CN109880325A - A kind of degradable new polyester composite material and preparation method - Google Patents
A kind of degradable new polyester composite material and preparation method Download PDFInfo
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- CN109880325A CN109880325A CN201910169753.8A CN201910169753A CN109880325A CN 109880325 A CN109880325 A CN 109880325A CN 201910169753 A CN201910169753 A CN 201910169753A CN 109880325 A CN109880325 A CN 109880325A
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Abstract
The present invention provides a kind of degradable new polyester composite material and preparation method.The degradable new polyester composite material includes the raw material of following parts by weight: 10-85 parts of the polyvinyl alcohol after thermoplastic modification；15-85 parts of polylactic acid；0.5-2.5 parts of compatilizer；30-45 parts of polyethylene glycol.The preparation method of the degradable new polyester composite material mainly comprises the steps that the preparation of (1) thermoplastic modification polyvinyl alcohol；(2) modified polyvinylalcohol/polylactic acid polyester composite preparation；(3) preparation of degradable new polyester composite material.Degradable new polyester composite material provided by the invention can be degraded in land by composting mode, and the small molecule of environmental sound can be voluntarily degraded into water body environment.Preparation method provided by the invention effectively improves the toughness of PVA/PLA polyester compound system, and has added the water body degradation rate of fast PVA/PLA polyester compound system.
Description
Technical field
The present invention relates to the technical field of sea environment-friendly, in particular to a kind of degradable new polyester composite material and its system
Preparation Method.
Background technique
In recent years, the plastics that produced every year of the whole world were more than 300,000,000, wherein 8,000,000 tons of plastic garbages of annual about generation pass through by
Directly abandon, storm washes away and inland river garbage fair current etc. directly or indirectly mode enters ocean, and pass through ocean current
It is widely present in them in entire marine ecosystems.These plastic garbage a part stop on the beach, a part floating
On sea or seabed is sunk to, seriously destroys the marine eco-environment, influences maritime traffic normal operation, endangers marine organisms multiplicity
Property.Meanwhile ocean rubbish causes indirect serious harm to the mankind by very long food chain.It is currently reported in human body
It inside detected plastic components.
In order to make plastics that can degrade as early as possible after being discarded into seawater, many water-soluble high-molecular materials meet this
Condition.But so that material is degraded in water body environment, and the product after degradation is the small molecule non-hazardous to environment, and
Meet material product in service life to the requirement of use intensity simultaneously.Based on considerations above, thermoplastic modification polyvinyl alcohol/
Polylactic acid polyester composite can satisfy requirement, can be degradable in the environment such as sewage sludge, river water, seawater, and drop
Solution period and service life can be regulated and controled by changing constituent mass ratio.But the polyester composite is deposited in practical applications
In the problem that mechanical property is poor, degradation cycle is too long.
Polyethylene glycol (PEG) has preferable amphipathic, biocompatibility and end group reactivity, and molecular weight ranges are wide, select
It is big to select leeway, pretends as one of most common polyester modification means.PEG is added in modified PVA/PLA polyester system, it can be obvious
Weaken polylactic acid molecule interchain active force, the crystallization rate for improving polylactic acid, the glass transition temperature for reducing polylactic acid, thus effectively
The elongation at break and hydrophilicity for improving polyester system, improve the water body degradation property of material, accelerate the degradation rate of material.
Summary of the invention
It is an object of the present invention to provide a kind of degradable new polyester composite materials.
It is another object of the present invention to provide a kind of preparation methods of degradable new polyester composite material.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
10-85 parts of polyvinyl alcohol after thermoplastic modification；
15-85 parts of polylactic acid；
0.5-2.5 parts of compatilizer；
30-45 parts of polyethylene glycol.
Preferably, the degradable new polyester composite material be standard batten in the seawater in 1 year weightlessness 20wt% with
Upper or the weightlessness 30wt% or more in the composting conditions next year of land polyester composite.
Preferably, the polyvinyl alcohol after the thermoplastic modification is by mixing polyvinyl alcohol and plasticizing modifier, through close
Envelope plasticizing, extruding pelletization are made；Wherein, the mass ratio of polyvinyl alcohol and plasticizing modifier is 75: 25-90: 10.
Preferably, the temperature of the plasticizing is 40-90 DEG C；Further, in certain specific embodiments of the invention,
For example, the temperature of the plasticizing is 40-50 DEG C, 40-60 DEG C, 60-70 DEG C, 70-80 DEG C, 80-90 DEG C etc..
