CN109880326A - A kind of water body that degradation cycle is controllable degradation polyester composite and preparation method thereof - Google Patents
A kind of water body that degradation cycle is controllable degradation polyester composite and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to TPVA/PLA blending toughening technical fields, and in particular to a kind of water body that degradation cycle is controllable degradation polyester composite and preparation method thereof.The controllable water body degradation polyester composite of the degradation cycle is made of the raw material of following parts by weight: 80-90 parts of thermoplastic modification polyvinyl alcohol (TPVA), 80-90 parts of polylactic acid (PLA), 25-30 parts of calcium carbonate, 0.5-2.5 parts of toughener, 0.5-2.5 parts of compatilizer.Wherein the mass ratio of polylactic acid and calcium carbonate is 1-3: 1.The weightlessness of degradation in 30 days to 60 days can be achieved than > 50% in a kind of controllable water body degradation polyester composite of degradation cycle provided by the invention in water body environment, and the content ratio of control polylactic acid and calcium carbonate can be passed through, it realizes the Effective Regulation to the polyester composite degradation cycle, while greatly improving the tensile strength of the material.
Description
Technical field
The present invention relates to TPVA/PLA blending toughening technical field, in particular to a kind of water body that degradation cycle is controllable degradation
Polyester composite and preparation method thereof.
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 material will can be carried out degradation, and produce the small molecule non-hazardous to environment.Based on considerations above, TPVA and PLA's is total to
Mixed compound system can satisfy requirement.It is carried out under the conditions of it can have existing for bacterium in the environment such as sewage sludge, river water complete
Biodegrade, and it is easy to process, with short production cycle, at low cost, production process will not generate pollution to environment, it is easy to accomplish industry
Change.
But since TPVA/PLA is incompatible two-phase system, dispersed phase TPVA is dispersed in PLA matrix with greater particle size
In, TPVA is significantly limited to PLA toughness improvement, makes that blended compound material performance pledge is hard and crisp, impact resistance
With the disadvantage of hydrophily difference, and degradation cycle be difficult to control, this greatly limits their application range.Therefore, how this is improved
It is urgently to be resolved to increase the problem of TPVA is to PLA toughening effect for compatibility both in system.
To solve the above-mentioned problems, Wang Hualin etc. changes the progress increase-volume of TPVA/PLA alloy using polyethylene glycol expanding material
Property, the compatibility for being modified the latter two all obtains different degrees of raising, but still cannot reach promising result, stability of material
Difference, lower-molecular substance easily occur infiltration, transport phenomena during materials'use and storage, finally decline material property.
Therefore, the present invention provides a kind of water body that degradation cycle is controllable degradation polyester composite and preparation method thereof, can
Effectively solve the above problems.
Summary of the invention
It is an object of the present invention to provide a kind of water body that degradation cycle is controllable degradation polyester composites.
It is another object of the present invention to provide a kind of systems of water body that degradation cycle is controllable degradation polyester composite
Preparation Method.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
80-90 parts of polyvinyl alcohol (TPVA) after thermoplastic modification；
80-90 parts of polylactic acid (PLA)；
25-30 parts of calcium carbonate；
0.5-2.5 parts of toughener；
0.5-2.5 parts of compatilizer.
Preferably, the mass ratio of the polylactic acid and calcium carbonate are as follows: 1-3: 1.
Preferably, the weight average molecular weight of the PLA is 600-20000.
Preferably, the weight average molecular weight of the TPVA is 800-30000.
Preferably, the calcium carbonate is stearic acid modified calcium carbonate.
Preferably, the mesh number of the stearic acid modified calcium carbonate is 2000 mesh, 2500 mesh or 3000 mesh.
Preferably, by mixing polyvinyl alcohol and plasticizer, sealed plasticizing, extruding pelletization is made the TPVA；Its
In, the mass ratio of polyvinyl alcohol and plasticizer is 75: 15-85: 5.
Preferably, the degree of polymerization of the polyvinyl alcohol be 500-2800, alcoholysis degree 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 plasticizer is selected from one of sorbierite, 1,4-butanediol, glycerol, ethylene glycol, citric acid or more
Kind.
Preferably, the compatilizer in ADR-4380, ADR-4370S, KH-560, KH-570, MDI and HDI one
Kind is a variety of.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of the water body that above-mentioned degradation cycle is controllable degradation polyester composite, includes the following steps:
1) preparation of TPVA: polyvinyl alcohol and plasticizing modifier are mixed, and sealing plasticizing, extruding pelletization is made；
2) preparation of polyester composite: PLA particle, compatilizer, calcium carbonate and TPVA particle are mixed in proportion
By double screw extruder extruding pelletization, a kind of water body that degradation cycle is controllable degradation polyester composite is made in injection molding.
