CN103834086B - A kind of efficiently controllable light oxidation-biodegradable plastic film and preparation method thereof - Google Patents
A kind of efficiently controllable light oxidation-biodegradable plastic film and preparation method thereof Download PDFInfo
- Publication number
- CN103834086B CN103834086B CN201410104064.6A CN201410104064A CN103834086B CN 103834086 B CN103834086 B CN 103834086B CN 201410104064 A CN201410104064 A CN 201410104064A CN 103834086 B CN103834086 B CN 103834086B
- Authority
- CN
- China
- Prior art keywords
- plastic film
- film
- biodegradable plastic
- controllable light
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The open a kind of efficiently controllable light oxidized-biodegradable plastic film and preparation method thereof of the present invention, described plastic sheeting includes the component of following percetage by weight: polymeric substrate 88 ~ 99%, hydrophilic modifying agent 0.5 ~ 5%, nano titanium oxide 0.5 ~ 5%, light stabilizer 0.1 ~ 2%.Preparation method of the present invention is melt blending, extrusion-blown modling.Plastic sheeting of the present invention has hydrophily, degradation efficiency is high, photocatalytic activity is high, light abstraction width is wide, degradation time is short, the features such as stationary phase is controlled, applied widely, production technology simple, raw material is easy to get, it is suitable for the fields such as packaging, agricultural film, polybag, and can degrade under natural environment after discarded.
Description
Technical field
The invention belongs to degradable plastic film technical field, be specifically related to a kind of efficiently controllable light oxidation-biodegradable
Plastic sheeting and preparation method thereof.
Background technology
Plastic sheeting consumption is very big, is widely used in the disposable product such as packaging material, agricultural mulching, but with after be difficult to
Reclaim, discard in nature the most degradable, ecological environment is caused the biggest harm.The tightest along with " white pollution "
Weight, people are constantly looking for the method that effectively solves problem, and through continuous effort, various degradative plastics are come out one after another.Currently,
Maximally efficient, economic degradation technique should be oxidation-biodegradable.Oxidation-biodegradable includes two stages: the first stage
Oxide breaks, second stage is biodegradable.And, the speed of biodegradation process depends on the oxide breaks that pro-oxidant induces
Stage, these pro-oxidants added can promote the oxygen generation oxidation reaction in polymer and air under the effect of light and heat and
Make macromolecular chain rupture, make relative molecular weight drop to from hundreds of thousands thousand of, after molecular weight is little to a certain extent, it will by certainly
So bacterium and the microorganism on boundary absorbs decomposition as hydrocarbon source, is finally degraded into carbon dioxide, water and humus.
Nano-TiO2There is good photocatalysis performance, low price, non-secondary pollution, be incorporated in depolymerization and take
Obtained certain achievement.But the hydrophobicity of conventional polyolefin/TiO2 plastic sheeting is poor, TiO2With H2The light-catalyzed reaction of O is main
Only occurring in the film surface with humidity, light-catalyzed reaction is difficult to occur in the inside of plastics, and degraded is slowly.
At present, plastic film applications scope augmentation day by day and the enhancing of environmental consciousness, degradation plastic film has wide city
Field prospect.But directly and plastic blend prepares film to there is many technical problems urgently to be resolved hurrily, such as bio-based materials simultaneously,
Cost is high, degraded not exclusively, the problem such as degrade uncontrollable；Using multi-layer compound film to prepare degradation plastic film, technique is multiple
Miscellaneous, layer does not mates with interlayer, and appearance cannot be the most compound, and degraded is not exclusively.Prior art is most by adding substantial amounts of biology
Material, reaches high degradation rate, but the mechanical performance of film cannot ensure, remaining plastics are difficult to continue degraded, do not drop
The fragment solved still can cause environmental pollution.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, it is provided that a kind of efficiently controllable light oxidation-biological fall
Solve plastic sheeting, this plastic sheeting have the preferable mechanical performance of common plastics film, processing characteristics, higher tearing strength,
Elongation at break and hot strength, simultaneously the plastic sheeting of the present invention can photooxidation-biodegradable, degraded thoroughly, will not be to ring
Border produces harm, can realize being controlled the degradation rate of plastic sheeting by the adjustment of each component ratio.
It is a further object to provide the preparation side of above-mentioned efficient controllable light oxidation-biodegradable plastic film
Method.
The above-mentioned purpose of the present invention is achieved by following technical solution:
A kind of efficiently controllable light oxidation-biodegradable plastic film, including the component of following percetage by weight: polymer base
Material 88～98.9%, hydrophilic modifying agent 0.5～5%, nano titanium oxide 0.5～5%, light stabilizer 0.1～2%；Described polymer
Base material is low density polyethylene (LDPE) (LDPE), LLDPE (LLDPE), polypropylene (PP), polyvinyl chloride (PVC), gathers
One or more in the polyolefin such as styrene (PS), molecular weight is 10K～60K；Described hydrophilic modifying agent is polyethylene glycol
(PEG) one or more, in the hydrophilic polymer such as polyoxyethylene (PEO), polyvinyl alcohol (PVA), molecular weight is 4K～500K.