Preferably, the time of the plasticizing is 3-7h；Further, in certain specific embodiments of the 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 140-170 DEG C；Further, in certain specific implementations of the invention
In mode, for example, the temperature of the extruding pelletization is 140-150 DEG C, 150-160 DEG C, 160-170 DEG C etc..
Preferably, the degree of polymerization of the polyvinyl alcohol is 500-2800, and the alcoholysis degree of the polyvinyl alcohol is 88%-
99%.
Preferably, the molecular weight polyethylene glycol is 600-20000.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of above-mentioned degradable new polyester composite material, includes the following steps:
(1) preparation of thermoplastic modification polyvinyl alcohol: polyvinyl alcohol and plasticizing modifier are mixed, and sealing plasticizing squeezes out
It is granulated and is made；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: by the polyvinyl alcohol, poly- after thermoplastic modification
Lactic acid and compatilizer mix in proportion, and modified polyvinylalcohol/polylactic acid polyester composite is made in extruding pelletization；
(3) preparation of degradable new polyester composite material: by modified polyvinylalcohol/polylactic acid polyester composite and gather
Ethylene glycol mixes in proportion, rapid strong stirring, is molded and degradable new polyester composite material is made.
Preferably, the temperature of plasticizing described in step (1) is 40-90 DEG C；Further, in certain specific realities of the invention
It applies in mode, for example, the temperature of step (1) described plasticizing is 40-50 DEG C, 40-60 DEG C, 60-70 DEG C, 70-80 DEG C, 80-90 DEG C
Deng.
Preferably, the time of step (1) described plasticizing is 3-7h；Further, in certain specific embodiment parties of the invention
In formula, for example, the time of step (1) described plasticizing is 3-4h, 3-5h, 4-5h, 4-6h, 5-6h etc..
Preferably, the temperature of step (1) described extruding pelletization is 140-170 DEG C；Further, in certain tools of the invention
In body embodiment, for example, the temperature of step (1) described extruding pelletization is 140-150 DEG C, 150-160 DEG C, 160-170 DEG C etc..
Preferably, the temperature of extruding pelletization described in step (2) is 140-170 DEG C；Further, of the invention certain
In specific embodiment, for example, the temperature of extruding pelletization described in step (2) is 140-150 DEG C, 150-160 DEG C, 160-170
DEG C etc..
Preferably, the temperature of injection molding described in step (3) is 160-190 DEG C；Further, of the invention certain specific
In embodiment, for example, the temperature of injection molding described in step (3) is 160-170 DEG C, 170-180 DEG C, 180-190 DEG C etc..
Beneficial effects of the present invention are as follows:
(1) PEG is added in modified PVA/PLA polyester system, the crystallization rate of polylactic acid can be significantly improved and reduces poly-
The glass transition temperature of lactic acid, to effectively improve the mechanical property of polyester system during use.
(2) PEG that uses of the present invention has a good biocompatibility, and segment is submissive and no biotoxicity, can be in not shadow
While ringing PVA/PLA polyester compound system biocompatibility, effectively weakens polylactic acid molecule interchain active force, accelerate the polyester
The formula degradation of bursting apart of compound system, significantly changes its water body degradation property.
(3) degradable new polyester composite material provided by the invention can realize fast fast-growing in land by composting mode
Object degradation can also realize fast degradation, to environment after realization high molecular products are discarded in water body environment especially briny environment
Absolute no pollution.
(4) degradable new polyester composite material of the present invention can be processed by melt blending, and simple process is controllable, energy consumption
It is low.
Specific embodiment
The present invention provides a kind of degradable new polyester composite materials, are made of the raw material of following parts by weight: thermoplastic
Property is polyvinyl alcohol 10-85 parts modified；15-85 parts of polylactic acid；0.5-2.5 parts of compatilizer；30-45 parts of polyethylene glycol.This hair
It is bright when preparing modified polyvinylalcohol/polylactic acid polyester composite, not only improved using the polyvinyl alcohol after thermoplastic modification
The water solubility of PLA, thermal stability and mechanical property, realize that technique when preparing the polyester composite is simplified and energy consumption drop
Low, polyethylene glycol effectively improves the biocompatibility and plasticity of the PVA/PLA polyester compound system.Degradable new polyester is made
Composite material has the service life for being not less than 1 year at normal temperature, enters in water body after discarding and apparent degradation occurs.
