CN108624020A - A kind of service life and the adjustable seawater degradable material of degradation cycle and preparation method thereof - Google Patents
A kind of service life and the adjustable seawater degradable material of degradation cycle and preparation method thereof Download PDFInfo
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- CN108624020A CN108624020A CN201810566827.7A CN201810566827A CN108624020A CN 108624020 A CN108624020 A CN 108624020A CN 201810566827 A CN201810566827 A CN 201810566827A CN 108624020 A CN108624020 A CN 108624020A
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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
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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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Abstract
The invention discloses a kind of service life and the adjustable seawater degradable material of degradation cycle and preparation method thereof.The service life and the adjustable seawater degradable material of degradation cycle are made of the raw material of following parts by weight：8 90 parts of polyvinyl alcohol after thermoplastic modification；8 90 parts of polyester；02 parts of compatilizer.The preparation method of the seawater degradable material, includes the following steps：1) polyvinyl alcohol thermoplastic is modified：By polyvinyl alcohol and plasticizer mixing, sealed plasticizing, extruding pelletization is made；2) preparation of seawater degradable material：By polyvinyl alcohol, polyester and the compatilizer after thermoplastic modification, mixing, extruded granulation, injection molding obtain service life and the adjustable seawater degradable material of degradation cycle in proportion.The seawater degradable material of the present invention is the PVA composite materials that can be processed by melt blending, it is simple for process it is controllable, low energy consumption, effectively overcome the problem that traditional handicraft based on PVA aqueous solutions is of high cost, efficiency is low.
Description
Technical field
The present invention relates to seawater cleaning technical fields.It is adjustable more particularly, to a kind of service life and degradation cycle
Seawater degradable material and preparation method thereof.
Background technology
In recent years, the whole world has been no less than 2.4 hundred million tons using plastics and its product every year, wherein has 480- according to conservative estimation
12700000 tons of plastic garbage is simply discarded or eventually enters into ocean from land by river, wind-force, and is made by ocean current
They are widely present in entire marine ecosystems.These plastic garbages by solar radiation (such as light degradation, embrittlement), weathering,
The effects that wave mechanical force and biota, ultimately forms the plastic flakes or particle of microminiature, can determine when diameter is less than 5mm
Justice is " micro- plastics ".All it is to exist and plastic garbage difficult to degrade in solid form from bulky plastic product to micro- plastics, it is right
The marine eco-environment causes serious destruction, therefore exploitation can voluntarily " vanish from sight " in briny environment and then energy is quick
The plastics of degradation are to solving the problems, such as that ocean plastic pollution is of great significance.
In order to make material " can vanish from sight " as early as possible after being discarded into seawater, many water-soluble high-molecular materials fill
Divide and meets this condition.But in order not to be polluted to marine environment, material is wanted to degrade, and production is non-hazardous to environment
Small molecule.Based on considerations above, polyvinyl alcohol (PVA) can be met the requirements, and not only had and changed with the degree of polymerization or alcoholysis degree
Become and adjustable water solubility, can be synthesized by non-petroleum chemical industry route, can also have bacterium in the wet environments such as sewage sludge, river water
Under the conditions of existing, carry out complete biodegradable, therefore petroleum resources increasingly depleted and land ocean plastic pollution day increasingly
Under acute background, using PVA as the key component of seawater degradable material, there is great application prospect.But since PVA is more
The characteristics of hydroxyl strong hydrogen bonding, keeps (230 DEG C) of its decomposition temperature (200~250 DEG C) and fusing point close, and thermoplasticity processing is difficult, because
This, the processing of PVA at present is almost all based on based on its aqueous solution.