In order to overcome polymeric substrate degraded not exclusively, the uncontrollable defect of degradation speed, the collaborative use of the present invention is hydrophilic
Modifying agent, improves the hydrophily of film, and then promotes TiO2Light-catalyzed reaction in film, the additionally addition of hydrophilic modifying agent
Be conducive to the microorganism attachment to film, improve the palliating degradation degree of film further.But the most all of hydrophilic modifying agent is all
Can be suitable for, reason is the poor compatibility of major part hydrophilic modifying agent and Inventive polymers base material, both can not melt blending, enter
And plastic sheeting of good performance can not be prepared.Being tested by great many of experiments, the present invention just show that described hydrophilic modifying agent is
PEG, PEO or PVA are good with polymeric matrix compatible of the present invention, can absorb the moisture in air simultaneously, improve film parent
Aqueous, make TiO2It is prone to contact wetting, promotes photooxidative degradation reaction.
Also being found by experiment, the molecular weight of hydrophilic modifying agent needs to control within the specific limits, if molecular weight is too low,
Hydrophilic effect is inconspicuous, and the absorption to moisture is limited；Molecular weight is excessive, and hydrophilic modifying agent is compatible with Inventive polymers base material
Property decline, easy crystal aggregation, cause TiO2Degradation efficiency reduce on the contrary, the hydrophilic modifying agent of the object of the invention can be realized
Molecular weight is 4K～500K.
Preferably, the molecular weight of described hydrophilic modifying agent is that 10K～50K, degradation of plastic film and mechanical performance are more excellent.?
Preferably, the molecular weight of described hydrophilic modifying agent is 10K, and degradation of plastic film and mechanical performance are optimum.
As a kind of preferred version, described hydrophilic modifying agent is one or both of PEG or PEO, PEG or PEO and this
Bright described polymeric matrix compatible is optimal, is more beneficial for melt blending and masking, and all kinds of performance of prepared plastic sheeting is more excellent,
Such as mechanical performance, hydrophilicity, degradation property etc..Most preferably, described hydrophilic modifying agent is PEG, and photooxidation-biodegradable is moulded
The best performances such as the degraded of material film and machinery.The synthetic method of PEG with PEO of the present invention is the most different with end group etc.,
Say on stricti jurise and be not belonging to same material, although molecular backbone structure is the same, but end group is different with molecular weight, both of which
For the conventional commercially available common agents in this area.
Hydrophilic modifying agent of the present invention need to control within the specific limits, if addition is very few, film hydrophilic performance increases
Add inconspicuous, cause plastic sheeting can not complete biodegradable, but the most not addition is the bigger the better, reason is hydrophilic modifying
Agent addition is too much, polymeric substrate can be caused to increase with hydrophilic modifying agent melt blending melt viscosity, film forming in film-forming process
Difficulty, is difficult to processing, and degradation property improves inconspicuous, and cost is high, and plastic sheeting product does not meets actual operation requirements, because of
And the addition controlling hydrophilic modifying agent could realize the object of the invention 0.5%～5%.
Polymeric substrate of the present invention selects one or more in LDPE, LLDPE, PP, PVC or PS, it is therefore an objective to for
Meeting the normal usage of this area plastic sheeting and for specific use such as preservative film, packaging film and heat shrink films etc., number is all
Molecular weight 10K～60K.As a kind of preferred version, described polymeric substrate is LDPE, and number-average molecular weight is 20K～50K, system
The plastic sheeting product tensile property and the degradation property that obtain are more excellent.
The present invention, using nano titanium oxide as photochemical catalyst, causes light-catalyzed reaction degradative plastics thin under illumination condition
Film, the particle diameter of nano titanium oxide is the least, and specific surface area is the biggest, and catalytic performance is higher, but particle diameter is the least, and preparation difficulty is the biggest,
Cost is the highest；Titanium dioxide has three kinds of crystal formations, anatase, rutile and brockite, and research shows that anatase photocatalysis efficiency is
Height, so as a kind of preferred version, the particle diameter of described nano titanium oxide is 10～50 nanometers, and crystal formation is based on anatase.
The effect of light stabilizer of the present invention is the degradation speed that collaborative hydrophilic modifying agent and photochemical catalyst control plastic sheeting,
As a kind of preferred version, described light stabilizer is that one or more of hindered amine light stabilizer (HALS) compound, HALS with
It is strong 2～4 times that effect compared by tradition light stabilizer, and low toxicity or nontoxic can meet the requirement of film article material.The present invention can select
By the commercially available kind of domestic hindered amine light stabilizer (HALS), including light stabilizer 622, light stabilizer 770, light stabilizer
783, one or more in light stabilizer 791, light stabilizer 944 or light stabilizer 3853.The present invention is found through experiments,
In the middle of light stabilizer commonly used in the art, described light stabilizer uses HALS to be more beneficial for the control of photodegradable speed of the present invention,
Reason is probably HALS can capture under optically catalytic TiO 2 the living radical generated in high molecular weight reactive, thus suppresses light
The process of oxidation, reaches light and stablizes purpose, and other kinds of light stabilizer commonly used in the art such as photomask agent, ultraviolet are inhaled
Receive agent and quencher effect is all inferior to HALS.
