CN103172981B - A kind of degradable polymer compositionss and preparation method thereof - Google Patents
A kind of degradable polymer compositionss and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of degradable polymer compositionss, contain：Polymer and dispersion two or more transition metal salts in the polymer, wherein, at least one of described two above transition metal salts are multivalent transition metal salt.The invention also discloses the method preparing above-mentioned composition：Polymer is mixed with transition metal salt, is heated to molten condition, cooling shaping, obtains final product.The degradable polymer compositionss of the present invention, select two or more transition metal to produce cooperative effect.In cooperative effect phenomenon, multivalent transition metal plays the effect of catalyst to produce initiation free radical.When having high-energy after free radical is by UV light or thermal excitation, it will have enough energy and collective effect is to overcome the activated energy barrier of complicated polymer.Long chain will be fractured into small molecule.As a result, cooperative effect significantly promotes degradation process.
Description
Technical field
The present invention relates to a kind of degradable polymer compositionss and preparation method thereof.
Background technology
Polyester is to contain ester functional group polymer in a kind of main chain.Polyester includes natural chemical substance, is such as present in
In the cutin of plant crust, also include the synthetic obtaining by step-growth polymerization, such as Merlon and poly- butyrate.Foundation
Its chemical constitution, polyester can be thermoplasticity or thermosetting.Modal polyester is thermoplastic.Polyester can be aliphatic, half virtue
Fragrant race or aromatic, this depends on the composition of its main chain, as shown in table 1.
The composition of table 1 polyester
| Main chain forms | Repetitives | Polyester is illustrated |
| Aliphatic | Homopolymer | Polyglycolide or polyglycolic acid（PGA） |
| Polylactic acid（PLA） | ||
| Polycaprolactone（PCL） | ||
| Copolymer | 10PE27（PEA） | |
| Polyhydroxy-alkanoate（PHA） | ||
| Semi-aromatic | Copolymer | Polyethylene terephthalate（PET） |
| Polybutylene terephthalate（PBT） | ||
| PTT Fiber（PTT） | ||
| PEN（PEN） | ||
| Aromatic series | Copolymer | Wholly aromatic polyester（As：Wei Ketelun Vectran） |
For example, polyethylene terephthalate（As shown in formula I）, usual abbreviation PET, is the thermoplasticity polymerization of polyester race
Resin, it is often combined for synthetic fibers with glass fibre, beverage, food and other liquid containers, thermoforming apply and
In engineering resin.Reported with plastics industry committee according to Canadian environment, 65000 tons of polyester beverage container are conveyed within 2002
Landfill or burning.This data is very huge, and these polyester beverage container can produce very big environment after treatment
Pollution.
Formula I
Polystyrene is an aromatic vinyl polymer（As formula II）.It has a long hydrocarbon chain, every one
Carbon atom connects a phenyl group.Polystyrene passes through the polymerization of free radical ethyl by monomer styrene and is obtained.Polystyrene is originally
It is thermoplastic in matter.Solid polystyrene is used as, for example, in disposable knife and fork, CD（Or DVD）Box and smoke detection
Device casing；Polyethylene foamed is almost ubiquitous, such as packaging material, heat-barrier material and expansion type goblet.
Formula II
Polyamide is a kind of polymer of the amino-compound monomer comprising to be coupled together by peptide bond（As shown in formula III）.People
Work polyamide includes nylon, the aromatic polyamide fibre obtaining by step-growth polymerization or solid phase synthesis（aramids）With
Poly (sodium aspartate)（sodium poly(aspartate)）.Polyamide according to the group constituent class of its main chain, as shown in table 2.Poly-
Amide, due to its fabulous durability and strength characteristics, is applied generally in textile, automobile, carpet and gym suit.
Formula III
The composition of table 2 polyamide
| Polyamide race | Main chain | Polyamide is illustrated |
| Fatty polyamide | Aliphatic | PA 6 and PA66 |
| Polyphtalamide | Semi-aromatic | PA 6T |
| Aromatic polyamide（Aramides） | Aromatic series | P-phenylenediamine+p-phthalic acid |
Now, process in plastics problem becomes increasingly severe, because the degraded of plastics takes long enough in nature
（As 100 years）.In order to cater to the trend of environmental protection, scientist is made that and makes great efforts to develop degradable and biodegradable in a large number
Plastics.Herein, " degradable " refers to, such as ethene polymerss, is degraded to relatively due to the effect of different additive or other materials
Small fragment, and microorganism produces impact to not this degraded；And " biodegradation " refers to one kind due to organism（As：Microorganism）
Effect and the degraded that produces.