In order to realize PVA low costs, efficient melt-processed, need that plasticizer such as polyalcohols, carboxylic acids object are added
Matter and with PVA formed hydrogen bond it is compound, inhibit PVA crystallization, so that fusing point is reduced, processing interval broadens, reach improve PVA thermoplastic processings
The purpose of service life and degradation cycle.If CN 106589852A disclose a kind of adjustable water body degradable material of degradation cycle,
However be wherein directly with aliphatic polyester, auxiliary agent melting extrusion using polyvinyl alcohol as hydrolytic accelerating agent it is worthless, because
PVA for not first thermoplastic modification is not only thermoformed difficulty, and product easily decomposes, and is lost using mechanical property, and does not have
There is good water solubility.Though being further noted that PVA fully biodegradables, its degradation is higher to degradation environmental requirement,
If in the marine environment characterized by low temperature, with high salt, high pressure, flowing and dilute nutrition, wherein microbe number and type is more native
It is very few for earth and river water, can affirms substantially, although the water solubility of PVA can make it dissolve thus promotes life in the seawater
Object is degraded, PVA degradation speeds or relatively slow.Meanwhile for PVA uses as product material, then showing water resistance
The defect of difference.How to ensure that PVA is water-soluble while poor water resistance when can overcome the problems, such as that PVA is used again, this is a rich
The technical barrier of challenge.
Therefore, the present invention provides a kind of service life and the adjustable seawater degradable material of degradation cycle and its preparation sides
Method at least solves the problems, such as one of above-mentioned.
Invention content
It is an object of the present invention to provide a kind of service life and the adjustable seawater degradable material of degradation cycle.
It is another object of the present invention to provide a kind of service life and the adjustable seawater degradable materials of degradation cycle
Preparation method.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
8-90 parts of polyvinyl alcohol after thermoplastic modification；
8-90 parts of polyester；
0-2 parts of compatilizer.
Preferably, the polyvinyl alcohol after the thermoplastic modification is by by polyvinyl alcohol and plasticizer mixing, sealed modeling
Change, extruding pelletization is made；Wherein, the mass ratio of polyvinyl alcohol and plasticizer is 80:20-90:10.
Preferably, the temperature of the plasticizing is -60 DEG C of room temperature；Further, in certain specific implementation modes of the present invention
In, for example, the temperature of the plasticizing is -30 DEG C of room temperature, -40 DEG C of room temperature, -50 DEG C of room temperature, 30-40 DEG C, 30-50 DEG C, 30-60
DEG C, 40-50 DEG C, 40-60 DEG C, 50-60 DEG C etc..
Preferably, the time of the plasticizing is 3-6h；Further, in certain specific implementation modes of the present invention, example
Such as, the time of the plasticizing is 3-4h, 3-5h, 4-5h, 4-6h, 5-6h etc..
Preferably, the temperature of the extruding pelletization is 160-200 DEG C；Further, in certain specific implementations of the present invention
In mode, for example, the temperature of the extruding pelletization is 160-170 DEG C, 170-200 DEG C etc..
Preferably, the degree of polymerization of the polyvinyl alcohol is 300-2600, and the alcoholysis degree of the polyvinyl alcohol is 88%-
99%.
Preferably, the model 0388 of the polyvinyl alcohol, 0488,0499,0588,0599,1099,1399,1599,
1788、1792、1795、1797、1799、2088、2099、2488、2499、2699。
Preferably, the one kind or more of the plasticizer in sorbierite, 1,4-butanediol, glycerine, ethylene glycol, citric acid
Kind.
Preferably, the polyester be standard batten in the seawater in 1 year weightlessness 30wt% or more polyester.
Preferably, the polyester is polycaprolactone and/or polyhydroxyalkanoates.
Preferably, the compatilizer in ADR-4380, ADR-4370S, KH-560, KH-570, MDI and HDI one
Kind is a variety of.
Preferably, the seawater degradable material is the material of alloy material or skin-core structure.
Preferably, in the seawater degradable material of the skin-core structure, cortical material is polyester, and core material changes for thermoplasticity
Polyvinyl alcohol after property.
To reach above-mentioned second purpose, the present invention uses following technical proposals：
A kind of preparation method of above-mentioned service life and the adjustable seawater degradable material of degradation cycle, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：
By polyvinyl alcohol and plasticizer mixing, sealed plasticizing, extruding pelletization is made；
2) preparation of seawater degradable material：By the mixing in proportion of polyvinyl alcohol, polyester and the compatilizer after thermoplastic modification,
Extruded granulation, injection molding obtain service life and the adjustable seawater degradable material of degradation cycle.