Optionally, the degree of polymerization of the polyvinyl alcohol is 500-2800, 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 plasticizing modifier is selected from one of glycerine, ethylene glycol, propylene glycol, sorbierite or a variety of.
Above-mentioned plasticizing modifier is common polyalcohols and carboxylic-acid substance, cheap and aobvious to the effect of PVA thermoplastic modification
It writes.
Preferably scheme, the compatilizer be selected from one of ADR-4380, ADR-4370S, KH-560, MDI or
It is a variety of；The compatilizer is common commercial goods coupling agent, plays and is remarkably reinforced to the interaction between PVA and polyester
Effect.
Optionally, the molecular weight polyethylene glycol is 600-20000.Polyethylene glycol in the molecular weight ranges is normal
The commercially available polyethylene glycol seen, raw material easily obtain, and property is stablized.Degradation property and crystal property to polylactic acid improve good.
Second part of the present invention provides a kind of preparation method of degradable new polyester composite material, mainly includes following step
It is rapid:
(1) preparation of thermoplastic modification polyvinyl alcohol: polyvinyl alcohol and plasticizing modifier are mixed, and sealing plasticizing squeezes out
It is granulated and is made；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: by the polyvinyl alcohol, poly- after thermoplastic modification
Lactic acid and compatilizer mix in proportion, and modified polyvinylalcohol/polylactic acid polyester composite is made in extruding pelletization；
(3) preparation of degradable new polyester composite material: by modified polyvinylalcohol/polylactic acid polyester composite and gather
Ethylene glycol mixes in proportion, rapid strong stirring, is molded and degradable new polyester composite material is made.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of foregoing invention, still fall within protection scope of the present invention.In addition, such as
Fruit is raw materials used to be all commercially available without other explanations.
Embodiment 1:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 30 parts；
Polylactic acid: 38.5 parts；
KH-560:1.5 parts；
Polyethylene glycol: 30 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 90: 10 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
30 parts of polyvinyl alcohol, 38.5 parts and 1.5 parts KH560 of polylactic acid be pre-mixed, obtain mixture, then pass through 170 DEG C of twin-screw
Under the conditions of extruding pelletization；
(3) preparation of degradable new polyester composite material: by modified polyvinylalcohol/polylactic acid obtained in step (2)
70 parts of polyester composite and 30 parts of polyethylene glycol premixings, obtain mixture, by extruding pelletization under the conditions of 170 DEG C of twin-screw,
Injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable new polyester is multiple
The seawater degradation property of condensation material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 2:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 40 parts；
Polylactic acid: 28.5 parts；
MDI:1.5 parts；
Polyethylene glycol: 30 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
40 parts of polyvinyl alcohol, 28.5 parts and 1.5 parts MDI of polylactic acid be pre-mixed, obtain mixture, pass through 170 DEG C of conditions of twin-screw
Lower extruding pelletization；
(3) modified polyvinylalcohol/polylactic acid poly the preparation of degradable new polyester composite material: will be made in step (2)
70 parts of ester composite material and 30 parts of polyethylene glycol premixings, obtain mixture, then by extruding pelletization under the conditions of 170 DEG C of twin-screw,
Injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable new polyester is multiple
The seawater degradation property of condensation material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 3:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0388 polyvinyl alcohol after thermoplastic modification: 20 parts；
Polylactic acid: 58.5 parts；
MDI:1.5 parts；
Polyethylene glycol: 20 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0388 polyvinyl alcohol and citric acid: being pressed 85: 15 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: again by thermoplastic modification made from step (1)
58.5 parts and 1.5 parts 20 parts of polyvinyl alcohol afterwards, polylactic acid MDI are pre-mixed, and are obtained mixture, are passed through 170 DEG C of items of twin-screw
Extruding pelletization under part；
(3) modified polyvinylalcohol/polylactic acid poly the preparation of degradable new polyester composite material: will be made in step (2)
80 parts of ester composite material and 20 parts of polyethylene glycol premixings, obtain mixture, by extruding pelletization under the conditions of 170 DEG C of twin-screw, 180
Injection molding obtains test bars under the conditions of DEG C, and degradable new polyester composite material is made.Obtained degradable new polyester is compound
The seawater degradation property of material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 4:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 60 parts；