The preparation method of the present invention efficient controllable light oxidation-biodegradable plastic film, concretely comprises the following steps above-mentioned specific
The component mixing of percentage by weight, melt blending, the master batch after melting mixing, prepare plastic sheeting through blowing.
The temperature of described melt blending is 160～210 DEG C.
The thickness of described plastic sheeting can adjust the most accordingly, as a kind of preferred version, described plastics
The thickness of film is 10～150 microns, and applicable situation is the widest.As one more preferably scheme, the thickness of described plastic sheeting is
80 microns.
Efficient controllable light oxidation-biodegradable plastic film of the present invention uses hydrophilic modifying agent and the light of special ratios
Stabilizer, synergic nano titanium dioxide prepares plastic sheeting.Ensure plastic sheeting have can meet actually used required
On the premise of associated mechanical intensity and mechanical strength, the use of hydrophilic modifying agent improves the hydrophily of plastic sheeting, can promote
Enter the photocatalytic degradation of nano titanium oxide, improve the palliating degradation degree of plastic sheeting；The use of light stabilizer simultaneously can realize
The control of plastic sheeting biodegradation rate, it is ensured that plastic sheeting can extend plastic sheeting on the premise of complete biodegradable
Service life.
The consumption of light stabilizer of the present invention is also required to control in specific scope, if consumption is very few, it is impossible to effectively
Play a role, cause the plastic sheeting in use fast degradation because of illumination, lose use value；If consumption is too much,
Degradation of plastic film speed can be caused the slowest, long-time discarded the most undegraded still pollute the environment completely, the light of excess is steady in addition
Determine agent and also can reduce the mechanical performance of plastic sheeting, increase difficulty of processing, improve cost.
The consumption of nano titanium oxide of the present invention is also required to control in specific scope, if consumption is very few, and plastics
Film product photocatalysis is inconspicuous, it is difficult to complete biodegradable；If consumption is too much, high cost, the nanometer two of excess
Titanium oxide does not make full use of, and causes waste, processing characteristics to affect, and reason is probably nano-TiO2Concentration reaches certain
Time, particle is easily reunited, and affects degradation effect, and utilization rate reduces.Additionally, the consumption of nano titanium oxide also needs to according to hydrophilic
Modifying agent and the consumption of light stabilizer and adjust accordingly, coordinate, the control to degradation of plastic film speed could be realized.The present invention
The consumption of described nano titanium oxide is defined to 0.5～5%, can realize induction period and the fall of photooxidation-biodegradable plastic film
Solve the most controlled of speed, practical.
Being tested by great many of experiments, the used in amounts of polymeric substrate of the present invention controls 88～99% guarantee institute
The performances such as the machinery of the plastic sheeting prepared, processing and mechanics can meet daily film and use demand.The present invention passes through
Control hydrophilic modifying agent, nano titanium oxide and the consumption of each component of light stabilizer, the efficient controllable light prepared oxidation-raw
The induction period of thing degradation plastic film is 1 month to 4 years, and it is 6 months to 3 years that brittle phase and degradable phase are greatly shortened
, it is adapted to the needs of the film product of different purposes.
Compared with prior art, there is advantages that
(1) the efficient controllable light oxidation-biodegradable plastic film of the present invention, by increasing film hydrophilic, degraded effect
Rate improves 30%, and its degradable film effect is notable, and degraded weight-loss ratio can reach 40～85%, i.e. material can be degraded to substantially without strong
The fractionlet of degree, even powder；Oxidative degradation rear film has good biological degradability, the diaphragm seal compost after illumination 300h
Within 45 days, biodegradable mineralization rate is up to 2.0～3.2%.
(2) the efficient controllable light oxidation-biodegradable plastic film of the present invention, induction period be 1 month by 4 years, crisp
It is 6 months to 3 years that change phase and degradable phase are greatly shortened, and is adapted to the needs of the film product of different purposes, as
The fields such as packaging and polybag, are particularly well-suited to controlled degradation film for agricultural use.
(3) efficient controllable light oxidation-biodegradable plastic film that the present invention provides, the inexpensive environmental protection of its raw material, prepare work
Skill is simple and has light degradation, biodegradable, photocatalysis and the several functions such as dust-proof；This hydrophilic modification method, titanium dioxide with
The composite modified technology of the resins such as polyolefin, extends to other plastics-production applications.