Preferably, the temperature of plasticizing described in step 1) is -65 DEG C of room temperature；Further, of the invention certain specific
In embodiment, the temperature of plasticizing described in step 1) is 30-40 DEG C of room temperature, 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 plasticizing described in step 1) is 2-5h；Further, in certain specific embodiment parties of the invention
In formula, the time of plasticizing described in step 1) is 2-3h, 2-4h, 3-4h, 4-5h etc..
Preferably, the temperature of extruding pelletization described in step 1) is 160-200 DEG C；Further, of the invention certain
In specific embodiment, the temperature of extruding pelletization described in step 1) is 160-200 DEG C etc..
Preferably, the temperature of extruding pelletization described in step 2) is 170-185 DEG C.
Preferably, the temperature of injection molding described in step 2) is 170-185 DEG C；Further, of the invention certain specific
In embodiment, the temperature of injection molding 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..
Excellent effect of the invention is as follows:
(1) a kind of controllable water body degradation polyester composite of degradation cycle provided by the invention can be real in water body environment
Existing 30 days to 60 days degradation weightlessness can be realized multiple to the polyester than > 50% by the proportion of control polylactic acid and calcium carbonate
The Effective Regulation of condensation material degradation cycle.
(2) a kind of controllable water body of degradation cycle provided by the invention is degraded polyester composite, the tristearin in ingredient
Sour modified calcium carbonate has self-lubricating function in TPVA/PLA compound system, increases the polyester compound system compatibility.
(3) a kind of controllable water body of degradation cycle provided by the invention is degraded polyester composite, the carbonic acid in ingredient
Calcium does not influence the flexible molecule chain structure of compatilizer, so that TPVA and PLA be promoted to be closely aligned, improves the stretching of composite material
Intensity.
Specific embodiment
Embodiment 1:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 80 parts；
Polylactic acid: 82.5 parts；
2000 mesh of resin acid modified calcium carbonate: 27 parts；
MDI:1.5 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 90: 10 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 80 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
82.5 parts, 27 parts of 2000 mesh of resin acid modified calcium carbonate, 1.5 parts of nitrile rubbers and 1.5 parts of MDI are pre-mixed, and mixture is obtained, and are led to
Extruding pelletization under the conditions of crossing 170 DEG C of twin-screw, injection molding obtains test bars under the conditions of 180 DEG C, and it is compound that water body degradation polyester is made
Material.The seawater degradation property and mechanical experimental results of water body degradation polyester composite are shown in Tables 1 and 2 respectively.
Embodiment 2:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 85 parts；
Polylactic acid: 82.5 parts；
2000 mesh of resin acid modified calcium carbonate: 27 parts；
ADR-4380:1.5 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 85 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
82.5 parts, 27 parts of 2000 mesh of resin acid modified calcium carbonate, 1.5 parts of nitrile rubbers and 1.5 parts of ADR-4380 are pre-mixed, and must be mixed
Object, 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 water body degradation polyester is made
Composite material.The seawater degradation property and mechanical experimental results of obtained water body degradation polyester composite are shown in Table 1 respectively
With table 2.
Embodiment 3:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0388 polyvinyl alcohol after thermoplastic modification: 90 parts；
Polylactic acid: 85 parts；
2000 mesh of resin acid modified calcium carbonate: 28 parts；
ADR-4380:1.5 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0388 polyvinyl alcohol and citric acid are pressed to 85: 15 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 90 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
85 parts, 28 parts of 2000 mesh of resin acid modified calcium carbonate, 1.5 parts of nitrile rubbers and 1.5 parts of ADR-4380 are pre-mixed, and must be mixed
Object, 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 water body degradation polyester is made
Composite material.The seawater degradation property and mechanical experimental results of obtained water body degradation polyester composite are shown in Table 1 respectively
With table 2.
Embodiment 4:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 90 parts；
Polylactic acid: 80 parts；
2000 mesh of resin acid modified calcium carbonate: 27 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 90: 10 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 90 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
80 parts, 27 parts of 2000 mesh of resin acid modified calcium carbonate and 1.5 parts of nitrile rubbers are pre-mixed, and are obtained mixture, are passed through twin-screw 170
Extruding pelletization under the conditions of DEG C, injection molding obtains test bars under the conditions of 180 DEG C, and water body is made and degrades polyester composite.It is obtained
The seawater degradation property and mechanical experimental results of water body degradation polyester composite are shown in Tables 1 and 2 respectively.
