CN107501725A - Degradation material and preparation method thereof - Google Patents
Degradation material and preparation method thereof Download PDFInfo
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- CN107501725A CN107501725A CN201710722010.XA CN201710722010A CN107501725A CN 107501725 A CN107501725 A CN 107501725A CN 201710722010 A CN201710722010 A CN 201710722010A CN 107501725 A CN107501725 A CN 107501725A
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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
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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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Abstract
The invention discloses a kind of degradation material and preparation method thereof, the present invention is participated in using dihydric alcohol and binary acid and the polymerisation of PLA, improve alcoholic extract hydroxyl group in PLA, carboxyl, the quantity of ester group isoreactivity group, increase degradable basic point, simultaneously, titanium dioxide, octyl ferrocene, the addition of polypropylene and lubricant, the overall mechanical performance of material is improved again, in above-mentioned preparation method, by plasma-induced, add the activity of degradable basic point, improve the degradable efficiency of material, further expressing technique improves the mechanical performance of material.Meanwhile this method is simple, cost of material is low, has preferable application value.
Description
Technical field
The present invention relates to degradation material, in particular it relates to degradation material and preparation method thereof.
Background technology
Plastics are a kind of cheap and good-quality materials, however as widely using for polybag and plastics thin article, Ren Menfa
The inherent life-span of existing plastics thin article is considerably longer than its service life.In plastics durability, make it in urban solid garbage
Ratio rise, the plastics thin article (such as polybag, plastics package, disposable plastic articles for use, mulch film) arbitrarily abandoned be even more
Environment is polluted for a long time, is increasingly becoming white pollution, turns into 21st century puzzlement human survival and the great difficulty of development
One of topic.
In order to reduce white pollution, preserve the ecological environment, the research of biodegradable plastics, exploitation and more next using seeming
It is more important and urgent.But biodegradable plastics tool still has the following disadvantages：(1) most of is PLA base material, can biology
The high expensive of degradative plastics；(2) physical and mechanical property of biodegradable plastics is poor, its tensile strength, elongation at break, top
Broken and tearing strength etc. does not all reach the requirement of application, influences its application.
The mechanical performance of degradation material how is improved, while is reduced with the production cost of degradation material, is degradable
Material is promoted, and the cheap, plastic products of lightweight, high specific strength, health can be continuing with by making us class, and and can avoids white
The key of pollution.
The content of the invention
The purpose of the present invention is degradation material and preparation method thereof, the material using polypropylene as matrix, by PLA and
Binary acid and dihydric alcohol composition degradation material combine, there is more degradable basic point, on the other hand, polypropylene with
Other components are combined, and are improved the overall mechanical performance of material, have been expanded degradation material application.
To achieve these goals, the invention provides a kind of preparation method of degradation material, the preparation method bag
Include following steps：(1) PLA, dihydric alcohol are subjected to prepolymerization, then add binary acid and butyl stannonic acid, polymerize；(2)
Gained mixture in step (1) is carried out plasma-induced；(3) mixture after being handled in step (2) is added to mixer
In, titanium dioxide, octyl ferrocene, polypropylene and lubricant are added, is further continued for stirring；(4) by after step (3) processing
Mixture add double screw extruder in carry out extruding pelletization.
The present invention also provides a kind of degradation material prepared according to previously described preparation method.
In the above-mentioned technical solutions, the present invention improves using dihydric alcohol and the polymerisation of binary acid participation and PLA
Alcoholic extract hydroxyl group, carboxyl, the quantity of ester group isoreactivity group in PLA, increase degradable basic point, meanwhile, titanium dioxide,
The addition of octyl ferrocene, polypropylene and lubricant, the overall mechanical performance of material is improved again, in above-mentioned preparation technology
In, by plasma-induced, the activity of degradable basic point is added, improves the degradable efficiency of material, further extrusion
Technique improves the mechanical performance of material.Meanwhile this method is simple, cost of material is low, has preferable application value.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of preparation method of degradation material, the preparation method comprises the following steps：(1) will be poly-
Lactic acid, dihydric alcohol carry out prepolymerization, then add binary acid and butyl stannonic acid, are polymerize；(2) it is gained in step (1) is mixed
Compound carries out plasma-induced；(3) mixture after handling in step (2) is added in mixer, adds titanium dioxide, just
Octyl ferrocene, polypropylene and lubricant, it is further continued for stirring；(4) mixture after step (3) processing is added into twin-screw
Extruding pelletization is carried out in extruder.
