plasticizing in step 1) is 3-4h, 3-5h, 4-6h, 5-6h, etc.
Preferably, the temperature of the extrusion granulation in the step 1) is 160-200 ℃; further, in certain embodiments of the present invention, for example, the temperature of the extrusion granulation in step 1) is 160-.
Preferably, the temperature of the extrusion granulation in the step 2) is 160-200 ℃; further, in certain embodiments of the present invention, for example, the temperature of the extrusion granulation in step 2) is 160-.
Preferably, the temperature of the injection molding in the step 2) is 170-210 ℃; further, in some embodiments of the present invention, for example, the temperature of the injection molding in step 2) is 170-.
The invention has the following beneficial effects:
(1) the raw materials of the seawater degradation material can be synthesized by a non-petrochemical route, and the seawater degradation material belongs to a completely biodegradable material, and meets the requirement of sustainable development.
(2) The seawater degradation material is a PVA composite material which can be processed by melt blending, the process is simple and controllable, the energy consumption is low, and the problems of high cost and low efficiency of the traditional process based on PVA aqueous solution are effectively solved.
(3) The seawater degradation material can be an alloy material structure with good compatibility, and can also be a skin-core structure, wherein the skin layer component is polyester, and the core layer component is polyvinyl alcohol subjected to thermoplastic modification, so that the moisture absorption of PVA during the use period is inhibited to a certain extent by the structures, and the service cycle of the product is greatly prolonged.
(4) The seawater degradation material of the invention has adjustable service cycle and seawater degradation cycle by changing the proportion of PVA type or PVA/polyester composite material.
(5) The seawater degradation material can meet the actual requirements of military or civil ships, some marine products and the like.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The invention provides a seawater degradation material with adjustable use period and degradation period, which is prepared from the following raw materials in parts by weight: 8-90 parts of thermoplastic modified polyvinyl alcohol; 8-90 parts of polyester; 0-2 parts of a compatilizer. When the seawater degradation material is prepared, the thermoplastic modified polyvinyl alcohol is used, so that the water solubility, the thermal stability and the mechanical property of PVA are improved, the PVA composite material can be prepared by the thermoplastic processing with simple and controllable process and low energy consumption, the obtained seawater degradation material has the service cycle of not less than 2 years at normal temperature, and waste is obviously degraded after entering seawater.
Wherein, the polyvinyl alcohol after the thermoplastic modification is used for promoting the water absorption of the seawater degradation material; the polyester functions to promote biodegradability of the seawater degradation material and inhibit water absorption of the seawater degradation material during use; the function of the compatilizer is to enhance the interaction between the polyvinyl alcohol and the polyester through a coupling mode.
One possible implementation manner of the thermoplastic modification is to add polyvinyl alcohol and a plasticizer into a high-speed stirrer according to the mass ratio of 80:20-90:10 for stirring for multiple times until the polyvinyl alcohol and the plasticizer are fully and uniformly mixed to prepare a premix, then seal the premix, place the premix in a room temperature-60 ℃ condition for plasticizing for 3-6h, take out the premix and extrude and granulate in a double-screw extruder at the temperature of 160 ℃ and 200 ℃ to prepare the polyvinyl alcohol after the thermoplastic modification. Wherein the plasticizer functions to plasticize the PVA.
Optionally, the degree of polymerization of the polyvinyl alcohol is 300-2600, and the degree of alcoholysis of the polyvinyl alcohol is 88-99%. The polyvinyl alcohol within the polymerization degree range and the alcoholysis degree range is common commercial polyvinyl alcohol, the raw materials are easy to obtain, the property is stable, and the water solubility is deteriorated along with the increase of the polymerization degree or the alcoholysis degree.
Further, the plasticizer is preferably one or more selected from sorbitol, 1, 4-butanediol, glycerol, ethylene glycol and citric acid; the plasticizer is common polyhydric alcohols and carboxylic acid substances, is low in price and has a remarkable thermoplastic modification effect on PVA.
Alternatively, to obtain a polyester that degrades in seawater and degrades faster, the polyester is preferably a polyester that has a weight loss of greater than 30 wt% of standard bars in seawater over a year.
Further, the polyester is polycaprolactone and/or polyhydroxyalkanoate, has excellent seawater degradation performance, can be synthesized through microbial fermentation, and meets the requirements of sustainable development.
Preferably, the compatilizer is selected from one or more of ADR-4380, ADR-4370S, KH-560, KH-570, MDI and HDI; the compatilizer is a common commercial coupling agent and has an obvious enhancement effect on the interaction between PVA and polyester.