Polylactic acid: 20 parts；
Polyethylene glycol: 20 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 90: 10 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
60 parts of polyvinyl alcohol, 20 parts of polylactic acid be pre-mixed, obtain mixture, then pass through extruding pelletization under the conditions of 170 DEG C of twin-screw；
(3) preparation of degradable new polyester composite material: by modified polyvinylalcohol/polylactic acid obtained in step (2)
80 parts of polyester composite and 20 parts of polyethylene glycol premixings, obtain mixture, by extruding pelletization under the conditions of 170 DEG C of twin-screw,
Injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable new polyester is multiple
The seawater degradation property of condensation material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 5:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 10 parts；
Polylactic acid: 48.5 parts；
KH-560:1.5 parts；
Polyethylene glycol: 40 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
10 parts of polyvinyl alcohol, 48.5 parts and 1.5 parts KH-560 of polylactic acid be pre-mixed, obtain mixture, pass through 170 DEG C of items of twin-screw
Extruding pelletization under part；
(3) preparation of degradable new polyester composite material: again by modified polyvinylalcohol obtained in step (2)/poly- cream
60 parts and 40 parts of the polyethylene glycol premixings of acid polyester composite material, obtain mixture, are made by squeezing out under the conditions of 170 DEG C of twin-screw
, injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable is novel poly-
The seawater degradation property of ester composite material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 6:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 10 parts；
Polylactic acid: 38.5 parts；
KH-560:1.5 parts；
Polyethylene glycol: 50 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
10 parts of polyvinyl alcohol, 38.5 parts and 1.5 parts KH-560 of polylactic acid be pre-mixed, obtain mixture, pass through 170 DEG C of items of twin-screw
Extruding pelletization under part；
(3) modified polyvinylalcohol/polylactic acid the preparation of degradable new polyester composite material: will be made in step (2) again
50 parts and 50 parts of polyethylene glycol premixings of polyester composite obtain mixture, then are made by squeezing out under the conditions of 170 DEG C of twin-screw
, injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable is novel poly-
The seawater degradation property of ester composite material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 7:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 40 parts；
Polylactic acid: 48.5 parts；
KH-560:1.5 parts；
Polyethylene glycol: 10 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
40 parts of polyvinyl alcohol, 48.5 parts and 1.5 parts KH-560 of polylactic acid be pre-mixed, obtain mixture, pass through 170 DEG C of items of twin-screw
Extruding pelletization under part；
(3) preparation of degradable new polyester composite material: by modified polyvinylalcohol/polylactic acid obtained in step (2)
90 parts of polyester composite and 10 parts of polyethylene glycol premixings, obtain mixture, by extruding pelletization under the conditions of 170 DEG C of twin-screw,
Injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable new polyester is multiple
The seawater degradation property of condensation material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 8:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 60 parts；
Polylactic acid: 20 parts；
Polyethylene glycol: 20 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
60 parts of polyvinyl alcohol, 20 parts of polylactic acid be pre-mixed, obtain mixture, pass through extruding pelletization under the conditions of 170 DEG C of twin-screw；
(3) modified polyvinylalcohol/polylactic acid the preparation of degradable new polyester composite material: will be made in step (2) again
80 parts of polyester composite and 20 parts of polyethylene glycol premixings, obtain mixture, by extruding pelletization under the conditions of 170 DEG C of twin-screw,
Injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable new polyester is multiple
The seawater degradation property of condensation material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 9:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 10 parts；
Polylactic acid: 8.5 parts；
KH-560:1.5 parts；
Polyethylene glycol: 80 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
10 parts of polyvinyl alcohol, 8.5 parts and 1.5 parts KH-560 of polylactic acid be pre-mixed, obtain mixture, pass through 170 DEG C of items of twin-screw
Extruding pelletization under part；
(3) preparation of degradable new polyester composite material: again by modified polyvinylalcohol obtained in step (2)/poly- cream
20 parts and 80 parts of the polyethylene glycol premixings of acid polyester composite material, obtain mixture, are made by squeezing out under the conditions of 170 DEG C of twin-screw
, injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable is novel poly-
The seawater degradation property of ester composite material and Tables 1 and 2 is seen respectively using mechanical property.