In the above-mentioned technical solutions, the present invention improves using dihydric alcohol and the polymerisation of binary acid participation and PLA
Alcoholic extract hydroxyl group, carboxyl, the quantity of ester group isoreactivity group in PLA, increase degradable basic point, meanwhile, titanium dioxide,
The addition of octyl ferrocene, polypropylene and lubricant, the overall mechanical performance of material is improved again, in above-mentioned preparation technology
In, by plasma-induced, the activity of degradable basic point is added, improves the degradable efficiency of material, further extrusion
Technique improves the mechanical performance of material.Meanwhile this method is simple, cost of material is low, has preferable application value.
Certainly, in the above-mentioned technical solutions, the amount of the addition of each component can be adjusted in relative broad range, in order to ensure
Material has preferable mechanical performance, while has good degradability, furthermore it is preferred that in parts by weight, PLA 5-
15 parts, dihydric alcohol 4-6 parts, binary acid 5-8 parts, butyl stannonic acid 2-3 parts, titanium dioxide 0.5-0.8 parts, octyl ferrocene 0.2-
0.5 part, polypropylene 30-40 parts, lubricant 3-5 parts.So, base material is mainly polypropylene in degradation material, and PLA
The degradation material of the more conventional PLA base material of amount of addition is low, and still, the degradability of material is not decreased obviously, separately
The mechanical performance of one square bar material disclosure satisfy that requirement of the daily plastic products to the mechanical property of materials.
In the above-mentioned technical solutions, the number-average molecular weight of PLA can be adjusted in relative broad range, poly- in order to improve
Lactic acid and binary acid polymerize basic point quantity with dihydric alcohol, it is preferable that the relatively low PLA of selective polymerization degree, it is more excellent in the present invention
In the embodiment of choosing, the number-average molecular weight of the PLA of PLA is 4000-12000.
Moreover, dihydric alcohol can be selected in relative broad range, excellent in order to improve polymerization basic point quantity in polymer
Selection of land, dihydric alcohol are the one or more in ethylene glycol, BDO, 1,2-PD and 1,3-PD.
Binary acid can be selected in relative broad range, in order to improve polymerization basic point quantity in polymer, it is preferable that binary
Acid is the one or more in succinic acid, glutaric acid and adipic acid.
For polyacrylic molecular weight, those skilled in the art can be selected in relative broad range, in order to improve poly- third
The syncretizing effect of alkene and PLA, it is preferable that the relatively low polypropylene of selective polymerization degree, in the preferred embodiment of the present invention
In, polyacrylic number-average molecular weight is 10000-15000.
In addition, lubricant can select in relative broad range, plastic products conventional lubricantss may be selected, in order to improve material
Syncretizing effect, while the toughness of reinforcing material, it is preferable that lubricant is stearic acid, hydroxy stearic acid, n-butyl stearate, list
Glyceryl stearate, methyl hydroxystearate, soybean oil, peanut oil, corn oil, rice bran oil, rapeseed oil, cottonseed oil, sunflower seeds
One or more in oil and camellia seed oil.
For plasma-induced condition, those skilled in the art can be selected in relative broad range, in order to improve base
The quantity of the polymerization activity basic point on material surface, it is preferable that plasma-induced condition includes:The mixture that step (1) is obtained
Insert on the bottom electrode medium of plasma device, in voltage 115-125kV, electric current 24-26mA, gap is 4-6mm operation
Under the conditions of irradiate.So, using initial stage, material is because surface aggregate is fine and close, and mechanical strength is higher, after use, due to positioned at material
Expect the fracture of the chemical bond of the polymerization activity basic point on surface, improve the degradation property of material.