In addition, the seawater degradation material can be an alloy material structure with good compatibility, and can also be a skin-core structure, wherein the skin layer component is polyester, and the core layer component is polyvinyl alcohol subjected to thermoplastic modification, so that the water absorption problem is inhibited to a certain extent, and the seawater degradation material is favorable for long-term use. The alloy material structure has the advantages that the PVA is subjected to the restraining effect of the polyester, and the effect can be enhanced by adding the compatilizer, so that the water absorption of the PVA is inhibited; the sheath-core structure inhibits the water absorption of the core layer PVA through the hydrophobic effect and the mechanical isolation effect of the sheath polyester.
In addition, the second aspect of the invention also provides a preparation method of the seawater degradation material with adjustable use period and degradation period, which comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol:
uniformly mixing polyvinyl alcohol and a plasticizer, sealing and plasticizing, and extruding and granulating to obtain the polyvinyl alcohol-plasticizer composite material;
2) preparing a seawater degradation material: uniformly mixing the thermoplastic modified polyvinyl alcohol, polyester and compatilizer according to a proportion, extruding, granulating and injecting to obtain the seawater degradation material with adjustable use period and degradation period.
Hereinafter, each step in the synthesis method will be described in detail.
One possible implementation manner in the step 1) is to add polyvinyl alcohol and a plasticizer into a high-speed stirrer according to a mass ratio of 80:20-90:10 for stirring for multiple times until the polyvinyl alcohol and the plasticizer are fully and uniformly mixed to obtain a premix, then seal the premix, place the premix in a room temperature-60 ℃ condition for plasticizing for 3-6h, take out the premix, and extrude and granulate in a double-screw extruder at a temperature of 160-.
One possible implementation manner in the step 2) is to premix the thermoplastic modified polyvinyl alcohol, the polyester and the compatilizer to obtain a mixture, and then extrude and granulate the mixture through a double screw at the temperature of 160 ℃ and 200 ℃ and perform injection molding at the temperature of 170 ℃ and 210 ℃ to obtain the seawater degradation material with adjustable use period and degradation period.
In the present invention, the production method is a conventional method unless otherwise specified, and the raw materials used are commercially available from public or can be produced according to the prior art without specifically specified.
Example 1
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 0388 polyvinyl alcohol: 8 parts of a mixture;
polycaprolactone: 90 parts of a mixture;
ADR-4380: and 2 parts.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 0388 polyvinyl alcohol and sorbitol into a high-speed stirrer according to a mass ratio of 80:20 for stirring for multiple times, wherein each stirring is carried out for 1-2 min until the materials are fully and uniformly mixed to prepare a premix, then sealing the premix, placing the premix under a room temperature condition for plasticizing for 6h, taking out the premix, and then extruding and granulating in a double-screw extruder at an extrusion temperature of 160 ℃ to prepare thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: premixing 8 parts of thermoplastic modified polyvinyl alcohol prepared in the step 1), 90 parts of polycaprolactone and 2 parts of ADR-4380 to obtain a mixture, extruding and granulating by using a double screw at 160 ℃, and performing injection molding at 170 ℃ to obtain a test sample strip to obtain the seawater degradation material with the alloy material structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 2
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 0388 polyvinyl alcohol: 90 parts of a mixture;
polyhydroxyalkanoate: 10 parts.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 0388 polyvinyl alcohol and 1, 4-butanediol into a high-speed stirrer according to a mass ratio of 90:10 for stirring for multiple times, stirring for 1-2 min each time until the polyvinyl alcohol and the 1, 4-butanediol are fully and uniformly mixed to prepare a premix, sealing the premix, placing the premix in a 60 ℃ drying oven for plasticizing for 3h, taking out the premix, and extruding and granulating in a double-screw extruder at an extrusion temperature of 160 ℃ to prepare thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: and then premixing 90 parts of the thermoplastic modified polyvinyl alcohol prepared in the step 1) and 10 parts of polyhydroxyalkanoate to obtain a mixture, extruding and granulating by a double screw at 160 ℃, and performing injection molding at 170 ℃ to obtain a test sample strip, thus obtaining the seawater degradation material with the skin-core structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 3
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 0588 polyvinyl alcohol: 20 parts of (1);
polyhydroxyalkanoate: 79 parts of;