The topic of biodegradable fiber has been investigated for 10 years.Many researcheres and scientist are not adding degradable to add
Plus in the polymer of the natural degradation of agent, carried out experiment and sunykatuib analyses.2004, Hispanic scientist's research existed
Degradation polyolefin under high temperature.Result shows, does not add the polyacrylic thermal degradation of degradability additive to occur in more than 200 DEG C.
Need such high temperature, be because that it needs the fracture to cause molecular linkage in polymer architecture for the enough heat energy.But, real
On border, degraded prepolymer just seems to have become as molten.An other document also elaborates to simulate polyphenyl second using modeling
Alkene（PS）Thermal degradation, result display PS 360 DEG C start thermal degradations.Accordingly, it would be desirable to big energy is starting degraded, and this
Technique is not environmentally.Additionally, so high temperature can not possibly be reached in nature with the situation not introducing degradability additive
Lower those materials of degraded.
Recently, traditional plastics are gradually replaced by degradable product, to reduce plastic pollution.First use is in the plastic
Biodegradable polyester is referred to as polyhydroxy-alkanoate (PHAs), and it is a kind of by the microorganism work on glycosyl medium
The spontaneous aliphatic polyester of skill, plays the effect of carbon and energy storage material in antibacterial.
Undoubtedly, plant based material can in nature complete biodegradable, but petroleum-based plastics are complete
Different.In 10 weeks composting cycle, the optimum condition of commercial general PHA degraded is：60 DEG C, humidity 55%, C:N ratio
For 18:1.Under this composting conditions, the degradation rate of PHA can reach close to 100%.Aliphatic polyester is as starch or fiber
Effect is to produce nonhumic substance such as CO2And methanol.
Compared with petroleum-based plastics, the plant base plastics in nature are very rigid and fragile.The machinery of plant base plastics
More far short of what is expected than corresponding petroleum-based plastics with hot property, this is because its chain has hydrophilic.This makes the machinery of mixture
Characteristic is poor.Plant based material not only poor-performing and also more expensive, this be strictly a fact.Renewable origin product（That is, plant
Thing base/starch plasticses）Tend to more expensive than the product obtaining from oil base resource.However, the commodity price of starch is significantly lower than
Oil.The more expensive main cause of starch base product is starch and the productivity ratio synthetic polymer of starch/synthetic polymer compound
Productivity ratio much lower.Therefore, the relatively poor efficiency of amyloid polymer improves ultimate cost.
In the past few decades, U.S. Patent number 3,454,510 disclose polyolefin film（Especially coverlay）In
Some enzymatic oxidation slaines can provide same environment-friendly degradable, but the displosure content is only defined in opaque coating.The U.S. is special
Profit number 3,320,695 and U.S. Patent number 3,341,357 further disclose some unsaturated hydrocarbons and add opaque polyolefin
Can promote in film to degrade.These opaque coatings can also be used for overlapping operation, and it needs some insatiable hungers of larger percentage by weight
And hydrocarbon, this will lead to produce " excessively soft " product it is generally recognized that being not suitable for the application of consumer goodss.
The global polyester product of estimation is as shown in table 3.In another study, it is said that global total polyester product in 2010 is every
Year is more than 5,000 ten thousand tons.
The global production of polyester of the annual market scale of table 3
| Product type | 2002 [million tons/year] | 2008 [million tons/year] |
| Textile synthetic fibers | 20 | 39 |
| Film | 1.2 | 1.5 |
| Bottle | 9 | 6 |
| Particular polyesters | 1 | 2.5 |
| Altogether | 31.2 | 49 |
According to upper table, polyethylene terephthalate is widely used in the manufacturing process with clothing industry of weaving.Polyester has ideal
High-wearing feature and agent of low hygroscopicity.Polyester has market potential and is worth, even and if be non-reproducible, it still dominates city
?.Half in annual 4.5 thousand ten thousand fibers consuming in the whole world is all manufactured by synthetic fibers according to estimates.Carry out according to the U.S.
Research, polyethylene terephthalate is petroleum based material, occupies the 50% of global synthetic fibers production.