Certainly, in above-mentioned embodiment, plasma-induced irradiation time can be adjusted in relative broad range,
In order to improve the quantity of the polymerization activity basic point of substrate surface, material premature breakdown is on the other hand prevented, at one of the invention more
In preferred embodiment, plasma-induced condition is 1.5-3min including irradiation time.
Moreover, can be adjusted for prepolymerized condition in step (1), those skilled in the art in relative broad range
It is whole, in order to improve prepolymerization efficiency, improve the quantity of active basic point in PLA, it is preferable that prepolymerized condition includes：In
70-90 DEG C in 100-120rpm prepolymerizations.
Wherein, prepolymerization time can be adjusted in relative broad range, in preferred embodiment of the invention, preferably
Ground, prepolymerization 15-25min.
For the condition of polymerization in step (1), those skilled in the art can be adjusted in relative broad range, in order to improve
Prepolymerization efficiency, improve the quantity of active basic point in PLA, it is preferable that prepolymerized condition includes：By temperature adjust to
180-220 DEG C polymerize in 240-320rpm.
Wherein, polymerization time can be adjusted in relative broad range, in preferred embodiment of the invention, preferably
Ground, it polymerize 20-30min.
Stirring condition in step (3) can be adjusted in relative broad range, in order to improve the syncretizing effect of material, preferably
Ground, the mixture after being handled in step (2) is added in mixer, adds titanium dioxide, octyl ferrocene and polypropylene,
Stir at a certain temperature, then cooling adds lubricant, is stirred for discharging after being well mixed.In this paper preferred embodiments
In, in order to improve the syncretizing effect of material, it is preferable that the mixture after being handled in step (2) is added in mixer, added
Titanium dioxide, octyl ferrocene and polypropylene, stir in the 160-180 DEG C of speed with 200-240rpm, be then cooled to
Lubricant is added at 130-140 DEG C, is stirred for discharging after being well mixed.
Certainly, the time of mixing can be adjusted in relative broad range, in order to improve the syncretizing effect of material, preferably
Ground, titanium dioxide, octyl ferrocene and polypropylene stirring 20-30min are added, 10-20min is stirred for after adding lubricant.
For the extrusion condition in step (4), those skilled in the art can be adjusted in relative broad range, in order that thing
Material is well mixed, while improves the mechanical performance of material, it is preferable that the temperature of each section of double screw extruder is 180- during extrusion
210℃。
Certainly, screw speed can be adjusted in relative broad range during extrusion, in order that material is well mixed, be improved simultaneously
The mechanical performance of material, it is preferable that screw speed 250-280rpm.
In addition, blanking velocity can be adjusted in relative broad range during extrusion, in order to improve blanking efficiency, it is preferable that under
Material speed is 30-40rpm.
The present invention also provides a kind of degradation material prepared according to previously described preparation method.
In the above-mentioned technical solutions, the present invention improves using dihydric alcohol and the polymerisation of binary acid participation and PLA
Alcoholic extract hydroxyl group, carboxyl, the quantity of ester group isoreactivity group in PLA, increase degradable basic point, meanwhile, titanium dioxide,
The addition of octyl ferrocene, polypropylene and lubricant, the overall mechanical performance of material is improved again.Meanwhile cost of material is low,
With preferable application value.
The present invention will be described in detail by way of examples below.The number-average molecular weight of PLA is 8000；Polypropylene
Number-average molecular weight be 12000；Other are conventional commercial products.
Embodiment 1
The preparation method of degradation material, comprises the following steps：
(1) by 5 parts of PLA, 4 parts of 1,2-PD in 100rpm prepolymerization 15min, then adds succinic acid 5 in 70 DEG C
2 parts of part and butyl stannonic acid, temperature is adjusted to 180 DEG C and polymerize 20min in 240rpm；
(2) mixture obtained in step (1) is inserted on the bottom electrode medium of plasma device, in voltage 115kV,
Electric current 24mA, gap are to irradiate 1.5min under 4mm operating condition；
(3) mixture after being handled in step (2) is added in mixer, adds 0.5 part of titanium dioxide, n-octyl two
Luxuriant 0.2 part of iron, 30 parts of polypropylene stir 20min in 160 DEG C of speed with 200rpm, lubrication are added when being then cooled to 130 DEG C
3 parts of stirring 10min of agent, discharge after well mixed；
(4) mixture after step (3) processing is carried out in double screw extruder in 180 DEG C of screw speeds for 250rpm
Extrusion, blanking velocity 30rpm, it is granulated.