ADR-4370 s: 1 part.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 0588 polyvinyl alcohol and glycerol into a high-speed stirrer according to a mass ratio of 85:15 for stirring for multiple times, wherein each stirring is carried out for 1-2 min until the materials are fully and uniformly mixed to prepare a premix, then sealing the premix, placing the premix in a 30 ℃ drying oven for plasticizing for 5h, taking out the premix, and then extruding and granulating in a double-screw extruder at an extrusion temperature of 160 ℃ to prepare thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: premixing 20 parts of thermoplastic modified polyvinyl alcohol, 79 parts of polyhydroxyalkanoate and 1 part of ADR-4370s prepared in the step 1) to obtain a mixture, extruding and granulating by using a double screw at 160 ℃, and performing injection molding at 170 ℃ to obtain a test sample strip to obtain the seawater degradation material with the alloy material structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 4
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 0588 polyvinyl alcohol: 80 parts of a mixture;
polycaprolactone: and 20 parts.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 0588 polyvinyl alcohol and ethylene glycol into a high-speed stirrer according to a mass ratio of 80:20 for stirring for multiple times, wherein each stirring is carried out for 1-2 min until the materials are fully and uniformly mixed to prepare a premix, then sealing the premix, placing the premix in a drying oven at 40 ℃ for plasticizing for 4h, taking out the premix, and then extruding and granulating in a double-screw extruder at an extrusion temperature of 160 ℃ to prepare thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: and then premixing 80 parts of the thermoplastic modified polyvinyl alcohol prepared in the step 1) and 20 parts of polycaprolactone to obtain a mixture, extruding and granulating by a double screw at 160 ℃, and performing injection molding at 170 ℃ to obtain a test sample strip, thus preparing the seawater degradation material with the skin-core structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 5
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 0599 polyvinyl alcohol: 30 parts of (1);
polyhydroxyalkanoate: 68.5 parts;
KH 560: 1.5 parts.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 0599 polyvinyl alcohol and citric acid into a high-speed stirrer according to a mass ratio of 90:10 for stirring for multiple times, wherein each stirring is carried out for 1-2 min until the materials are fully and uniformly mixed to prepare a premix, then sealing the premix, placing the premix in a 50 ℃ drying oven for plasticizing for 3h, taking out the premix, and then extruding and granulating in a double-screw extruder at an extrusion temperature of 170 ℃ to prepare thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: premixing 30 parts of thermoplastic modified polyvinyl alcohol prepared in the step 1), 68.5 parts of polyhydroxyalkanoate and 1.5 parts of KH560 to obtain a mixture, extruding and granulating by using a double screw at the temperature of 170 ℃, and performing injection molding at the temperature of 200 ℃ to obtain a test sample strip, thereby preparing the seawater degradation material with the alloy material structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 6
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 0599 polyvinyl alcohol: 70 parts of (B);
polycaprolactone: 30 parts of.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 0599 polyvinyl alcohol and sorbitol into a high-speed stirrer according to a mass ratio of 80:20 for stirring for multiple times, wherein each stirring is carried out for 1-2 min until the materials are fully and uniformly mixed to prepare a premix, then sealing the premix, placing the premix under a room temperature condition for plasticizing for 6h, taking out the premix, and then extruding and granulating in a double-screw extruder at an extrusion temperature of 170 ℃ to prepare thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: premixing 70 parts of the thermoplastic modified polyvinyl alcohol prepared in the step 1) and 30 parts of polycaprolactone to obtain a mixture, extruding and granulating by a double screw at the temperature of 170 ℃, and performing injection molding at the temperature of 200 ℃ to obtain a test sample strip, thus preparing the seawater degradation material with the skin-core structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 7
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 1788 polyvinyl alcohol: 40 parts of a mixture;
polycaprolactone: 59.5 parts of;
MDI: 0.5 part.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 1788 polyvinyl alcohol and 1, 4-butanediol into a high-speed stirrer according to a mass ratio of 90:10, stirring for multiple times, stirring for 1-2 min each time until the polyvinyl alcohol and the 1, 4-butanediol are fully mixed to obtain a premix, sealing the premix, placing the premix in a 60 ℃ drying oven for plasticizing for 3h, taking out the premix, and extruding and granulating in a double-screw extruder at an extrusion temperature of 170 ℃ to obtain thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: premixing 40 parts of thermoplastic modified polyvinyl alcohol prepared in the step 1), 59.5 parts of polycaprolactone and 0.5 part of MDI to obtain a mixture, extruding and granulating by a double screw at the temperature of 170 ℃, and performing injection molding at the temperature of 180 ℃ to obtain a test sample strip, thus preparing the seawater degradation material with the alloy material structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 8