Embodiment 10:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 20 parts；
Polylactic acid: 28 parts；
KH-560:2 parts；
Polyethylene glycol: 50 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
20 parts of polyvinyl alcohol, 28 parts and 2 parts KH-560 of polylactic acid be pre-mixed, mixture is obtained, under the conditions of 170 DEG C of twin-screw
Extruding pelletization；
(3) preparation of degradable new polyester composite material: by modified polyvinylalcohol/polylactic acid obtained in step (2)
50 parts of polyester composite and 50 parts of polyethylene glycol premixings, obtain mixture, by extruding pelletization under the conditions of 170 DEG C of twin-screw,
Injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable new polyester is multiple
The seawater degradation property of condensation material and Tables 1 and 2 is seen respectively using mechanical property.
The seawater degradation property of 1 degradable new polyester composite material of table
| Embodiment | After degradation 30 days weightless (wt%) | After degradation 60 days weightless (wt%) |
| 1 | 13 | 22 |
| 2 | 8 | 17 |
| 3 | 5 | 10 |
| 4 | 46 | 54 |
| 5 | 57 | 75 |
| 6 | 73 | 89 |
| 7 | 3 | 9 |
| 8 | 22 | 48 |
| 9 | 97 | 99 |
| 10 | 64 | 83 |
2 degradable new polyester composite material service performance of table
Comparative example 1:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 50 parts；
Polylactic acid: 48 parts；
KH-560:2 parts；
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
50 parts of polyvinyl alcohol, 48 parts and 2 parts KH-560 of polylactic acid be pre-mixed, mixture is obtained, under the conditions of 170 DEG C of twin-screw
Extrusion is made, and injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable is new
The seawater degradation property of type polyester composite and Tables 1 and 2 is seen respectively using mechanical property.
The result shows that: weightlessness 3wt% after seawater degradable material seawater made from the comparative example is degraded 30 days, it is weightless after 60 days
5wt%, respectively well below the 97wt% and 99wt% of embodiment 4.Thus it is added without poly- cream that is poly ethyldiol modified and being formed
The seawater degradation property of sour composite material, the composite material is very poor, or even does not degrade.
Comparative example 2:
A kind of degradable new polyester composite material, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 10 parts；
Polycaprolactone: 38.5 parts；
KH-560:1.5 parts；
Polyethylene glycol: 50 parts.
Above-mentioned degradable new polyester composite material preparation, includes the following steps:
(1) 0599 polyvinyl alcohol and citric acid: being pressed 80: 20 mass ratio by the preparation of thermoplastic modification polyvinyl alcohol,
It sequentially adds in high-speed mixer and is repeatedly stirred, stir 1~2min every time, until being sufficiently mixed uniformly, premix is made,
Then premix sealing is placed in 60 DEG C of baking ovens and is plasticized 4h, after taking-up in double screw extruder, at 150 DEG C of extrusion temperature
The polyvinyl alcohol of thermoplastic modification is made in extruding pelletization；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: after thermoplastic modification made from step (1)
10 parts of polyvinyl alcohol, 38.5 parts and 1.5 parts KH-560 of polycaprolactone be pre-mixed, obtain mixture, pass through 170 DEG C of twin-screw
Under the conditions of extruding pelletization；
(3) preparation of degradable new polyester composite material: by modified polyvinylalcohol/polylactic acid obtained in step (2)
50 parts of polyester composite and 50 parts of polyethylene glycol premixings, obtain mixture, by extruding pelletization under the conditions of 170 DEG C of twin-screw,
Injection molding obtains test bars under the conditions of 180 DEG C, and degradable new polyester composite material is made.Obtained degradable new polyester is multiple
The seawater degradation property of condensation material and Tables 1 and 2 is seen respectively using mechanical property.
The result shows that: weightlessness 11wt% after seawater degradable material seawater made from the comparative example is degraded 30 days loses after 60 days
Weight 19wt%, degradation rate are more slow.Thus using slow or even non-degradable polyester such as polycaprolactone of degrading in the seawater
With polyvinyl alcohol blending, composite material is formed by poly ethyldiol modified, the seawater degradation property of the composite material is improved
It is not obvious.
Claims (6)
1. a kind of degradable new polyester composite material, which is characterized in that be made of the raw material of following parts by weight:
10-85 parts of polyvinyl alcohol after thermoplastic modification；
15-85 parts of polylactic acid；
0.5-2.5 parts of compatilizer；
30-45 parts of polyethylene glycol.