Embodiment 2
The preparation method of degradation material, comprises the following steps：
(1) by 15 parts of PLA, 6 parts of 1,2-PD in 120rpm prepolymerization 25min, then adds succinic acid in 90 DEG C
8 parts and 3 parts of butyl stannonic acid, temperature is adjusted to 220 DEG C in 320rpm polyase 13s 0min；
(2) mixture that step (1) obtains is inserted on the bottom electrode medium of plasma device, in voltage 125kV, electricity
26mA is flowed, gap is to irradiate 3min under 6mm operating condition；
(3) mixture after being handled in step (2) is added in mixer, adds 0.8 part of titanium dioxide, n-octyl two
Luxuriant 0.5 part of iron, 40 parts of polypropylene stir 30min in 180 DEG C of speed with 240rpm, lubrication are added when being then cooled to 140 DEG C
5 parts of stirring 20min of agent, discharge after well mixed；
(4) mixture after step (3) processing is carried out in double screw extruder in 210 DEG C of screw speeds for 280rpm
Extrusion, blanking velocity 40rpm, it is granulated.
Embodiment 3
The preparation method of degradation material, comprises the following steps：
(1) by 10 parts of PLA, 5 parts of 1,2-PD in 110rpm prepolymerization 20min, then adds succinic acid in 80 DEG C
6.5 parts and 2.5 parts of butyl stannonic acid, temperature is adjusted to 200 DEG C and polymerize 25min in 280rpm；
(2) mixture that step (2) obtains is inserted on the bottom electrode medium of plasma device, in voltage 120kV, electricity
25mA is flowed, gap is to irradiate 2.25min under 5mm operating condition；
(3) mixture after being handled in step (2) is added in mixer, adds 0.65 part of titanium dioxide, n-octyl
0.35 part of ferrocene, 35 parts of polypropylene stir 25min in 170 DEG C of speed with 220rpm, profit are added when being then cooled to 135 DEG C
4 parts of stirring 15min of lubrication prescription, discharge after well mixed；
(4) mixture after step (3) processing is carried out in double screw extruder in 195 DEG C of screw speeds for 265rpm
Extrusion, blanking velocity 35rpm, it is granulated.
Comparative example 1
According to embodiment 3 method prepare degradation material, unlike, be added without in step (1) 1,2-PD and
Succinic acid, step (1) is adjusted to：By PLA, 10 parts are kneaded 20min in 80 DEG C in 110rpm, then add butyl stannonic acid
2.5 parts, temperature is adjusted to 200 DEG C and is kneaded 25min in 280rpm, other conditions are same as Example 3.
Comparative example 2
Degradation material is prepared according to the method for embodiment 3, unlike, step is added without polypropylene in (3), other
Part is same as Example 3.
Comparative example 3
Degradation material is prepared according to the method for embodiment 3, unlike, omit step (2).
Comparative example 4
Degradation material is prepared according to the method for embodiment 3, unlike, polypropylene is added without in step (3), and will step
Suddenly the amount of the addition of PLA is adjusted to 45 parts in (1), and other conditions are in the same manner as in Example 3.
Detect example 1
Degradation material made from embodiment 1-3 and comparative example 1-4 is carried out according to national standard GB/T 12914-2008 method
Tensile strength and elongation at break, concrete outcome are shown in Table 1.
Detect example 2
The obtained degradation material of embodiment 1-3 and comparative example 1-4 is made to 100 × 50 × 5 (unit, mm) sample,
It is immersed in the phosphate buffer that pH is 5.5, places 60 days.The weight of sample before and after testing is weighed, calculates degradation rate, specific knot
Fruit is shown in Table 1.