Accompanying drawing explanation
Fig. 1 is the hydrophilic controllable light oxidation-biodegradable plastic film ultraviolet lighting being not added with light stabilizer of the present invention
Under weight-loss ratio curve map, a-h corresponding to comparative example 1,2, embodiment 14-19.
Fig. 2 is the hydrophilic controllable light oxidation-biodegradable plastic film light adding different content light stabilizer of the present invention
Weight-loss ratio curve map under according to, a-e corresponds to embodiment 1-5.
Fig. 3 is the hydrophilic controllable light oxidation-biodegradable plastic film of present invention hot strength under ultraviolet lighting, a-
I corresponding to comparative example 1,2, embodiment 14-19, embodiment 2.
Fig. 4 is the hydrophilic controllable light oxidation-biodegradable plastic film of present invention elongation at break under ultraviolet lighting,
A-i corresponding to comparative example 1,2, embodiment 14-19, embodiment 2.
Fig. 5 is that the hydrophilic controllable light oxidation-biodegradable plastic film of present invention scanning electron after ultraviolet lighting shows
Micro mirror image, a-f corresponding to comparative example 1,2, embodiment 14,15, embodiment 17,19.
Fig. 6 is under the sealing compost after the hydrophilic controllable light oxidation-biodegradable plastic film illumination 300 hours of the present invention
Biodegradable mineralization rate curve map, a-d corresponding to comparative example 1,2, embodiment 14,19.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further explained, but specific embodiment is not to the present invention
It is limited in any way.Unless stated otherwise, involved in embodiment reagent, method are reagent commonly used in the art and method.
(1) formula of each embodiment and comparative example (consumption of each component is by weight percentage) as shown in table 1 below.
The each embodiment of table 1 and the formula of comparative example
(2) preparation method of each embodiment and comparative example plastic sheeting is as follows:
Weigh principle by the proportioning of each embodiment of table 1 or comparative example, mix in high-speed mixer, standby.Extruder bar
Part a: district 100～120 DEG C, two districts 120～140 DEG C, three districts 140～160 DEG C, four districts 160～180 DEG C, five districts 165～185
DEG C, head 165～185 DEG C.After temperature reaches to stablize, the raw material that will mix adds in feeding hopper, and regulation main frame and feeding machine turn
Speed, extrudes raw materials melt, crosses water, dries up, be cut into master batch, then by dried for master batch standby.Inflation film manufacturing machine temperature is then set:
One district 100～110 DEG C, two districts 125～135 DEG C, three districts 145～155 DEG C, die head 145～155 DEG C.After temperature reaches to stablize, beat
Opening host switch, regulate rotating speed, add master batch, extrusion-blown modling film forming, film thickness is about 80 microns.
(3) dependence test step
Film sample is placed in ultraviolet device for fast detecting aged sample internal radiation, and sample, away from light source 10cm, is weighed at set intervals,
Calculate the weight-loss ratio of film, characterize film light with high-temperature gel permeation chromatography (HTGPC) and ESEM (SEM) and shine front and back
The change of molecular weight and the change of surface topography, with the omnipotent test machine of material by the " survey of plastic tensile performance of GB GB/T1040.3
Determine third portion: film and the experimental condition of thin slice " test its hot strength and elongation at break, light degradation was put into after 300 hours
Biological compost device is carried out biodegradable, and draw samples mineralized rate.It is converted into induction period number of days and fall according to light radiation
Number of days needed for the solution phase, and contrast with actual environment degraded situation.Guangzhou total solar radiation whole year amount (45 °) is 4463MJ m-2,
Ultraviolet radiation amount accounts for 4%, and annual Solar Ultraviolet Radiation Over amount is 178.5MJ m-2, experimental condition Radiant UV Power is 150W m-2, 1 hour amount of radiation of illumination is 0.54MJ m-2, be equivalent to the actual environment illumination ultraviolet radiation of 1.1 days.
(4) film degradation performance
1, comparative example and the comparison of embodiment
Embodiment compares (such as Fig. 1 and Fig. 3) with comparative example, draws due to photochemical catalyst nano titanium oxide and hydrophilic modifying
Add while agent, make film degradation speed be improved largely；Additionally light stabilizer with the use of so that film light according to front
There is induction period in phase, and in induction period, film performance reduces little, meets actual operation requirements, and the degradative phase after induction period again can be fast
Prompt drop solution, has bigger weight-loss ratio and biologically digesting.The equal surface of test result, the photooxidation that the present invention prepares-biodegradable
The degradation property of plastic sheeting is the most controlled, is the degradation plastic film of function admirable.
The test result of embodiment all illustrate to regulate each recipe ingredient described in this patent can reach different film performances and
Degradation effect, for different use environment, requirement, can design a series of photooxidation-biodegradable plastic film, have very
Strong practicality.