2. a kind of degradable new polyester composite material according to claim 1, which is characterized in that the degradable is novel
Polyester composite is standard batten weightlessness 20wt% or more or in the composting conditions next year of land in 1 year in the seawater
The polyester composite of weightless 30wt% or more.
3. a kind of degradable new polyester composite material according to claim 1, which is characterized in that the thermoplastic modification
Polyvinyl alcohol afterwards is by the way that by polyvinyl alcohol and plasticizing modifier mixing, sealing is plasticized, and extruding pelletization is made；Wherein, polyethylene
The mass ratio of pure and mild plasticizing modifier is 75: 25-90: 10.
4. a kind of degradable new polyester composite material according to claim 3, which is characterized in that the plasticization temperature is
40-90℃；The fusion time is 3-7h；The temperature of the extruding pelletization is 140-170 DEG C；The degree of polymerization of the polyvinyl alcohol
For 500-2800, the alcoholysis degree of the polyvinyl alcohol is 88%-99%.
5. a kind of degradable new polyester composite material according to claim 1, which is characterized in that the polyethylene glycol point
Son amount is 600-20000.
6. a kind of preparation method of degradable new polyester composite material described in a kind of Claims 1 to 5, which is characterized in that
The preparation method comprises the following steps:
(1) preparation of thermoplastic modification polyvinyl alcohol: polyvinyl alcohol and plasticizing modifier are mixed, sealing plasticizing, extruding pelletization
It is made；
(2) modified polyvinylalcohol/polylactic acid polyester composite preparation: by the polyvinyl alcohol after thermoplastic modification, polylactic acid
It is mixed in proportion with compatilizer, extruding pelletization is made；
(3) preparation of degradable new polyester composite material: modified polyvinylalcohol/polylactic acid polyester composite is heated to melting
Melt state, polyethylene glycol is added, rapid strong stirring is molded and degradable new polyester composite material is made.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573961A (en) * | 2022-02-18 | 2022-06-03 | 广西科学院 | High-toughness film capable of being degraded in water environment and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11199766A (en) * | 1998-01-14 | 1999-07-27 | Mitsui Chem Inc | Air bubble sheet |
| WO2013074099A1 (en) * | 2011-11-16 | 2013-05-23 | Empire Technology Development Llc | Three-dimensional porous biodegradable cell scaffold |
| CN103319865A (en) * | 2013-06-08 | 2013-09-25 | 上海博疆新材料科技有限公司 | Polylactic acid alloy membrane and application thereof |
| CN105524383A (en) * | 2014-09-29 | 2016-04-27 | 中国石化集团四川维尼纶厂 | Thermoplastic polyvinyl alcohol composition and preparation method thereof |
| CN106589852A (en) * | 2016-12-15 | 2017-04-26 | 中国科学院理化技术研究所 | Water body degradation material with adjustable degradation period and preparation method thereof |
| CN108624020A (en) * | 2018-06-05 | 2018-10-09 | 中国科学院理化技术研究所 | A kind of service life and the adjustable seawater degradable material of degradation cycle and preparation method thereof |
-
2019
- 2019-03-06 CN CN201910169753.8A patent/CN109880325A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11199766A (en) * | 1998-01-14 | 1999-07-27 | Mitsui Chem Inc | Air bubble sheet |
| WO2013074099A1 (en) * | 2011-11-16 | 2013-05-23 | Empire Technology Development Llc | Three-dimensional porous biodegradable cell scaffold |
| CN103319865A (en) * | 2013-06-08 | 2013-09-25 | 上海博疆新材料科技有限公司 | Polylactic acid alloy membrane and application thereof |
| CN105524383A (en) * | 2014-09-29 | 2016-04-27 | 中国石化集团四川维尼纶厂 | Thermoplastic polyvinyl alcohol composition and preparation method thereof |
| CN106589852A (en) * | 2016-12-15 | 2017-04-26 | 中国科学院理化技术研究所 | Water body degradation material with adjustable degradation period and preparation method thereof |
| CN108624020A (en) * | 2018-06-05 | 2018-10-09 | 中国科学院理化技术研究所 | A kind of service life and the adjustable seawater degradable material of degradation cycle and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573961A (en) * | 2022-02-18 | 2022-06-03 | 广西科学院 | High-toughness film capable of being degraded in water environment and preparation method and application thereof |
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