According to the application market information carrying out for 2007（Applied Market Information Ltd.）Research, gathers
Amide has the continuable position of development in every way in plastics industry, and the final application of e.g., from about 92% polyamide needs
Seeking Truth is in the ejection formation of automobile, electricity and industrial market.But, when as garbage disposal, these synthetic polymers big
Amount consumes and environment is created with very big pollution.In nature, these polymer need the time of many decades to degrade.
In order to reduce the environmental pollution postponing at waste product, the application of biodegradable fiber is a suitable solution.Thing
In reality, natural fiber such as cellulose is used in mixed way with synthetic fibers, pollutes the impact to environment to reduce after waste disposal.
But, quality is unsatisfactory (such as：Easily wrinkle, not easy cleaning), and production cost is very high.In addition, compared with cellulose fibre,
Another advantage of biodegradable fiber is that synthetic fibers are easy to be blended each other.Compared with cellulose fibre, synthetic fibers are other
Major advantage is easy retentivity and modernity.The production technology of synthetic fibers is more simply too much than cellulose fibre, and synthesizes fibre
Dimension has more preferable mechanical characteristic.Therefore, these are all development degradable synthetic fibers so that final products can be in the environment
The reason biological decomposition.
Due to the problem of many people all concern for the environment pollutions, the packaging material of degradation plastic are increasingly subject to vigorously in Hong Kong
Meet.It is used as degradable reagent oxidation additive more, be added in production engineering in packaging material to produce degradation plastic.Phase
Same idea can be applicable to industrial textile.For traditional synthetic fibers, i.e. nylon and polyester, due to they have very long and
The strong carbochain closed containing nitrogen or oxygen key, they can not easily be degraded in nature.It is true that degradable textile
Idea attempts application in Hong Kong several years ago.These textile fibers are mainly by cellulosic polymer（For example, viscose rayon and vinegar
Acid）, plant extract and modified plant fibers make, biodegradable filler adds in synthetic fibers, and be referred to as can be biological
Degraded.
There is very long carbon backbone chain in synthetic polymer structure.They can be reacted with the oxygen of in the air to generate naturally
Hydroperoxides（hydroperoxide）.This reaction is referred to as oxygen degraded（oxo-degradation）.But, this be one non-
The reaction often taking（As the centuries）, here it is why this material is difficult to the main cause degraded in nature.More closely
Year, on market, typical degradability additive can reduce main chain by the backbone breaking of atarting material, e.g., molecular weight, comes
Accelerated degradation.After adding additive, its role causes free radical M to generate as catalyst, and M is by UV light or warm
Unstable after exciting, and there is high-energy.This mechanism is as follows：
When metal ion is in high-energy form（For example, free radical）When, it splits long chain by having enough energy
Solve as short.Therefore, there occurs degradation process.
Application in PP and PE packaging material for the degradation technique is highly developed, and can commercially buy.But, more
How such application of complicated polymer is not reported, such as polyester, polyamide, polystyrene etc..Existing drop
Solution additive can be good at being applied in polypropylene and polyethylene, but to these complicated polymer and inoperative.This can
Can be the labyrinth due to these polymer, such as：Carboxyl in structure, phenyl ring and amide functional group.And in polyolefin, only
There is the simple structure of a long carbon backbone chain.But as the functional group of aforementioned increase will form one by force in complicated polymer
Bonding, in order to this bonding that ruptures then needs more energy in degraded.
Content of the invention
The technical problem to be solved in the present invention is that existing synthesizing polymeric material is difficult to degrade in nature, and can drop
The plant base polymeric material performance of solution is not good.
In order to solve above-mentioned technical problem, the present invention provides an environment-friendly degradable polymer composition, and it is fine that it contains synthesis
Peacekeeping transition metal ionss, when being discarded in environment, the product of this group and thing is degraded by chelating technology.Therefore, it is possible to add
The degradation process of fast polymer waste.
A kind of degradable polymer compositionss that the present invention provides, contain：Polymer and dispersion are in the polymer
Two or more transition metal salts, wherein, at least one of described two above transition metal salts are multivalent transition metal salt.
Wherein, described polymer is polyester, polyamide or polystyrene.Described polyester is polyethylene terephthalate,
Polybutylene terephthalate, PTT Fiber, PEN or Wholly aromatic polyester.Described
Polyamide is fatty polyamide, polyphtalamide or aromatic polyamide.
