CN109679305A - A kind of starch-based degradable PP/PHB composite material and preparation method - Google Patents
A kind of starch-based degradable PP/PHB composite material and preparation method Download PDFInfo
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- CN109679305A CN109679305A CN201811564991.0A CN201811564991A CN109679305A CN 109679305 A CN109679305 A CN 109679305A CN 201811564991 A CN201811564991 A CN 201811564991A CN 109679305 A CN109679305 A CN 109679305A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Health & Medical Sciences (AREA)
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Abstract
A kind of starch-based degradable PP/PHB composite material and preparation method, wherein, starch-based degradable PP/PHB composite material includes 20-40 parts of copolymerized type propene polymer resin in parts by weight, 30-40 parts of poly butyric ester resin, 20-30 parts of starch, 2-4 parts of toughening compatilizer, 1-2 parts of plasticizer, 0.5-1 parts of coupling agent, 0.1-0.5 parts of Photodegradation catalyst, 0.2-0.5 parts and lubrication dispersing agent 0.5-1 parts of antioxidant.The advantages that present invention has fast degradation, reduces environmental pollution, reduces poly butyric ester resin cost, and have excellent mechanical performances, processing performance and solvent resistance, it is widely used, it is practical.
Description
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of starch-based degradable PP/PHB composite material and
Preparation method.
Background technique
Polypropylene (PP) is one of five big general-purpose plastics, since the bent property of light, nontoxic, easy to process, anti-interference, price are low
The advantages that honest and clean, durable, is widely used in industry.But polypropylene (PP) also has the shortcomings that be difficult to degrade,
Discarded polypropylene plastics, which buries time for voluntarily degrading in the ground, to be had seriously polluted the environment up to centuries.
Poly butyric ester resin (PHB) is the bioabsorbable polymer material developed rapidly in recent years, is many micro- lifes
A kind of natural polymer biomaterial -- the intracellular polyester of object synthesis.Poly butyric ester resin (PHB) is that a kind of performance is excellent
Good environment friendly biological plastics, while there is good bio-compatible performance, the hot-working character of biodegradability and plastics,
Decomposition product can all biological utilisations.There are also preferable barrier properties for gases, hydrolytic stability for poly butyric ester resin (PHB)
And the advantages that low volatility, it can be produced in packaging material, jointing material, sprayed on material and dress material, utensil class material, electronics
It is widely used in the fields such as product, durable consumer goods, agricultural products, automated production, chemical mediator and solvent.But it is poly-
The shortcomings that butyric ester resin (PHB) is high production cost, and the market price is even more polyacrylic 4-6 times, greatly limits it
Using.
Current most of degradable polypropylene plastics are all natural by simply filling starch, fiber etc. in polypropylene
Degradable macromolecule improves, but these material degradation rates are slower, and tensile strength, elongation at break and impact strength are equal
It is very low, it is not able to satisfy certain requirements.
Therefore, it is necessary to be further improved.
Summary of the invention
The purpose of the present invention is intended to provide a kind of starch-based degradable PP/PHB composite material and preparation method, is a kind of
Green environmental protection degradable composite material reduces environmental pollution with fast degradation, reduces poly butyric ester resin cost
Advantage, and have good mechanical property, processing performance and solvent resistance, it is widely used, it is practical.
A kind of starch-based degradable PP/PHB composite material designed by this purpose, it is characterised in that: wrap in parts by weight
Include 20-40 parts of copolymerized type propene polymer resin, 30-40 parts of poly butyric ester resin, 20-30 parts of starch, toughening compatilizer 2-4
Part, 1-2 parts of plasticizer, 0.5-1 parts of coupling agent, 0.1-0.5 parts of Photodegradation catalyst, 0.2-0.5 parts of antioxidant and lubrication are dispersed
0.5-1 parts of agent.
The starch is one of tapioca, cornstarch, potato starch or multiple combinations.
The toughening compatilizer is one of POE-g-GMA, POE-g-MAH, EMA-GMA, ACR, EVA or a variety of groups
It closes.
The plasticizer is one of epoxidized soybean oil, glycerol, DOP or multiple combinations.
The coupling agent is one of silane coupling agent, titanate coupling agent, aluminate coupling agent or multiple combinations.
The photodegradable aid is one of cerium stearate, stearic acid caesium, ferric stearate and nano-titanium dioxide or a variety of
Combination.
The lubrication dispersing agent is one of EBS, PE wax or multiple combinations.
The antioxidant is one of phosphorous acid esters, polynary Hinered phenols or multiple combinations.
The preparation method of above-mentioned starch-based degradable PP/PHB composite material, it is characterised in that: the following steps are included:
Step 1, the weight of each material in precise claim 1；
Starch and coupling agent, lubrication dispersing agent are added in high-speed mixer and stir to get modified starch by step 2；
Step 3, by copolymerized type propene polymer resin, poly butyric ester resin, toughening compatilizer and plasticizer, according to suitable
Sequence is added sequentially to high-speed mixer stirring；Then the modified starch and Photodegradation catalyst and resist that step 2 obtains are added
Oxygen agent, then mixture is stirred to get with high-speed mixer；
Step 4, the mixture that step 3 is obtained are sent in double screw extruder, obtain environmental protection easily after squeezing out pelletizing
The starch base PP/PHB composite material of degradation.