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 1788 polyvinyl alcohol: 60 parts;
polyhydroxyalkanoate: 40 parts of the components.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 1788 polyvinyl alcohol and glycerol into a high-speed stirrer according to a mass ratio of 85:15, stirring for multiple times, stirring for 1-2 min each time until the materials are fully mixed to obtain a premix, sealing the premix, placing the premix in a 30 ℃ drying oven for plasticization for 5h, taking out the premix, and extruding and granulating in a double-screw extruder at an extrusion temperature of 170 ℃ to obtain thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: premixing 60 parts of the thermoplastic modified polyvinyl alcohol prepared in the step 1) and 40 parts of polyhydroxyalkanoate to obtain a mixture, extruding and granulating by a double screw at the temperature of 170 ℃, and performing injection molding at the temperature of 190 ℃ to obtain a test sample strip, thus preparing the seawater degradation material with the skin-core structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 9
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 1792 polyvinyl alcohol: 90 parts of a mixture;
polyhydroxyalkanoate: 8 parts of a mixture;
KH-570: and 2 parts.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 1792 polyvinyl alcohol and ethylene glycol into a high-speed stirrer according to a mass ratio of 80:20 for stirring for multiple times, stirring for 1-2 min each time until the materials are fully mixed to obtain a premix, sealing the premix, placing the premix in a drying oven at 40 ℃ for plasticizing for 4h, taking out the premix, and extruding and granulating in a double-screw extruder at an extrusion temperature of 170 ℃ to obtain thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: premixing 90 parts of thermoplastic modified polyvinyl alcohol, 8 parts of polyhydroxyalkanoate and 2 parts of KH-570 prepared in the step 1) to obtain a mixture, extruding and granulating by using a double screw at the temperature of 170 ℃, and performing injection molding at the temperature of 190 ℃ to obtain a test sample strip, thereby preparing the seawater degradation material with the alloy material structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
Example 10
A seawater degradation material with adjustable use period and degradation period is prepared from the following raw materials in parts by weight:
thermoplastic modified 2699 polyvinyl alcohol: 50 parts of a mixture;
polycaprolactone: 48 parts of a mixture;
HDI: and 2 parts.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 2699 polyvinyl alcohol and ethylene glycol into a high-speed stirrer according to a mass ratio of 80:20 for stirring for multiple times, wherein each stirring is carried out for 1-2 min until the materials are fully and uniformly mixed to obtain a premix, sealing the premix, placing the premix in a drying oven at 40 ℃ for plasticizing for 4h, taking out the premix, and carrying out extrusion granulation in a double-screw extruder at an extrusion temperature of 200 ℃ to obtain thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: and then premixing 50 parts of the thermoplastic modified polyvinyl alcohol prepared in the step 1), 48 parts of polycaprolactone and 2 parts of HDI to obtain a mixture, extruding and granulating by using a double screw at 200 ℃, and performing injection molding at 210 ℃ to obtain a test sample strip to obtain the seawater degradation material with the alloy material structure. The seawater degradation performance and the service mechanical property of the prepared seawater degradation material are respectively shown in tables 1 and 2.
TABLE 1 seawater degradability of seawater-degradable Material
| Examples | Weight loss (wt%) after 30 days of degradation | Weight loss (wt%) after 60 days of degradation |
| 1 | 7 | 15 |
| 2 | 95 | 98 |
| 3 | 11 | 23 |
| 4 | 69 | 89 |
| 5 | 6 | 13 |
| 6 | 15 | 31 |
| 7 | 9 | 19 |
| 8 | 31 | 59 |
| 9 | 21 | 49 |
| 10 | 4 | 9 |
TABLE 2 mechanical properties of seawater degradation material
Comparative example 1
A seawater degradation material is prepared from the following raw materials in parts by weight:
1788 polyvinyl alcohol: 40 parts of a mixture;
polycaprolactone: 59.5 parts of;
MDI: 0.5 part.
The preparation of the seawater degradation material comprises the following steps:
premixing 40 parts of polyvinyl alcohol, 59.5 parts of polycaprolactone and 0.5 part of MDI to obtain a mixture, extruding and granulating by a double screw at 220 ℃, and performing injection molding at 230 ℃ to obtain a test sample strip to obtain the seawater degradation material.
The results show that: compared with the example 7, the polyvinyl alcohol in the comparative example is not subjected to thermoplastic modification in advance, so that the obtained seawater degradation material can only be subjected to melt extrusion at a higher temperature of 220 ℃, obvious thermal degradation and mechanical property loss occur, the water solubility is poor, the weight loss is 3 wt% after seawater degradation for 30 days, and the weight loss is 7 wt% after 60 days, which are far lower than 9 wt% and 19 wt% of the example 7 respectively.