Preferably, the metal ion gross weight of described two above transition metal salts is described degradable polymer compositionss
The 0.001 ~ 10.0% of weight, more preferably 0.01 ~ 5.0%.
Preferably, the described degradable polymer compositionss also weight containing antioxidant described in antioxidant is described degradable
The 0.001 ~ 5.0% of polymer composition weight.
Preferably, described transition metal salt is transition metal organic salt or inorganic salt.Preferably, described transition metal has
Machine salt is stearate, acetate, caprylate, naphthenate, acetylacetonate or the oleate of transition metal, such as：Stearic acid
Manganese, silver stearate, cobaltous octadecanate, ferric stearate, copper stearate, lead stearate, cerium stearate, manganese oleate, Oleic acid silver, Oleic acid
Cobalt, copper oleate, zinc oleate, iron oleate, cobalt naphthenate, iron naphthenate or zinc naphthenate etc..The inorganic salt of described transition metal is
The sulfate of transition metal, nitrate or chloride, e.g., iron sulfate, copper sulfate, zinc chloride, copper nitrate, cobaltous chloride, nickel sulfate
Or zinc sulfate etc..
Preferably, described transition metal salt is the organic salt of transition metal, it is highly preferred that described transition metal salt is V,
The organic salt of Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ag, Ce or Pr.
The present invention provides the method preparing above-mentioned degradable polymer compositionss, and step is：By polymer and transition gold
Belong to salt mixing, be heated to molten condition, cooling shaping, obtain final product.According to actual needs, by antioxidant, transition metal salt and can gather
Compound mixes.
Preferably, the step of said method is：Described polymer is added in double helical mixer together with transition metal salt,
After mixing, the long filament of molten condition is extruded by spinneret, and long filament is cured, and passes through water cooling, is then cut into granulated
Formula.Wherein, the rotating speed of double helical mixer is preferably 50 ~ 500 rpm, more preferably 100 ~ 280 rpm.
The beneficial effect of the degradable polymer compositionss of the present invention：
1st, the degradable polymer compositionss of the present invention, select plural transition metal to produce cooperative effect.?
In cooperative effect phenomenon, multivalent transition metal plays the effect of catalyst to produce initiation free radical.When free radical is by UV light or heat shock
After sending out when having high-energy, it will have enough energy and collective effect is to overcome complicated polymer（Polyester, polyamide and
Polystyrene）Activated energy barrier.Long chain will be fractured into small molecule.As a result, cooperative effect significantly promotes degradation process.
2nd, the degradable polymer compositionss of the present invention have controlled service life.
Brief description
Fig. 1 is the infrared spectrogram before the degradable polymer compositionss degraded of embodiment 1.
Fig. 2 is the infrared spectrogram after the degradable polymer compositionss degraded of embodiment 1.
Fig. 3 is the infrared spectrogram before the degradable polymer compositionss degraded of embodiment 2.
Fig. 4 is the infrared spectrogram after the degradable polymer compositionss degraded of embodiment 2.
Fig. 5 is the infrared spectrogram before the degradable polymer compositionss degraded of embodiment 3.
Fig. 6 is the infrared spectrogram after the degradable polymer compositionss degraded of embodiment 3.
Specific embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings, so that those skilled in the art is permissible
It is better understood from the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
The present invention provides a kind of degradable polymer compositionss, and it contains fluoropolymer resin and is dispersed in fluoropolymer resin
Two or more transition metal salts.In order to control the length of degradation time, also contain appropriate in the polymer composition of the present invention
Antioxidant.Suitable percentage by weight by suitable transition metal ionss and antioxidant in careful control polymer can
Reach degradable within the specific time, that is, several years or shorter.
The degradable polymer compositionss of the present invention, refer in particular to the degradable combination of polyester, polyamide or polystyrene
Thing, target resinous polymer therein is typically the thermoplastic polymer of powder type.For example, the copolymer of polyester resin, its
It is made up of terephthalic acids ester group, for example polyethylene terephthalate（PET）, polybutylene terephthalate（PBT）, it is right to gather
Phthalic acid propylene diester fiber（PTT）, PEN（PEN）Or Wholly aromatic polyester（Vectran）.Polyamide resin
Fat can be for fatty polyamide (as PA 6, PA66;PA 6T) and aromatic polyamide（Aramides）
Paraphenylenediamine + terephthalic acid（P-phenylenediamine+p-phthalic acid）.