Preferably, the temperature being plasticized described in step 1) is -60 DEG C of room temperature；Further, in the certain specific of the present invention
In embodiment, for example, the temperature being plasticized described in step 1) is -30 DEG C of room temperature, -40 DEG C of room temperature, -50 DEG C of room temperature, 30-40
DEG C, 30-50 DEG C, 30-60 DEG C, 40-50 DEG C, 40-60 DEG C, 50-60 DEG C etc..
Preferably, the time being plasticized described in step 1) is 3-6h；Further, in certain specific embodiment parties of the present invention
In formula, for example, the time being plasticized described in step 1) is 3-4h, 3-5h, 4-5h, 4-6h, 5-6h etc..
Preferably, the temperature of extruding pelletization described in step 1) is 160-200 DEG C；Further, in the certain of the present invention
In specific implementation mode, for example, the temperature of extruding pelletization described in step 1) is 160-170 DEG C, 170-200 DEG C etc..
Preferably, the temperature of extruding pelletization described in step 2) is 160-200 DEG C；Further, in the certain of the present invention
In specific implementation mode, for example, the temperature of extruding pelletization described in step 2) is 160-170 DEG C, 170-200 DEG C etc..
Preferably, the temperature being molded described in step 2) is 170-210 DEG C；Further, in the certain specific of the present invention
In embodiment, for example, the temperature being molded described in step 2) is 170-180 DEG C, 170-190 DEG C, 180-190 DEG C, 180-210
DEG C, 190-210 DEG C etc..
Beneficial effects of the present invention are as follows：
(1) seawater degradable material of the invention, raw material can be synthesized by non-petroleum chemical industry route, and belong to complete biology
Degradable material meets the requirement of sustainable development.
(2) seawater degradable material of the invention is the PVA composite materials that can be processed by melt blending, it is simple for process can
Control, low energy consumption, effectively overcomes the problem that traditional handicraft based on PVA aqueous solutions is of high cost, efficiency is low.
(3) seawater degradable material of the invention both can be the good alloy material structure of compatibility, or core-skin
Structure, wherein cortex group are divided into polyester, and sandwich layer group is divided into the polyvinyl alcohol after thermoplastic modification, these structures press down to a certain extent
The hygroscopicity of PVA during use has been made, the service life of product is substantially prolonged.
(4) seawater degradable material of the invention makes seawater by change PVA models or the ratio of PVA/ polyester composites
Degradable material is provided with adjustable service life and seawater degradation cycle.
(5) seawater degradable material of the invention disclosure satisfy that in the ship of military or civilian and some sea stores etc.
Actual demand.
Specific implementation mode
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.
The present invention provides a kind of service life and the adjustable seawater degradable material of degradation cycle, by following parts by weight
Raw material is made：8-90 parts of polyvinyl alcohol after thermoplastic modification；8-90 parts of polyester；0-2 parts of compatilizer.The present invention is preparing seawater
When degradable material, water solubility, thermal stability and the mechanical property of PVA are not only improved using the polyvinyl alcohol after thermoplastic modification
Can, also it can prepare PVA composite materials, obtained seawater degradable material by thermoplasticity processing simple for process controllable and that low energy consumption
With the service life for being not less than 2 years at normal temperatures, after entering seawater apparent degradation occurs for waste.
Wherein, the water imbibition for acting as promoting seawater degradable material of the polyvinyl alcohol after thermoplastic modification；The work of polyester
With the water imbibition of biological degradability and inhibition seawater degradable material during use to promote seawater degradable material；Compatilizer
It act as, by coupling mode, enhancing the interaction between polyvinyl alcohol and polyester.
Thermoplastic modification one is possible to be achieved in that, by by polyvinyl alcohol and plasticizer in mass ratio 80:20-
90:It is repeatedly stirred in 10 addition homogenizers, until being sufficiently mixed uniformly, obtained premix is then close by premix
Envelope is plasticized 3-6h under the conditions of being positioned over -60 DEG C of room temperature, squeezes out and makes under the conditions of 160-200 DEG C in double screw extruder after taking-up
The polyvinyl alcohol after thermoplastic modification is made in grain.Wherein, plasticizer act as being plasticized PVA.