Weight × 100% of sample before degradation rate=(weight of sample after weight-experiment of sample before experiment)/experiment
Table 1
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of degradation material, it is characterised in that the preparation method comprises the following steps：
(1) PLA, dihydric alcohol are subjected to prepolymerization, then add binary acid and butyl stannonic acid, polymerize；
(2) gained mixture in step (1) is carried out plasma-induced；
(3) mixture after being handled in step (2) is added in mixer, adds titanium dioxide, octyl ferrocene, poly- third
Alkene and lubricant, it is further continued for stirring；
(4) mixture after step (3) processing is added in double screw extruder and carries out extruding pelletization.
2. preparation method according to claim 1, wherein, in parts by weight, PLA 5-15 parts, dihydric alcohol 4-6 parts, two
The sour 5-8 parts of member, butyl stannonic acid 2-3 parts, titanium dioxide 0.5-0.8 parts, octyl ferrocene 0.2-0.5 parts, polypropylene 30-40
Part, lubricant 3-5 parts.
3. the preparation method according to right wants 1 or 2, wherein, plasma-induced condition includes:Step (1) is obtained
Mixture is inserted on the bottom electrode medium of plasma device, in voltage 115-125kV, electric current 24-26mA, gap 4-6mm
Operating condition under bar irradiation 1.5-3min.
4. the preparation method according to right wants 1 or 2, wherein, prepolymerized condition includes：In 70-90 DEG C in 100-
120rpm prepolymerizations 15-25min.
5. the preparation method according to right wants 1 or 2, wherein, the condition of polymerisation includes：Temperature is adjusted to 180-
220 DEG C polymerize in 240-320rpm；
And/or polymerization 20-30min.
6. the preparation method according to right wants 1 or 2, wherein, the stirring condition in step (3) includes：It will locate in step (2)
Mixture after reason is added in mixer, adds titanium dioxide, octyl ferrocene and polypropylene, in 160-180 DEG C with
200-240rpm speed stirring, lubricant is added when being then cooled to 130-140 DEG C, is stirred for discharging after being well mixed；
And/or titanium dioxide, octyl ferrocene and polypropylene stirring 20-30min are added, add mixing time after lubricant
For 10-20min.
7. the preparation method according to right wants 1 or 2, wherein, extrusion condition includes in step (4)：Twin-screw squeezes during extrusion
The temperature for going out each section of machine is 180-210 DEG C；
And/or screw speed 250-280rpm；
And/or blanking velocity 30-40rpm.
8. the preparation method according to right wants 1 or 2, wherein, the number-average molecular weight of PLA is 4000-12000；
And/or dihydric alcohol is the one or more in ethylene glycol, BDO, 1,2-PD and 1,3-PD；
And/or binary acid is the one or more in succinic acid, glutaric acid and adipic acid.
9. the preparation method according to right wants 1 or 2, wherein, polyacrylic number-average molecular weight is 10000-15000；
And/or lubricant is stearic acid, hydroxy stearic acid, n-butyl stearate, single stearic acid glycerine lipoprotein, hydroxy stearic acid first
One kind or more in ester, soybean oil, peanut oil, corn oil, rice bran oil, rapeseed oil, cottonseed oil, sunflower oil and camellia seed oil
Kind.
A kind of 10. degradation material prepared by preparation method according to any one of claim 1-9.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838855A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Biodegradable composite, disposable product and preparation method thereof |
| CN106987045A (en) * | 2017-05-18 | 2017-07-28 | 聂超 | It is a kind of to trigger environmental protection macromolecule new material of multiple degrading and preparation method thereof |
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- 2017-08-22 CN CN201710722010.XA patent/CN107501725A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838855A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Biodegradable composite, disposable product and preparation method thereof |
| CN106987045A (en) * | 2017-05-18 | 2017-07-28 | 聂超 | It is a kind of to trigger environmental protection macromolecule new material of multiple degrading and preparation method thereof |
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Application publication date: 20171222 |