2, the efficient controllable light oxidation-biodegradable plastic of embodiment 1～5 interpolation different content light stabilizer (HALS) is thin
Film
Embodiment 1～5 adds the efficient controllable light oxidation-biodegradable plastic film of different content light stabilizer, at purple
Under outer illumination, along with the increase of light stabilizer HALS content, film induction period extends accordingly, and content increases to 2.0% from 0.1%
Time, induction period increased to 1500 hours from 40 hours, becomes aging induction in actual environment according to equivalent ultraviolet irradiation Energy Conversion
Phase is about February～4 years, illustrates that the efficient controllable light oxidation-biodegradable plastic film of this patent can be according to the actually used phase
Limit regulation light stabilizer content realizes controllability；Degradative phase after induction period, photooxidation-biodegradable plastic film is the most real
Having showed efficient degradation, embodiment 1～5 degradation period all can reach 80% by weight-loss ratio in relatively short period of time (400 hours), film
Fractionlet, biodegradable (weight-loss ratio curve is as shown in Figure 2) that part is the most powdered, follow-up are split into.
3, embodiment 6～9 adds the efficient controllable light oxidation-biodegradable plastic film of different content nano TiO 2
Embodiment 6～9 adds different content nano-TiO2Efficient controllable light oxidation-biodegradable plastic film, at light
Induction period, embodiment 6 nano-TiO is all occurred in that according to lower photooxidation-biodegradable plastic film2Content is minimum, and induction period is the longest
It it is 250 hours, due to nano-TiO2The increase of content, degradation rate increases, and corresponding induction period shortens to the 180 of embodiment 9
Hour, induction period does not disappear, and degradation of plastic film remains controllability.Degraded test result is it is also shown that nano-TiO2Content
Time low, increase TiO2Content, degradation effect is obvious, after 3%, increases TiO2Content, degradation effect is inconspicuous.
4, embodiment 10～13 adds the efficient controllable light oxidation-biodegradable plastic film of variety classes hydrophilic modifying agent
Embodiment 10～13 adds the efficient controllable light oxidation-biodegradable plastic film of variety classes hydrophilic modifying agent,
Compare with comparative example 2, the interpolation of hydrophilic modifying agent, the degradation property of plastic sheeting can be greatly improved.Hydrophilic modifying agent PEG improves
Effect is the most obvious, and PEO takes second place, and PVA is minimum, but difference is little, all can well promote photooxidation-biodegradable plastic film
Degraded, can select suitable hydrophilic modifying agent, the beneficially popularization of photooxidation-biodegradable plastic film to answer according to actual conditions
With.
And comparative example 3,4 uses polyacrylamide (powder) or Sodium Polyacrylate (powder) to be hydrophilic modifying agent, due to upper
State two kinds of hydrophilic polymers to melt within the scope of certain temperature, the mixed of molecular level can not be reached with polymeric substrate
Closing, only physical dispersion, although prepared plastic sheeting improves the hydrophily of film, but hydrophilic polymer is not coated with and receives
Rice TiO2, Photocatalytic Degradation Property improves limited, and film surface has particle, affects outward appearance and mechanical performance.
5, the efficient controllable light oxidation-biodegradable plastic of embodiment 14～19 interpolation different molecular weight hydrophilic modifying agent is thin
Film
The efficient controllable light oxidation-biodegradable plastic that embodiment 14～19 adds different molecular weight hydrophilic modifying agent is thin
Film, weight-loss ratio curve under ultraviolet lighting is as it is shown in figure 1, the degraded speed of as can be seen from the figure embodiment 14～19 rate membrane
Rate relatively comparative example 2 rate membrane is greatly improved, PEG(or PEO is described) add the degradation rate of plastic sheeting had bigger
Improve.Molecular weight is PEG(or PEO of 10K to 50K) degraded facilitation higher (embodiment 15,16) to plastic sheeting,
PEG(or PEO) molecular weight to improve plastic sheeting degraded weight-loss ratio there is optimal value, molecular weight is not to be the bigger the better,
Possible cause is PEG(or PEO of macromolecule) easily crystal aggregation, cause TiO2Degradation efficiency reduce.PEG(or PEO)
All can have greatly improved the hydrophily of plastic sheeting, film surface moisture can enter internal, thus promotes within film
TiO2 reacts, and improves degradation efficiency, it will be seen from figure 1 that the degraded of plastic sheeting is promoted by the PEG that molecular weight is 10K
With the strongest (embodiment 15).
6, the efficient controllable light oxidation of embodiment 20～23 interpolation different content hydrophilic modifying agent (PEG10K)-biodegradable
Plastic sheeting
Embodiment 20～23 adds the efficient controllable light oxidation-biodegradable plastic film of different content hydrophilic modifying agent,
Under ultraviolet lighting, along with the increase of hydrophilic modifying agent (PEG10K) content, hydrophily increases, and degradation rate increases.But experiment
During, when PEG10K content is more than 5%, during blown film, melt viscosity is very big, film forming difficulty, is difficult to processing, is unfavorable for work in the future
Industry metaplasia is produced, and degradation property improves inconspicuous, it is impossible to by the content of raising PEG.