Optionally, the degree of polymerization of the polyvinyl alcohol is 300-2600, and the alcoholysis degree of the polyvinyl alcohol is 88%-
99%.It is common commercial polyethylene alcohol in the polyvinyl alcohol of the polymerization scope and alcoholysis degree range, raw material easily obtains, property
Matter is stablized, and water solubility is deteriorated with the increase of the degree of polymerization or alcoholysis degree.
Further, the plasticizer preferably is selected from one kind in sorbierite, 1,4-butanediol, glycerine, ethylene glycol, citric acid
Or it is a variety of；Above-mentioned plasticizer is common polyalcohols and carboxylic-acid substance, not only cheap, and to PVA thermoplastic modifications
Significant effect.
Optionally, to obtain to degrade in the seawater and faster polyester of degrading to obtain, the polyester are preferably standard batten
In the seawater in 1 year weightlessness 30wt% or more polyester.
Further, the polyester is polycaprolactone and/or polyhydroxyalkanoates, and the polyester not only has excellent sea
Water degradation property can also be synthesized by microbial fermentation, meet the requirement of sustainable development.
Preferably scheme, the compatilizer be selected from ADR-4380, ADR-4370S, KH-560, KH-570, MDI and
It is one or more in HDI；The compatilizer is common commercial goods coupling agent, the phase interaction between PVA and polyester
With playing the role of being remarkably reinforced.
In addition, the seawater degradable material of the present invention both can be the good alloy material structure of compatibility, or skin
Cored structure, wherein cortex group are divided into polyester, and sandwich layer group is divided into the polyvinyl alcohol after thermoplastic modification, these structures are to a certain extent
Water suction sex chromosome mosaicism is all inhibited, is used to be conducive to longer-term.Containing of the alloy material structure by polyester to PVA
Effect, and this effect can be enhanced by adding compatilizer, to inhibit the water imbibition of PVA；The skin-core structure is logical
Hydrophobic effect and the mechanical isolation effect for crossing cortex polyester, to inhibit the water imbibition of sandwich layer PVA.
In addition, the second aspect of the present invention additionally provides a kind of above-mentioned service life and the adjustable seawater degradation of degradation cycle
The preparation method of material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：
By polyvinyl alcohol and plasticizer mixing, sealed plasticizing, extruding pelletization is made；
2) preparation of seawater degradable material：By the mixing in proportion of polyvinyl alcohol, polyester and the compatilizer after thermoplastic modification,
Extruded granulation, injection molding obtain service life and the adjustable seawater degradable material of degradation cycle.
Hereinafter, to each step in synthetic method, it is described in detail.
In step 1) one it is possible be achieved in that, by by polyvinyl alcohol and plasticizer in mass ratio 80:20-90:
It is repeatedly stirred in 10 addition homogenizers, until being sufficiently mixed uniformly, premix is made, then puts premix sealing
Be placed under the conditions of -60 DEG C of room temperature and be plasticized 3-6h, after taking-up in double screw extruder extruding pelletization, system under the conditions of 160-200 DEG C
Obtain the polyvinyl alcohol after thermoplastic modification.
In step 2) one it is possible be achieved in that, by polyvinyl alcohol, polyester and the compatilizer after thermoplastic modification into
Row premixing, obtains mixture, then by extruding pelletization under the conditions of 160-200 DEG C of twin-screw, is molded and obtains under the conditions of 170-210 DEG C
Service life and the adjustable seawater degradable material of degradation cycle.
In the present invention, preparation method is then conventional method unless otherwise specified, and raw material used is equal unless otherwise instructed
It can obtain from disclosed commercial sources or be made according to the prior art.