In degradable polymer compositionss, two or more transition metal salts can be the organic salt or inorganic of any transition metal
Salt, wherein at least one slaine is multivalent transition metal, preferably the organic salt of multivalent transition metal（The present invention is through many experiments
Find：One of which has to as multivalent transition metal salt, and can not all univalent metal salts.Otherwise, degradable polymer
The degraded of compositionss can be impacted）, most preferably in metal, electron transfer such as periodic chart occurs in 3d shell or 4f with being defined
The organic salt of the multivalent transition metal of shell.They are element in the period 4 that atomic number is 21 to 30, atomic number
Element in the period 6 of the element in the period 5 of several 39 to 48 and atomic number 57 to 71.Specific at these
Transition metal in, electron transfer occur 3d shell transition metal be the 4th and period 5 V, Cr, Mn, Fe,
Co, Ni, Cu, Zn, Zr and Ag, there is Ce or Pr that the transition metal in 4f shell is the period 6 in electron transfer.
According in the degradable polymer compositionss of the present invention, select suitable multivalent transition metal use in conjunction.Suitably
Multivalent transition metal organic salt be typically Metallic stearates, mol ratio of metal acetate, sad slaine, metal naphthenate or
Acetylacetone,2,4-pentanedione（acetylacetonate）Slaine, is only used as illustrating, such as：Manganese stearate, silver stearate, cobaltous octadecanate, Hard Fat
Sour ferrum, copper stearate, lead stearate, cerium stearate, manganese oleate, Oleic acid silver, cobalt oleate, copper oleate, zinc oleate, iron oleate, ring
Alkanoic acid cobalt, iron naphthenate, zinc naphthenate etc., but be not restricted to that above-mentioned salt, if it is desired, other organic groups also can make
With.On the other hand, suitable multivalent transition metal inorganic salt according to the present invention, can illustrate such as：Iron sulfate, copper sulfate, chlorination
Zinc, copper nitrate, cobaltous chloride, nickel sulfate, zinc sulfate etc..
The Degradable master batch of the degradable polymer compositionss of the present invention passes through a blender preparation, double spiral shells of this blender
Oar constant speed is 50 ~ 500 rpm, preferably 100 ~ 280 rpm.Target polymerization resin and the prooxidant mistake of appropriate amount
Cross metal ion powder, be added into the feeder being monitored by feed system.At least two multivalent transition metal add target polymerization
In resin, metal ion wherein generally in the slaine percentage by weight in degradable polymer compositionss is 0.001 ~
10.0%.Most preferably percentage by weight in degradable polymer compositionss for the metal ion in slaine be 0.01 ~
5.0%.After mixing, the long filament remaining as molten condition is extruded by spinneret.Long filament is cured, and is cooled down by a water pot,
It is then cut into particle form.Thus, the Degradable master batch of the present invention is prepared and is completed.
The master batch of the particle form of about 0.5 ~ 20g, most preferably about 1 ~ 5g, are 120 ~ 350 DEG C with temperature, most preferably
180 ~ 260 DEG C of heat extruder, heats 5 ~ 80 minutes, most preferably heats 10 ~ 30 minutes, this depends on the amount of master batch, Ran Houying
For corresponding stripper plate.The degradable films of one degradable polymer compositionss are finally made.
In order to evaluate to the degradability making product, product is carried out UV process 5 ~ 60 days, most preferably 10 ~ 30
My god, it depends on the percentage by weight of the transition metal of the type of subject polymer and interpolation.During this period, about 0.1 ~ 5g,
Sample after the UV of preferably 1 ~ 2g is processed is removed with Fourier transform infrared spectroscopy（FTIR）Detection structure change.Change it
The time of structure shows to help degradation agent（I.e. transition metal ionss）Effect, the shorter time shows that transition metal ionss show more
Good helps degradation effect.The degradability of sample is measured by international method simultaneously, e.g., measures degradable polymerization using stretching experiment
The ASTM D3826 of thing degraded terminal, and/or Study Polymer Melts weight average molecular weight（Mw）ASTM D6954.