In step 2, the speed of agitator of high-speed mixer is 600r/min, mixing time 5min；In step 3, high speed
The speed of agitator of the first task of blender is 300r/min, mixing time 3min, and the second task of high-speed mixer stirs
Mix revolving speed be 300r/min, mixing time 3min；In step 4, the double screw extruder is parallel dual-screw extruding machine,
The temperature established standards of each warm area of the double screw extruder are 170-200 DEG C.
The present invention has following effective effect:
1. a starch-based degradable PP/PHB composite material is exposed to soil surface, due to by illumination, in light degradation
Light degradation can quickly occur under the action of catalyst；After burying to underground, due to containing poly butyric ester resin (PHB)
Biodegrade can also quickly occur with starch component, not will receive the limitation of environmental factor, and greatly reduce plastics to ring
The pollution in border；
2. starch-based degradable PP/PHB composite material is by using polypropylene (PP), poly butyric ester resin
(PHB) and composite material is made in starch, greatly reduces the cost of poly butyric ester resin (PHB), and have good power
It is more extensive to learn performance, processing performance and good solvent resistance, application；
3. starch-based degradable PP/PHB composite material tensile strength, elongation at break and impact strength are high, have non-
Often big practicability.
Specific embodiment
The present invention will be further described below with reference to examples.
This starch-based degradable PP/PHB composite material includes copolymerized type propene polymer resin (PP) 20-40 in parts by weight
Part, 30-40 parts of poly butyric ester resin (PHB), 20-30 parts of starch, 2-4 parts of toughening compatilizer, 1-2 parts of plasticizer, coupling
0.5-1 parts of agent, 0.1-0.5 parts of Photodegradation catalyst, 0.2-0.5 parts and lubrication dispersing agent 0.5-1 parts of antioxidant.Wherein, poly- hydroxyl
Microbial degradation can not only occur for base butyrate resin, but also the tensile strength of composite material can be improved；By the way that copoly type is gathered
Allyl resin (PP), poly butyric ester resin (PHB) and starch are combined degradation material, when poly butyric ester resin
(PHB) and after starch generation microbial degradation, so that remaining copolymerized type propene polymer resin (PP) becomes very loose or becomes
At small tablet, specific surface area is increased, meanwhile, daylight, heat, oxygen etc. cause Photodegradation catalyst, lead to high polymer point
Subchain fracture, molecular weight and molecular weight；This starch-based degradable PP/PHB composite material can be used for making beverage bottle cap, disposable meal
The consumptive materials such as tool, toy, packaging, 3D printing.
Furtherly, starch is one of tapioca, cornstarch, potato starch or multiple combinations.Starch comes
Source is extensive, cheap, can not only increase the degradability of material, but also can substantially reduce the cost of material.
Furtherly, toughening compatilizer is one of POE-g-GMA, POE-g-MAH, EMA-GMA, ACR, EVA or more
Kind combination.In this toughening compatilizer, PE segment and PP resin compatible are good, and methyl propenoic acid glycidyl copolymerized therewith
Ester functional group or maleic anhydride can in poly butyric ester resin terminal hydroxy group and carboxyl end group chemically react so that
Both difficult compatible polymer of copolymerized type propene polymer resin (PP) and poly butyric ester resin (PHB) are combined together, and are obtained
The composite material compatibility arrived is good, and performance is stablized, while the elongation at break of composite material and impact strength also greatly improve.
Furtherly, plasticizer is one of epoxidized soybean oil, glycerol, DOP or multiple combinations.
Furtherly, coupling agent is one of silane coupling agent, titanate coupling agent, aluminate coupling agent or a variety of groups
It closes.
Furtherly, photodegradable aid be one of cerium stearate, stearic acid caesium, ferric stearate and nano-titanium dioxide or
Multiple combinations.Photodegradable aid can improve high molecular light degradation rate by absorbing luminous energy.
Furtherly, one of lubrication dispersing agent EBS, PE wax or multiple combinations.
Furtherly, antioxidant is one of phosphorous acid esters, polynary Hinered phenols or multiple combinations.
The preparation method of above-mentioned starch-based degradable PP/PHB composite material, comprising the following steps:
Step 1, the weight of each material in precise claim 1；
Starch and coupling agent, lubrication dispersing agent are added in high-speed mixer by step 2, and the stirring of high-speed mixer turns
Speed is 600r/min, mixing time is 5min work, stirs to get modified starch；
Step 3, by copolymerized type propene polymer resin, poly butyric ester resin, toughening compatilizer and plasticizer, according to suitable
Sequence is added sequentially to high-speed mixer stirring, and the speed of agitator of high-speed mixer is 300r/min, mixing time 3min；Then
Modified starch, Photodegradation catalyst and antioxidant that step 2 obtains are added, then is stirred with high-speed mixer, high-speed mixer
Speed of agitator be 300r/min, mixing time 3min, stir to get mixture；
Step 4, the mixture that step 3 is obtained are sent in double screw extruder, obtain environmental protection easily after squeezing out pelletizing
The starch base PP/PHB composite material of degradation；Wherein, double screw extruder is parallel dual-screw extruding machine, the double screw extruder
The temperature established standards of each warm area are 170-200 DEG C.