Embodiment 1
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
0388 polyvinyl alcohol after thermoplastic modification：8 parts；
Polycaprolactone：90 parts；
ADR-4380：2 parts.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：0388 polyvinyl alcohol and sorbierite are pressed 80:20 mass ratio, sequentially adds
It is repeatedly stirred in homogenizer, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will be pre-
Batch mixing sealing is positioned over is plasticized 6h under room temperature, after taking-up in double screw extruder, squeezes out and makes at 160 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in grain；
2) preparation of seawater degradable material：By 8 parts of polyvinyl alcohol, the polycaprolactone after thermoplastic modification made from step 1)
90 parts and 2 parts of ADR-4380 are pre-mixed, and obtain mixture, then pass through extruding pelletization under the conditions of 160 DEG C of twin-screw, 170 DEG C of items
Injection molding obtains test bars under part, and the seawater degradable material of alloy material structure is made.The sea of obtained seawater degradable material
Water degradation property and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 2
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
0388 polyvinyl alcohol after thermoplastic modification：90 parts；
Polyhydroxyalkanoates：10 parts.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：0388 polyvinyl alcohol and 1,4- butanediols are pressed 90:10 mass ratio, successively
It is added in homogenizer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made, then
Premix sealing is positioned in 60 DEG C of baking ovens and is plasticized 3h, after taking-up in double screw extruder, is squeezed out at 160 DEG C of extrusion temperature
It is granulated, the polyvinyl alcohol of thermoplastic modification is made；
2) preparation of seawater degradable material：Again by 90 parts of polyvinyl alcohol, the poly- hydroxyl after thermoplastic modification made from step 1)
10 parts of base alkanoic acid ester is pre-mixed, and obtains mixture, then passes through extruding pelletization under the conditions of 160 DEG C of twin-screw, 170 DEG C of conditions bets
Modeling obtains test bars, and the seawater degradable material of skin-core structure is made.The seawater degradation property of obtained seawater degradable material
With use mechanical property to see Tables 1 and 2 respectively.
Embodiment 3
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
0588 polyvinyl alcohol after thermoplastic modification：20 parts；
Polyhydroxyalkanoates：79 parts；
ADR-4370s：1 part.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：0588 polyvinyl alcohol and glycerine are pressed 85:15 mass ratio, sequentially adds height
It is repeatedly stirred in fast blender, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will premix
Material sealing, which is positioned in 30 DEG C of baking ovens, is plasticized 5h, after taking-up in double screw extruder, extruding pelletization at 160 DEG C of extrusion temperature,
The polyvinyl alcohol of thermoplastic modification is made；
2) preparation of seawater degradable material：Again by 20 parts of polyvinyl alcohol, the poly- hydroxyl after thermoplastic modification made from step 1)
79 parts and 1 part ADR-4370s of base alkanoic acid ester is pre-mixed, and obtains mixture, then is made by being squeezed out under the conditions of 160 DEG C of twin-screw
, it is molded under the conditions of 170 DEG C and obtains test bars, the seawater degradable material of alloy material structure is made.Obtained seawater drop
It solves the seawater degradation property of material and sees Tables 1 and 2 respectively using mechanical property.
Embodiment 4
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
0588 polyvinyl alcohol after thermoplastic modification：80 parts；
Polycaprolactone：20 parts.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：0588 polyvinyl alcohol and ethylene glycol are pressed 80:20 mass ratio, sequentially adds
It is repeatedly stirred in homogenizer, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will be pre-
Batch mixing sealing, which is positioned in 40 DEG C of baking ovens, is plasticized 4h, after taking-up in double screw extruder, squeezes out and makes at 160 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in grain；
2) preparation of seawater degradable material：Again by after thermoplastic modification made from step 1) 80 parts of polyvinyl alcohol, gather oneself
20 parts of lactone is pre-mixed, and obtains mixture, then by extruding pelletization under the conditions of 160 DEG C of twin-screw, is molded under the conditions of 170 DEG C
To test bars, the seawater degradable material of skin-core structure is made.The seawater degradation property of obtained seawater degradable material and make
Tables 1 and 2 is seen respectively with mechanical property.