Embodiment 5:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 80 parts；
Polylactic acid: 80 parts；
2000 mesh of resin acid modified calcium carbonate: 27 parts；
MDI:1.5 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 80 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
80 parts, 27 parts of 2000 mesh of resin acid modified calcium carbonate, 1.5 parts of nitrile rubbers and 1.5 parts of MDI are pre-mixed, and are obtained mixture, are passed through
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 water body is made and degrades polyester composite wood
Material.The seawater degradation property and mechanical experimental results of obtained water body degradation polyester composite are shown in Tables 1 and 2 respectively.
Embodiment 6:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 85 parts；
Polylactic acid: 85 parts；
2000 mesh of resin acid modified calcium carbonate: 28 parts；
MDI:1.5 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 85 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
85 parts, 28 parts of 2000 mesh of resin acid modified calcium carbonate, 1.5 parts of nitrile rubbers and 1.5 parts of MDI are pre-mixed, and are obtained mixture, are passed through
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 water body is degraded polyester composite.Institute
The seawater degradation property and mechanical experimental results that water body degradation polyester composite is made are shown in Tables 1 and 2 respectively.
Embodiment 7:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 80 parts；
Polylactic acid: 90 parts；
2000 mesh of resin acid modified calcium carbonate: 30 parts；
MDI:1.5 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 80 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
90 parts, 30 parts of 2000 mesh of resin acid modified calcium carbonate, 1.5 parts of nitrile rubbers and 1.5 parts of MDI are pre-mixed, and are obtained mixture, are passed through
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 water body is made and degrades polyester composite wood
Material.The seawater degradation property and mechanical experimental results of obtained water body degradation polyester composite are shown in Tables 1 and 2 respectively.
Embodiment 8:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 90 parts；
Polylactic acid: 80 parts；
2000 mesh of resin acid modified calcium carbonate: 27 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 90 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
80 parts, 27 parts of 2000 mesh of resin acid modified calcium carbonate and 1.5 parts of nitrile rubbers are pre-mixed, and are obtained mixture, are passed through twin-screw 170
Extruding pelletization under the conditions of DEG C, injection molding obtains test bars under the conditions of 180 DEG C, and water body is made and degrades polyester composite.It is obtained
The seawater degradation property and mechanical experimental results of water body degradation polyester composite are shown in Tables 1 and 2 respectively.
Embodiment 9:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 82.5 parts；
Polylactic acid: 82.5 parts；
2000 mesh of resin acid modified calcium carbonate: 27 parts；
MDI:1.5 parts；
Nitrile rubber: 1.5 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 82.5 parts of polyvinyl alcohol, poly- cream after step (1) to be made to thermoplastic modification
82.5 parts of acid, 27 parts of 2000 mesh of resin acid modified calcium carbonate, 1.5 parts of nitrile rubbers and 1.5 parts of MDI are pre-mixed, and mixture is obtained,
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 it is multiple that water body degradation polyester is made
Condensation material.The seawater degradation property and mechanical experimental results of obtained water body degradation polyester composite are shown in Table 1 He respectively
Table 2.
Embodiment 10:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 82.5 parts；
Polylactic acid: 85 parts；
2000 mesh of resin acid modified calcium carbonate: 28 parts；
MDI:2 parts；
Nitrile rubber: 2 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 82.5 parts of polyvinyl alcohol, poly- cream after step (1) to be made to thermoplastic modification
85 parts of acid, 28 parts of 2000 mesh of resin acid modified calcium carbonate, 1.5 parts of nitrile rubbers and 2 parts of MDI are pre-mixed, and are obtained mixture, are passed through
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 water body is made and degrades polyester composite wood
Material.The seawater degradation property and mechanical experimental results of obtained water body degradation polyester composite are shown in Tables 1 and 2 respectively.
Comparative example 1:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 90 parts；
Polylactic acid: 80 parts；
MDI:2 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: 90 parts of polyvinyl alcohol, polylactic acid after step (1) to be made to thermoplastic modification
80 parts and 2 parts of MDI are pre-mixed, and mixture is obtained, and are made by squeezing out under the conditions of 170 DEG C of twin-screw, are molded under the conditions of 180 DEG C
To test bars, water body degradation polyester composite is made.The seawater degradation property of obtained water body degradation polyester composite
Tables 1 and 2 is seen respectively with mechanical experimental results.
The result shows that: weightlessness 83wt% after seawater degradable material seawater made from the comparative example is degraded 30 days loses after 60 days
Heavy 90wt%, it is very nearly the same with the 92wt% and 92wt% of embodiment 9, but tensile strength declines to a great extent.
Comparative example 2:
A kind of water body that degradation cycle is controllable degradation polyester composite, is made of the raw material of following parts by weight:
0599 polyvinyl alcohol after thermoplastic modification: 90 parts；
80 parts of polycaprolactone；
MDI:2 parts.