Here is the formula contrast table of different comparative examples from different embodiments:
Performance test methods:
1. the plastic pellet that extruding pelletization obtains is molded into national standard batten with injection molding machine, test tensile strength, fracture are stretched
Long rate and impact strength.
2. the plastic pellet that extruding pelletization obtains is molded into colour table with injection molding machine, colour table is then placed on soil respectively
It surface and buries to underground, allows its natural degradation, record natural degradation time.
Following table is the performance test results:
Above-mentioned is preferred embodiment of the invention, and basic principles and main features and the present invention of the invention have been shown and described
The advantages of.Those skilled in the art should be recognized that the present invention is not limited to the above embodiments, above embodiments and description
Described in merely illustrate the principles of the invention, without departing from the spirit and scope of the present invention the present invention also have it is various
Changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by institute
Attached the spirit and scope of the invention define.
Claims (10)
1. a kind of starch-based degradable PP/PHB composite material, it is characterised in that: in parts by weight include copolymerized type propene polymer tree
It is 20-40 parts of rouge, 30-40 parts of poly butyric ester resin, 20-30 parts of starch, 2-4 parts of toughening compatilizer, 1-2 parts of plasticizer, even
Agent 0.5-1 parts of connection, 0.1-0.5 parts of Photodegradation catalyst, 0.2-0.5 parts and lubrication dispersing agent 0.5-1 parts of antioxidant.
2. starch-based degradable PP/PHB composite material according to claim 1, it is characterised in that: the starch is para arrowroot
One of powder, cornstarch, potato starch or multiple combinations.
3. starch-based degradable PP/PHB composite material according to claim 2, it is characterised in that: the toughening compatilizer is
One of POE-g-GMA, POE-g-MAH, EMA-GMA, ACR, EVA or multiple combinations.
4. starch-based degradable PP/PHB composite material according to claim 3, it is characterised in that: the plasticizer is epoxy
One of soybean oil, glycerol, DOP or multiple combinations.
5. starch-based degradable PP/PHB composite material according to claim 4, it is characterised in that: the coupling agent is silane
One of coupling agent, titanate coupling agent, aluminate coupling agent or multiple combinations.
6. starch-based degradable PP/PHB composite material according to claim 5, it is characterised in that: the photodegradable aid is hard
One of resin acid cerium, stearic acid caesium, ferric stearate and nano-titanium dioxide or multiple combinations.
7. starch-based degradable PP/PHB composite material according to claim 6, it is characterised in that: the lubrication dispersing agent is
One of EBS, PE wax or multiple combinations.
8. starch-based degradable PP/PHB composite material according to claim 7, it is characterised in that: the antioxidant is phosphorous
One of esters of gallic acid, polynary Hinered phenols or multiple combinations.
9. the preparation method of starch-based degradable PP/PHB composite material as described in claim any one of 1-8, it is characterised in that:
The following steps are included:
Step 1, the weight of each material in precise claim 1；
Starch and coupling agent, lubrication dispersing agent are added in high-speed mixer and stir to get modified starch by step 2；
Step 3, by copolymerized type propene polymer resin, poly butyric ester resin, toughening compatilizer and plasticizer, in sequence according to
It is secondary to be added to high-speed mixer stirring；Then the modified starch and Photodegradation catalyst and antioxidant that step 2 obtains are added,
Mixture is stirred to get with high-speed mixer again；
Step 4, the mixture that step 3 is obtained are sent in double screw extruder, and it is degradable to obtain environmental protection after extrusion pelletizing
Starch base PP/PHB composite material.
10. the preparation method of starch-based degradable PP/PHB composite material according to claim 9, it is characterised in that: step
In two, the speed of agitator of high-speed mixer is 600r/min, mixing time 5min；In step 3, high-speed mixer is for the first time
The speed of agitator of work is 300r/min, mixing time 3min, and the speed of agitator of the second task of high-speed mixer is 300r/
Min, mixing time 3min；In step 4, the double screw extruder is parallel dual-screw extruding machine, the double screw extruder
The temperature established standards of each warm area are 170-200 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138722A (en) * | 2020-01-14 | 2020-05-12 | 浙江绿禾生态科技股份有限公司 | Starch-based degradable material and preparation method thereof |
| CN111909457A (en) * | 2020-08-24 | 2020-11-10 | 苏州润佳高分子材料有限公司 | Degradable soft touch polypropylene composite material |
| CN112920576A (en) * | 2021-01-29 | 2021-06-08 | 赵敏 | Disposable degradable lunch box and preparation method thereof |
| CN114395190A (en) * | 2022-01-26 | 2022-04-26 | 岳阳兴长石化股份有限公司 | Photodegradable polypropylene material and preparation method thereof |
| CN116003913A (en) * | 2023-01-31 | 2023-04-25 | 上海琦识医疗科技有限公司 | Precise medical catheter and preparation method thereof |
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Application publication date: 20190426 |