Embodiment 5
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
0599 polyvinyl alcohol after thermoplastic modification：30 parts；
Polyhydroxyalkanoates：68.5 parts；
KH560：1.5 part.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：0599 polyvinyl alcohol and citric acid are pressed 90:10 mass ratio, sequentially adds
It is repeatedly stirred in homogenizer, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will be pre-
Batch mixing sealing, which is positioned in 50 DEG C of baking ovens, is plasticized 3h, after taking-up in double screw extruder, squeezes out and makes at 170 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in grain；
2) preparation of seawater degradable material：Again by 30 parts of polyvinyl alcohol, the poly- hydroxyl after thermoplastic modification made from step 1)
68.5 parts and 1.5 parts KH560 of base alkanoic acid ester are pre-mixed, and obtain mixture, then are made by being squeezed out under the conditions of 170 DEG C of twin-screw
, it is molded under the conditions of 200 DEG C and obtains test bars, the seawater degradable material of alloy material structure is made.Obtained seawater drop
It solves the seawater degradation property of material and sees Tables 1 and 2 respectively using mechanical property.
Embodiment 6
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
0599 polyvinyl alcohol after thermoplastic modification：70 parts；
Polycaprolactone：30 parts.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：0599 polyvinyl alcohol and sorbierite are pressed 80:20 mass ratio, sequentially adds
It is repeatedly stirred in homogenizer, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will be pre-
Batch mixing sealing is positioned over is plasticized 6h under room temperature, after taking-up in double screw extruder, squeezes out and makes at 170 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in grain；
2) preparation of seawater degradable material：Again by after thermoplastic modification made from step 1) 70 parts of polyvinyl alcohol, gather oneself
30 parts of lactone is pre-mixed, and obtains mixture, then by extruding pelletization under the conditions of 170 DEG C of twin-screw, is molded under the conditions of 200 DEG C
To test bars, the seawater degradable material of skin-core structure is made.The seawater degradation property of obtained seawater degradable material and make
Tables 1 and 2 is seen respectively with mechanical property.
Embodiment 7
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
1788 polyvinyl alcohol after thermoplastic modification：40 parts；
Polycaprolactone：59.5 parts；
MDI：0.5 part.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：1788 polyvinyl alcohol and 1,4- butanediols are pressed 90:10 mass ratio, successively
It is added in homogenizer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made, then
Premix sealing is positioned in 60 DEG C of baking ovens and is plasticized 3h, after taking-up in double screw extruder, is squeezed out at 170 DEG C of extrusion temperature
It is granulated, the polyvinyl alcohol of thermoplastic modification is made；
2) preparation of seawater degradable material：Again by after thermoplastic modification made from step 1) 40 parts of polyvinyl alcohol, gather oneself
59.5 parts and 0.5 part MDI of lactone is pre-mixed, and obtains mixture, then by extruding pelletization under the conditions of 170 DEG C of twin-screw, 180 DEG C
Under the conditions of injection molding obtain test bars, the seawater degradable material of alloy material structure is made.Obtained seawater degradable material
Seawater degradation property and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 8
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
1788 polyvinyl alcohol after thermoplastic modification：60 parts；
Polyhydroxyalkanoates：40 parts.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：1788 polyvinyl alcohol and glycerine are pressed 85:15 mass ratio, sequentially adds height
It is repeatedly stirred in fast blender, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will premix
Material sealing, which is positioned in 30 DEG C of baking ovens, is plasticized 5h, after taking-up in double screw extruder, extruding pelletization at 170 DEG C of extrusion temperature,
The polyvinyl alcohol of thermoplastic modification is made；
2) preparation of seawater degradable material：Again by 60 parts of polyvinyl alcohol, the poly- hydroxyl after thermoplastic modification made from step 1)
40 parts of base alkanoic acid ester is pre-mixed, and obtains mixture, then passes through extruding pelletization under the conditions of 170 DEG C of twin-screw, 190 DEG C of conditions bets
Modeling obtains test bars, and the seawater degradable material of skin-core structure is made.The seawater degradation property of obtained seawater degradable material
With use mechanical property to see Tables 1 and 2 respectively.