7, the efficient controllable light oxidation-biodegradable plastic film embodiment 24 of the different polymeric substrate of embodiment 24～28
～28 be the efficient controllable light oxidation-biodegradable plastic film of different polymeric substrate.Under ultraviolet lighting, different polymer bases
All there is certain degraded induction period in the film of material, and has preferable degradation effect, can degrade rapidly after induction period.Dioxy is described
Change the addition of titanium photochemical catalyst, all can improve the degradation property of the TPO plastic sheetings such as LDPE, LLDPE, PP, PVC or PS,
Wherein, the degradation property of LDPE laminated film is more excellent, and mechanical performance is the most excellent.
8, embodiment 29～32 exemplary potent controllable light oxidation-biodegradable plastic film
Embodiment 29～32 exemplary potent controllable light oxidation-biodegradable plastic film.Embodiment 29 be degradation rate
Fast maximum plastic sheeting, adds 0.1% light stabilizer, and induction period is 30 hours, and degradative phase film weight-loss ratio reaches 80%
Needing 150 hours, being converted into actual environment induction period is 1 month, and degradative phase is about 6 months, is fragment and powder after degraded,
And molecular weight is relatively low, it is easy to biodegradable.Embodiment 32 is that induction period is the longest, is 1400 hours, and degradative plastics is the slowest, degraded
Phase weightlessness reaches 80% needs 1000 hours, is converted into actual environment induction period and is about 48 months, and degradative phase is about 36
Month, it is suitable for using and applicable cases that degraded demand is the highest of long period.The plastics that embodiment 30, embodiment 31 prepare are thin
It is 6 months, 18 months that film induction period is accurately controlled, and degradative phase is 9 months, 12 months.
9, efficient controllable light oxidation-biodegradable plastic film performance characterization
Number-average molecular weight (M before and after comparative example and embodiment plastic sheeting ultraviolet lightingn) and weight average molecular weight (Mw) as
Shown in table 2.
Molecular weight before and after table 2 plastic sheeting ultraviolet lighting
From table 2 it can be seen that after illumination 300 hours, the number-average molecular weight (Mn) of comparative example 1 and weight average molecular weight (Mw) only
Reduce 73.8% and 64.9% respectively, the M of comparative example 2nAnd MwReduce 82.7% and 88.0% respectively, and the M of embodiment 2nAnd Mw
Reduce 85.1% and 88.1% respectively, the M of embodiment 8nAnd MwReduce 90.0% and 91.1% respectively, the M of embodiment 15nAnd Mw
Reduce 92.6% and 93.0% respectively, the M of embodiment 16nAnd MwReduce 93.9% and 94.2% respectively, adding of titanium dioxide is described
Enter and can improve film degradation, and the addition of hydrophilic modifying agent can improve the palliating degradation degree of film further, membrane molecular amount
Reduce the biodegradability being conducive to film.
Comparative example and the hot strength of embodiment plastic sheeting and elongation at break as shown in Figure 3, Figure 4, as seen from the figure,
Plastic sheeting is respectively provided with higher mechanical performance, and before illumination, hot strength major part is more than 15MPa, and elongation at break is all higher than
130%, the film of different formulations, performance difference is little, complies fully with actual operation requirements, and after degraded, film mechanical strength ruptures
Percentage elongation reduces rapidly, the easy fragmentation of film is described, becomes fritter and powder, it is easy to contact with microorganism, accelerate biodegradable
Speed.
Scanning electron microscope diagram after comparative example and embodiment plastic sheeting ultraviolet lighting as it is shown in figure 5, wherein a-f divide
Not corresponding comparative example 1, comparative example 2, embodiment 14, embodiment 15, embodiment 17, embodiment 19.From fig. 5, it can be seen that ultraviolet
After illumination 300 hours, upper substantially it is not changed in for ldpe film is apparent, LDPE/TiO2Film surface creates some holes,
And add the film heavy damage after hydrophilic modifier, a large amount of pore space structure occurs, in spongy, hydrophilic modifying agent (PEG is described
Or PEO) interpolation be greatly improved photocatalysis performance and the biodegradability of film.
Biodegradable mineralization rate curve under comparative example and embodiment plastic sheeting ultraviolet lighting sealing compost after 300 hours
As shown in Figure 6, from fig. 6, it can be seen that ultraviolet lighting is after 300 hours, the mineralization rate of comparative example film is relatively low, and not higher than 1.5%,
But add the mineralization rate of embodiment after hydrophilic modifying agent to significantly improve, the highest more than 3.2%, illustrate hydrophilic modifying agent (PEG or
PEO) interpolation is greatly improved photocatalysis performance and the biodegradability of film, is conducive to preparing oxidation-biodegradable plastic
Film, promotes significant to efficient controllable light oxidation-biodegradable plastic film.