In the present invention, the new technique of research and development is referred to as many metal catalytics degradation technique.In the art, the mesh in order to degrade
, play and help two or more different transition metal of degradation agent effect to be added in polymer, but the speed of depolymerization
Rate depends on the addition of slaine.These add polymer in transition metal salt, serve as catalyst, its produce free radical with
Induction degraded, the mechanism of the decomposition of its catalysis hydroperoxides is as follows：
Wherein, M1 ‧+ M2 ‧Represent the free radical of two kinds of transition metal.
Transition metal salt content is higher, and degradation rate is faster.In order to control the shelf-life of polymer, the slaine of appropriate amount
The controlled shelf-life is obtained in addition system.To long quality guarantee period product, degraded lentamente occurs, due to the transition of low concentration
Metal ion adds to provide a degenerated product with the expected shelf-life.On the contrary, the metal ion of higher concentration adds
To provide the product of short expected shelf-life.Select appropriate transition metal salt and its amount, desirable and rational product can be obtained
Shelf-life.
In the degradable polymer compositionss of the present invention, the antioxidant of suitable deal can be added to be used to control degradable poly
The length of the degradable time of compound.And the number of antioxidant deal is depending on the practical use of manufactured goods, based on total polymerization
The gross weight of compositions, typically can be in 0.001 to about 5.0 percentage by weight.Antioxidant in the present invention does not do especially
Limit, for slowing down or prevent the material of Oxidation, in the present invention application for commercially available antioxidant product, for example：
IRGANOX® 1010, TINUVIN® P, IRGANOX® 1098, Uvinul® 3008, Tinuvin 320,
IRGAFOS® 168, Sovchem AO1010, Sovchem AO1076, Sovchem AO1330, Sovchem AO245,
Sovchem AO3114, Sovchem MD1024 , Sovchem AO1098, Sovchem B215, Sovchem B220,
Sovchem B561, Sovchem B900, Sovchem B921 , Sovchem B225, Sovchem AO168,
Sovchem AO-TBM6, etc..
Under typical conditions, one of these transition metal salts have enough energy to cause polyolefinic degraded
Process.But, from former constructed observation to when only a kind of slaine is applied to polyester, this process is inoperative.This can return
Because in the labyrinth of polymer.There are in polyolefin the simple chemical constitution of straight long carbon backbone chain, a kind of transition metal ionss
Can act.But, polyester has bulk and labyrinth, this may require that extra energy with the strong bonding that ruptures to cause
Its degraded.Therefore, the present invention shows and adds polyester together with degradation process quilt when producing cooperative effect when multiple transition metal salts
Significantly promote.It is that metal ion is cost efficient using the advantage that many metal cation salts research and develop degradable polymer
's.With the polymer phase ratio of business degradability additive and plant base, they have relatively low cost.In addition, after treatment
These transition metal environmental sounds, therefore transition metal ionss salt are eco-friendly.
Measure through FTIR spectrum, be dispersed with the polyamide of two or more transition metal salts and polyester sample at 3 days and 10 days
After UV is processed, the carbonyl (C=O) in polyester sample structure is in 1560 cm-1The intensity of absorption band significantly increase, polyamide exists
1736 cm-1Peak be significantly enhanced.It was observed that the maximum intensity at this peak after irradiating to 14 days UV of polyester sample.Remembered according to document
Carry, show in FTIR that the presence at this peak reflects due to the photooxidative degradation in sample, and there occurs chain interruption.The intensity at this peak
Increase the summation owing to the contribution that overlaps being derived from product after degradation process, mechanism is as follows：
The oxidizing process mechanism of polyester：
Wherein, M1 ‧+ M2 ‧Represent the free radical of two kinds of transition metal.
The oxidizing process mechanism of polyamide：
Wherein, M1 ‧+ M2 ‧Represent the free radical of two kinds of transition metal.
Initiation reaction is relevant with impurity present in polymer chain and defect.This decomposes the life that may lead to unstable species
Become, it will be by the further accelerated degradation reaction of branched oxidative chain.After prolonged exposure, find that unstable species will be free in
In more stable secondary oxidation product.As a result, polyester is in 1560 cm-1And polyamide is in 1736 cm-1Peak can also be observed that by force
Degree significantly increases.As shown in table 4 after 30 days UV are processed, it is dispersed with the polystyrene sample of two or more transition metal salts
Weight average molecular weight Mw significantly reduces.Weight average molecular weight according to polymer（Mw）International standard ASTM D6954 research, this table
Bright sample starts to degrade after being exposed in UV light.