Embodiment 9
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
1792 polyvinyl alcohol after thermoplastic modification：90 parts；
Polyhydroxyalkanoates：8 parts；
KH-570：2 parts.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：1792 polyvinyl alcohol and ethylene glycol are pressed 80:20 mass ratio, sequentially adds
It is repeatedly stirred in homogenizer, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will be pre-
Batch mixing sealing, which is positioned in 40 DEG C of baking ovens, is plasticized 4h, after taking-up in double screw extruder, squeezes out and makes at 170 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in grain；
2) preparation of seawater degradable material：Again by 90 parts of polyvinyl alcohol, the poly- hydroxyl after thermoplastic modification made from step 1)
8 parts and 2 parts KH-570 of base alkanoic acid ester are pre-mixed, and obtain mixture, then by extruding pelletization under the conditions of 170 DEG C of twin-screw, and 190
Injection molding obtains test bars under the conditions of DEG C, and the seawater degradable material of alloy material structure is made.Obtained seawater degradable material
Seawater degradation property and see Tables 1 and 2 respectively using mechanical property.
Embodiment 10
A kind of service life and the adjustable seawater degradable material of degradation cycle, are made of the raw material of following parts by weight：
2699 polyvinyl alcohol after thermoplastic modification：50 parts；
Polycaprolactone：48 parts；
HDI：2 parts.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：2699 polyvinyl alcohol and ethylene glycol are pressed 80:20 mass ratio, sequentially adds
It is repeatedly stirred in homogenizer, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will be pre-
Batch mixing sealing, which is positioned in 40 DEG C of baking ovens, is plasticized 4h, after taking-up in double screw extruder, squeezes out and makes at 200 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in grain；
2) preparation of seawater degradable material：Again by after thermoplastic modification made from step 1) 50 parts of polyvinyl alcohol, gather oneself
48 parts and 2 parts HDI of lactone are pre-mixed, and obtain mixture, then pass through extruding pelletization under the conditions of 200 DEG C of twin-screw, 210 DEG C of conditions
Lower injection molding obtains test bars, and the seawater degradable material of alloy material structure is made.The seawater of obtained seawater degradable material
Degradation property and Tables 1 and 2 is seen respectively using mechanical property.
The seawater degradation property of 1 seawater degradable material of table
| Embodiment | After degradation 30 days weightless (wt%) | After degradation 60 days weightless (wt%) |
| 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 |
The use mechanical property of 2 seawater degradable material of table
Comparative example 1
A kind of seawater degradable material, is made of the raw material of following parts by weight：
1788 polyvinyl alcohol：40 parts；
Polycaprolactone：59.5 parts；
MDI：0.5 part.
The preparation of above-mentioned seawater degradable material, includes the following steps：
59.5 parts and 0.5 part 40 parts of polyvinyl alcohol, polycaprolactone MDI are pre-mixed, obtain mixture, then pass through double spiral shells
Extruding pelletization under the conditions of 220 DEG C of bar, under the conditions of 230 DEG C injection molding obtain test bars, seawater degradable material is made.
The result shows that：Compared with Example 7, the polyvinyl alcohol in the comparative example does not carry out thermoplastic modification in advance, because
Obtained from seawater degradable material can only the melting extrusion under 220 DEG C of higher temperature conditions, apparent thermal degradation, mechanical property occurs
The loss of energy, water-soluble poor, weightlessness 3wt%, weightlessness 7wt% after 60 days, respectively well below embodiment 7 after seawater is degraded 30 days
9wt% and 19wt%.
Comparative example 2
A kind of seawater degradable material, is made of the raw material of following parts by weight：
0588 polyvinyl alcohol after thermoplastic modification：80 parts；
Polylactic acid：20 parts.
The preparation of above-mentioned seawater degradable material, includes the following steps：
1) polyvinyl alcohol thermoplastic is modified：0588 polyvinyl alcohol and ethylene glycol are pressed 80:20 mass ratio, sequentially adds
It is repeatedly stirred in homogenizer, stirs 1~2min every time, until being sufficiently mixed uniformly, premix is made, it then will be pre-
Batch mixing sealing, which is positioned in 40 DEG C of baking ovens, is plasticized 4h, after taking-up in double screw extruder, squeezes out and makes at 160 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in grain；
2) preparation of seawater degradable material：Again by 80 parts of polyvinyl alcohol, the poly- breast after thermoplastic modification made from step 1)
20 parts of acid is pre-mixed, and obtains mixture, then by extruding pelletization under the conditions of 170 DEG C of twin-screw, is molded and is obtained under the conditions of 180 DEG C
Seawater degradable material is made in test bars.