Claims (9)
1. efficient controllable light oxidation-biodegradable plastic film, it is characterised in that include the group of following percetage by weight
Point: polymeric substrate 88 ~ 98.9%, hydrophilic modifying agent 0.5 ~ 5%, nano titanium oxide 0.5 ~ 5%, light stabilizer 0.1 ~ 2%；Described
Polymeric substrate be the one in low density polyethylene (LDPE), LLDPE, polypropylene, polyvinyl chloride, polystyrene or
Multiple, molecular weight is 10K ~ 60K；Described hydrophilic modifying agent is the one in polyethylene glycol, polyoxyethylene, polyvinyl alcohol or many
Kind, molecular weight is 4K ~ 500K；Described light stabilizer is hindered amine light stabilizer.
The most efficient controllable light oxidation-biodegradable plastic film, it is characterised in that described hydrophilic change
The molecular weight of property agent is 4K ~ 50K.
The most efficient controllable light oxidation-biodegradable plastic film, it is characterised in that described hydrophilic change
The molecular weight of property agent is 10K.
The most efficient controllable light oxidation-biodegradable plastic film, it is characterised in that described hydrophilic change
Property agent be polyethylene glycol or polyoxyethylated one or both.
The most efficient controllable light oxidation-biodegradable plastic film, it is characterised in that described hydrophilic change
Property agent is polyethylene glycol.
The most efficient controllable light oxidation-biodegradable plastic film, it is characterised in that described polymer
Base material is low density polyethylene (LDPE), and molecular weight is 20K ~ 50K.
The most efficient controllable light oxidation-biodegradable plastic film, it is characterised in that described nanometer two
The particle diameter of titanium oxide is 10 ~ 50 nanometers, and crystal formation is based on anatase.
8. the preparation method of efficient controllable light oxidation-biodegradable plastic film described in any one of claim 1 ~ 7, its feature exists
In, concretely comprising the following steps and the component of percentage by weight described in claim 1 is mixed, melt blending, blowing prepares plastic sheeting.
Preparation method the most according to claim 8, it is characterised in that the thickness of described plastic sheeting is 10 ~ 150 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410104064.6A CN103834086B (en) | 2014-03-19 | 2014-03-19 | A kind of efficiently controllable light oxidation-biodegradable plastic film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410104064.6A CN103834086B (en) | 2014-03-19 | 2014-03-19 | A kind of efficiently controllable light oxidation-biodegradable plastic film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103834086A CN103834086A (en) | 2014-06-04 |
| CN103834086B true CN103834086B (en) | 2016-08-17 |
Family
ID=50798005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410104064.6A Active CN103834086B (en) | 2014-03-19 | 2014-03-19 | A kind of efficiently controllable light oxidation-biodegradable plastic film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103834086B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151632B (en) * | 2014-07-17 | 2016-03-02 | 安徽巢湖南方膜业有限责任公司 | A kind of natural rubber-polyvinyl alcohol double degradation plastic film formula and preparation method thereof |
| CN105104017A (en) * | 2015-08-19 | 2015-12-02 | 安徽九禾农业发展有限公司 | Grape planting greenhouse |
| CN106519474B (en) * | 2016-12-13 | 2018-09-25 | 山东中塑泰富科技有限公司 | A kind of environmentally friendly heat shrink films and preparation method thereof of the high grade of transparency and high tenacity |
| CN107298787A (en) * | 2017-08-17 | 2017-10-27 | 桐城市钰锦塑料包装有限公司 | A kind of degradable combination film and preparation method thereof |
| CN108373563A (en) * | 2018-03-28 | 2018-08-07 | 方建波 | A kind of preparation method of biodegradable agricultural film |
| CN108659319A (en) * | 2018-06-01 | 2018-10-16 | 安徽永豪日用品有限公司 | A kind of polyethylene preservative film of addition medical stone |
| CN110066451A (en) * | 2019-04-20 | 2019-07-30 | 青岛科技大学 | A kind of plastic film anti-droplet master batch and preparation method thereof |
| CN110406223B (en) * | 2019-08-09 | 2021-08-06 | 广东安德力新材料有限公司 | Degradable environment-friendly polyolefin heat shrinkable film and preparation method thereof |
| CN111911139A (en) * | 2020-08-14 | 2020-11-10 | 青岛大地新能源技术研究院 | Slow-release tracing controllable system for water exploration of oil and gas well, preparation method and application |
| CN112608549A (en) * | 2020-12-03 | 2021-04-06 | 福建利新德塑胶制品有限公司 | Corrosion-resistant PE composite material for septic tank and preparation method thereof |
| CN114045115B (en) * | 2021-11-12 | 2024-01-16 | 安徽国风新材料股份有限公司 | Degradable BOPP precoating film and preparation method thereof |