Comparative example 2
A seawater degradation material is prepared from the following raw materials in parts by weight:
thermoplastic modified 0588 polyvinyl alcohol: 80 parts of a mixture;
polylactic acid: and 20 parts.
The preparation of the seawater degradation material comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol: sequentially adding 0588 polyvinyl alcohol and ethylene glycol into a high-speed stirrer according to a mass ratio of 80:20 for stirring for multiple times, wherein each stirring is carried out for 1-2 min until the materials are fully and uniformly mixed to prepare a premix, then sealing the premix, placing the premix in a drying oven at 40 ℃ for plasticizing for 4h, taking out the premix, and then extruding and granulating in a double-screw extruder at an extrusion temperature of 160 ℃ to prepare thermoplastic modified polyvinyl alcohol;
2) preparing a seawater degradation material: premixing 80 parts of the thermoplastic modified polyvinyl alcohol prepared in the step 1) and 20 parts of polylactic acid to obtain a mixture, extruding and granulating by a double screw at the temperature of 170 ℃, and performing injection molding at the temperature of 180 ℃ to obtain a test sample strip, thus obtaining the seawater degradation material.
The results show that: the weight loss of the seawater degradation material prepared by the comparative example is 29 wt% after seawater degradation for 30 days, and 43 wt% after 60 days, which are far lower than those of the seawater degradation material prepared by the example 4 in 69 wt% and 89 wt%. Therefore, the polyester which is slowly degraded or not degraded in seawater, such as polylactic acid, is used to form the composite material with polyvinyl alcohol, which is not beneficial to promoting the seawater degradation performance of the composite material.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (6)
1. A seawater degradation material with adjustable use period and degradation period is characterized by being prepared from the following raw materials in parts by weight:
8-90 parts of thermoplastic modified polyvinyl alcohol;
8-90 parts of polyester;
0-2 parts of a compatilizer;
the thermoplastic modified polyvinyl alcohol is prepared by uniformly mixing polyvinyl alcohol and a plasticizer, sealing and plasticizing, extruding and granulating; wherein the mass ratio of the polyvinyl alcohol to the plasticizer is 80:20-90: 10;
the plasticizing temperature is room temperature-60 ℃; the plasticizing time is 3-6 h; the temperature of the extrusion granulation is 160-200 ℃;
the polymerization degree of the polyvinyl alcohol is 300-2600, and the alcoholysis degree of the polyvinyl alcohol is 88-99 percent;
the polyester is the polyester with the weight loss of more than 30 wt% of a standard sample strip in seawater within one year.
2. The seawater degradation material with adjustable use period and degradation period as claimed in claim 1, wherein the plasticizer is selected from one or more of sorbitol, 1, 4-butanediol, glycerol, ethylene glycol and citric acid.
3. The seawater degradation material with adjustable use period and degradation period as claimed in claim 1, wherein the polyester is polycaprolactone and/or polyhydroxyalkanoate.
4. The seawater degradation material with adjustable use period and degradation period as claimed in claim 1, wherein the compatilizer is selected from one or more of ADR-4380, ADR-4370S, KH-560, KH-570, MDI and HDI.
5. The seawater degradation material with adjustable use period and degradation period as claimed in claim 1, wherein the seawater degradation material is an alloy material or a material with a skin-core structure; in the seawater degradation material with the skin-core structure, the skin layer material is polyester, and the core layer material is thermoplastic modified polyvinyl alcohol.
6. The preparation method of the seawater degradation material with adjustable use period and degradation period as claimed in any one of claims 1 to 5, which comprises the following steps:
1) thermoplastic modification of polyvinyl alcohol:
uniformly mixing polyvinyl alcohol and a plasticizer, sealing and plasticizing, and extruding and granulating to obtain the polyvinyl alcohol-plasticizer composite material;
2) preparing a seawater degradation material:
uniformly mixing the thermoplastic modified polyvinyl alcohol, polyester and compatilizer according to a proportion, extruding, granulating and injecting to obtain the seawater degradation material with adjustable use period and degradation period.
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| CN106589852A (en) * | 2016-12-15 | 2017-04-26 | 中国科学院理化技术研究所 | Water degradation material with adjustable degradation period and preparation method thereof |
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| CN105199412A (en) * | 2015-09-09 | 2015-12-30 | 青岛鑫铁成汽车配件有限公司 | Interpenetrating polymer network enhanced fully-degradable biomass matrix composite material and preparation method thereof |
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