The controllable water body degradation polyester composite preparation of above-mentioned degradation cycle, includes the following steps:
(1) preparation of TPVA: 0599 polyvinyl alcohol and citric acid are pressed to 80: 20 mass ratio, sequentially add high-speed stirring
It mixes in machine and is repeatedly stirred, stir 2~3min every time, until being sufficiently mixed uniformly, premix is made, it is then that premix is close
Envelope is placed in 65 DEG C of baking ovens and is plasticized 5h, after taking-up in the double screw extruder that extrusion temperature is 160 DEG C extruding pelletization, be made
The polyvinyl alcohol of thermoplastic modification；
(2) preparation of polyester composite: by step (1) be made thermoplastic modification after 90 parts of polyvinyl alcohol, gather in oneself
80 parts and 2 parts MDI of ester are pre-mixed, and mixture is obtained, and pass through extruding pelletization under the conditions of 170 DEG C of twin-screw, 180 DEG C of condition bets
Modeling obtains test bars, and water body degradation polyester composite is made.The seawater degradation of obtained water body degradation polyester composite
Performance and mechanical experimental results are shown in Tables 1 and 2 respectively.
The result shows that: weightlessness 53wt% after seawater degradable material seawater made from the comparative example is degraded 30 days loses after 60 days
Weight 61wt%, degradation rate slow down compared with comparative example 1, and tensile strength declines to a great extent.
The seawater degradation property of 1 water body of table degradation polyester composite
| Embodiment | After degradation 30 days weightless (wt%) | After degradation 60 days weightless (wt%) |
| 1 | 14 | 23 |
| 2 | 6 | 14 |
| 3 | 4 | 12 |
| 4 | 43 | 59 |
| 5 | 54 | 71 |
| 6 | 77 | 82 |
| 7 | 2 | 7 |
| 8 | 27 | 42 |
| 9 | 92 | 92 |
| 10 | 62 | 83 |
| Comparative example 1 | 83 | 90 |
| Comparative example 2 | 53 | 61 |
2 water body of table degradation polyester composite service performance
Claims (6)
- The polyester composite 1. a kind of water body that degradation cycle is controllable is degraded, which is characterized in that by the raw material of following parts by weight It is made:80-90 parts of thermoplastic modification polyvinyl alcohol (TPVA)；80-90 parts of polylactic acid (PLA)；25-30 parts of calcium carbonate；0.5-2.5 parts of toughener；0.5-2.5 parts of compatilizer.
- The polyester composite 2. a kind of controllable water body of degradation cycle according to claim 1 is degraded, which is characterized in that institute The mass ratio for stating polylactic acid and calcium carbonate is 1-3: 1.
- The polyester composite 3. a kind of controllable water body of degradation cycle according to claim 1 is degraded, which is characterized in that institute The weight average molecular weight for stating PLA is 600-20000, and the degree of polymerization of polyvinyl alcohol is 500-2800, alcoholysis degree 88%-99%, again Average molecular weight is 800-30000.
- The polyester composite 4. a kind of controllable water body of degradation cycle according to claim 1 is degraded, which is characterized in that institute Stating calcium carbonate is stearic acid modified calcium carbonate.
- The polyester composite 5. a kind of controllable water body of degradation cycle according to claim 4 is degraded, which is characterized in that institute The mesh number for stating stearic acid modified calcium carbonate is 3000 mesh, 3500 mesh or 4000 mesh.
- 6. a kind of preparation side of the controllable water body degradation polyester composite of degradation cycle as described in any one in claim 1-5 Method, it is characterised in that include the following steps:(1) preparation of TPVA: polyvinyl alcohol and plasticizing modifier are mixed, and sealing plasticizing, extruding pelletization is made；(2) it the preparation of polyester composite: is passed through after PLA particle, compatilizer, calcium carbonate and TPVA particle are mixed in proportion A kind of water body that degradation cycle is controllable degradation polyester composite is made in double screw extruder extruding pelletization, injection molding.
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| CN (1) | CN109880326A (en) |
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| CN102250454A (en) * | 2011-05-31 | 2011-11-23 | 常州大学 | Low-cost fully-degradable high-flexibility polylactic acid composite material and preparation method thereof |
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| 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 |
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| CN102250454A (en) * | 2011-05-31 | 2011-11-23 | 常州大学 | Low-cost fully-degradable high-flexibility polylactic acid composite material and preparation method thereof |
| US20140120062A1 (en) * | 2011-11-16 | 2014-05-01 | 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 |
| CN106674923A (en) * | 2016-12-13 | 2017-05-17 | 常州绿之源高分子材料有限公司 | Controllable-degradation PBAT/PLA (poly(butyleneadipate-co-terephthalate)/polylactic acid) composite film 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 |
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Application publication date: 20190614 |