| CN114230901A (en) * | 2022-01-28 | 2022-03-25 | 孙琇芳 | LDPE (Low-Density polyethylene)/PEO (polyethylene oxide) water swelling type fast-degrading film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850626A (en) * | 2012-08-30 | 2013-01-02 | 苏州市德莱尔建材科技有限公司 | Degradable mulch film and preparation method thereof |
| CN103102582A (en) * | 2012-11-13 | 2013-05-15 | 铜陵亿亨达电子有限责任公司 | Capacitor thin film containing modified nano-titanium dioxide and preparation method thereof |
| CN103146045A (en) * | 2011-12-07 | 2013-06-12 | 张庆之 | Photodegradable high-temperature-resistant plastic preservative film |
| CN103408793A (en) * | 2013-07-23 | 2013-11-27 | 华南农业大学 | Nonmetal-doped titanium dioxide, preparation method thereof and degradable plastic film |
| CN103601950A (en) * | 2013-10-20 | 2014-02-26 | 安徽嘉木橡塑工业有限公司 | Antimicrobial plastic wrap |
-
2014
- 2014-03-19 CN CN201410104064.6A patent/CN103834086B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146045A (en) * | 2011-12-07 | 2013-06-12 | 张庆之 | Photodegradable high-temperature-resistant plastic preservative film |
| CN102850626A (en) * | 2012-08-30 | 2013-01-02 | 苏州市德莱尔建材科技有限公司 | Degradable mulch film and preparation method thereof |
| CN103102582A (en) * | 2012-11-13 | 2013-05-15 | 铜陵亿亨达电子有限责任公司 | Capacitor thin film containing modified nano-titanium dioxide and preparation method thereof |
| CN103408793A (en) * | 2013-07-23 | 2013-11-27 | 华南农业大学 | Nonmetal-doped titanium dioxide, preparation method thereof and degradable plastic film |
| CN103601950A (en) * | 2013-10-20 | 2014-02-26 | 安徽嘉木橡塑工业有限公司 | Antimicrobial plastic wrap |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103834086A (en) | 2014-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103834086B (en) | A kind of efficiently controllable light oxidation-biodegradable plastic film and preparation method thereof | |
| KR102058392B1 (en) | Manufacturing Method of Biodegradation Film and Mulching Film prepared therefrom | |
| CN102504345B (en) | Disposable controlled completely-degradable plastic packing bag and preparation method thereof | |
| JP6942323B2 (en) | Manufacturing method and application of reinforced toughening and permeable masterbatch | |
| CN113736069B (en) | Biodegradable polyester resin composition, nonwoven fabric, film and method for producing same | |
| CN110591316B (en) | Shell powder modified polylactic acid composite material and preparation method and application thereof | |
| CN101805499B (en) | Full-degradable thermoplastic composite material and sheet thereof | |
| CN106832807B (en) | Controllable full-degradable mulching film of cellulose-reinforced starch and preparation method thereof | |
| CN105802168A (en) | Biodegradable nanometer filling function master batch and preparation method and application thereof | |
| JP2020521834A5 (en) | ||
| CN101993558A (en) | Thin film produced by using starch fiber waste plastic | |
| CN1771281A (en) | Biodegradable resin film or sheet and process for producing the same | |
| CN107365482B (en) | A kind of special reinforced toughened anti-reflection master batch of ultra-thin whole life cycle design | |
| CN107345053B (en) | Ultra-thin super transparent full-biodegradable film blown film grade material of one kind and preparation method thereof | |
| CN106192217A (en) | Plant base biodegradable non-woven fabrics and manufacture method thereof | |
| CN113292832A (en) | Polylactic acid foaming composite material and preparation method and application thereof | |
| CN106479132B (en) | A kind of degradation of plastic film master batch and the preparation method and application thereof | |
| CN105504704A (en) | Ethanolamine activated Na-montmorillonite and polymer composite biodegradable film blowing resin and preparation method | |
| CN103788603B (en) | A kind of poly(lactic acid) two-way stretch frosted film and preparation method thereof | |
| CN109233230A (en) | A kind of hybrid polydactyl acid membrane material and preparation method thereof | |
| CN109206727A (en) | A kind of degradable polyethylene agricultural film and preparation method thereof | |
| CN109988400A (en) | A kind of environment-friendly type degradable packaging composite film and preparation method thereof | |
| CN109082135A (en) | A kind of high-strength composite packaging material and preparation method thereof | |
| CN106336634A (en) | Improved biodegradable shopping bag and preparation method thereof | |
| CN113462132A (en) | Biodegradable composite material, preparation method thereof and biodegradable breathable film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180705 Address after: 515071 1, 2, 3, 5 buildings of E09-2, E06-3 and E08-3 plots in Shantou Free Trade Zone, Shantou, Guangdong. Patentee after: Octoplas Technologies Company Limited Address before: No. 483, five mountain road, Tianhe District, Guangzhou, Guangdong Patentee before: South China Agricultural University |
|
| TR01 | Transfer of patent right |