The result shows that：Weightlessness 29wt% after seawater degradable material seawater made from the comparative example is degraded 30 days, loses after 60 days
Weight 43wt%, respectively well below the 69wt% and 89wt% of embodiment 4.It is not dropped even slowly using degradation in the seawater thus
The polyester of solution such as polylactic acid forms composite material with polyvinyl alcohol, is unfavorable for promoting the seawater degradation property of the composite material.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical solution is extended out still in protection scope of the present invention.
Claims (10)
1. a kind of service life and the adjustable seawater degradable material of degradation cycle, which is characterized in that by the original of following parts by weight
Material is made：
8-90 parts of polyvinyl alcohol after thermoplastic modification；
8-90 parts of polyester；
0-2 parts of compatilizer.
2. service life according to claim 1 and the adjustable seawater degradable material of degradation cycle, which is characterized in that described
Polyvinyl alcohol after thermoplastic modification is by the way that by polyvinyl alcohol and plasticizer mixing, sealed plasticizing, extruding pelletization is made；Its
In, the mass ratio of polyvinyl alcohol and plasticizer is 80:20-90:10.
3. service life according to claim 2 and the adjustable seawater degradable material of degradation cycle, which is characterized in that described
The temperature of plasticizing is -60 DEG C of room temperature；The time of the plasticizing is 3-6h；The temperature of the extruding pelletization is 160-200 DEG C.
4. service life according to claim 1 and the adjustable seawater degradable material of degradation cycle, which is characterized in that described
The degree of polymerization of polyvinyl alcohol is 300-2600, and the alcoholysis degree of the polyvinyl alcohol is 88%-99%.
5. service life according to claim 2 and the adjustable seawater degradable material of degradation cycle, which is characterized in that described
Plasticizer is one or more in sorbierite, 1,4- butanediols, glycerine, ethylene glycol, citric acid.
6. service life according to claim 1 and the adjustable seawater degradable material of degradation cycle, which is characterized in that described
Polyester be standard batten in the seawater in 1 year weightlessness 30wt% or more polyester.
7. service life according to claim 1 and the adjustable seawater degradable material of degradation cycle, which is characterized in that described
Polyester is polycaprolactone and/or polyhydroxyalkanoates.
8. service life according to claim 1 and the adjustable seawater degradable material of degradation cycle, which is characterized in that described
Compatilizer is one or more in ADR-4380, ADR-4370S, KH-560, KH-570, MDI and HDI.
9. service life according to claim 2 and the adjustable seawater degradable material of degradation cycle, which is characterized in that described
Seawater degradable material is the material of alloy material or skin-core structure；In the seawater degradable material of the skin-core structure, cortical material
For polyester, core material is the polyvinyl alcohol after thermoplastic modification.
The material 10. a kind of adjustable seawater of service life and degradation cycle as described in claim 1~9 any claim is degraded
The preparation method of material, which is characterized in that include the following steps：
1) polyvinyl alcohol thermoplastic is modified：
By polyvinyl alcohol and plasticizer mixing, sealed plasticizing, extruding pelletization is made；
2) preparation of seawater degradable material：
By polyvinyl alcohol, polyester and the compatilizer after thermoplastic modification, mixing, extruded granulation, injection molding were obtained using week in proportion
Phase and the adjustable seawater degradable material of degradation cycle.
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| CN109880325A (en) * | 2019-03-06 | 2019-06-14 | 南京工程学院 | A kind of degradable new polyester composite material and preparation method |
| CN109880326A (en) * | 2019-03-06 | 2019-06-14 | 南京工程学院 | A kind of water body that degradation cycle is controllable degradation polyester composite and preparation method thereof |
| CN112694726A (en) * | 2021-03-05 | 2021-04-23 | 海南赛诺实业有限公司 | Modified PGA material with higher processing performance and preparation method thereof |
| CN115537968A (en) * | 2022-09-09 | 2022-12-30 | 明新梅诺卡(江苏)新材料有限公司 | Polylactic acid sea-island fiber and preparation method thereof |
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