The degradable polymer compositionss that the present invention provides can be applied to manufacture biodegradable fiber, degradable polymer
The degradable polymer products such as film, degradable polymer plate.When manufacturing biodegradable fiber, how golden it is by using the present invention
Belong to ion technology to produce Degradable master batch, polymer filaments production process adds Degradable master batch to make degradable conjunction
Become fiber.This many metal ions oxidation technology is brand-new, and occurs in textile industry first.
For the present invention is further described, enumerate specific examples below.
Embodiment 1
Take polyester（10PE27）100g and transition metal salt（Copper stearate 2g, silver stearate 0.5g and chlorine
Change zinc 0.5g）Add in double helical mixer together, after mixing, the long filament of molten condition is extruded by spinneret, and long filament is cured,
And pass through water cooling, it is then cut into particle form.Wherein, rotating speed 100 ~ 280 rpm of double helical mixer.
Measure through FTIR spectrum and find, the degradable polymer compositionss that the present embodiment is obtained were in 3 days and UV process in 10 days
Afterwards, the carbonyl in sample structure (C=O) is in 1560 cm-1The intensity of absorption band significantly increase（See Fig. 1 and Fig. 2）.To degradable
It was observed that the maximum intensity at this peak after 14 days UV of polymer composition irradiate.Root it is documented that, show depositing of this peak in FTIR
Reflecting due to the photooxidative degradation in sample, and there occurs chain interruption.
Embodiment 2
Described polyester（Polyethylene terephthalate）100g and transition metal salt（Manganese oleate 5g and cobalt oleate 3g）And
0.05g antioxidant IRGANOX 1010 adds in double helical mixer together, and after mixing, the long filament of molten condition is by spinneret
Extrusion, long filament is cured, and passes through water cooling, is then cut into particle form.Wherein, the rotating speed of double helical mixer is
100~280 rpm.
Measure through FTIR spectrum and find, the degradable polymer compositionss that the present embodiment is obtained were in 3 days and UV process in 10 days
Afterwards, the carbonyl in sample structure (C=O) is in 1560 cm-1The intensity of absorption band significantly increase（See Fig. 3 and Fig. 4）.To degradable
It was observed that the maximum intensity at this peak after 14 days UV of polymer composition irradiate.Root it is documented that, show depositing of this peak in FTIR
Reflecting due to the photooxidative degradation in sample, and there occurs chain interruption.
Embodiment 3
Described polyamide（Polyphtalamide）100g and transition metal salt（2.5g copper oleate, 0.05g zinc oleate, 0.5g
Cerium stearate）Add in double helical mixer together, after mixing, the long filament of molten condition is extruded by spinneret, and long filament is cured,
And pass through water cooling, it is then cut into particle form.Wherein, the rotating speed of double helical mixer is 100 ~ 280 rpm.
Measure through FTIR spectrum and find, the degradable polymer compositionss that the present embodiment is obtained were in 3 days and UV process in 10 days
Afterwards, the carbonyl in sample structure (C=O) is in 1736cm-1The intensity of absorption band significantly increase（See Fig. 5 and Fig. 6）.To degradable
It was observed that the maximum intensity at this peak after 14 days UV of polymer composition irradiate.Root it is documented that, show depositing of this peak in FTIR
Reflecting due to the photooxidative degradation in sample, and there occurs chain interruption.
Embodiment 4
Described polystyrene 100g and transition metal salt（1.5g cobalt naphthenate and 0.05g zinc naphthenate）Add double spiral shells together
In oar blender, after mixing, the long filament of molten condition is extruded by spinneret, and long filament is cured, and passes through water cooling, is then cut
It is segmented into particle form.Wherein, the rotating speed of double helical mixer is 100 ~ 280 rpm.
After 30 days UV are processed, weight average molecular weight Mw of the degradable polymer compositionss of the present embodiment significantly reduces.Root
Weight average molecular weight according to polymer（Mw）International standard ASTM D6954 research, this shows that sample is opened after being exposed in UV light
Begin to degrade.
Number-average molecular weight (the M of the pure polystyrene of table 4 and the polystyrene being mixed with transition metal saltn) and weight average molecular weight
(Mw) contrast
Embodiment described above is only the preferred embodiment lifted for absolutely proving the present invention, the protection model of the present invention
Enclose not limited to this.Equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, all in the present invention
Protection domain within.Protection scope of the present invention is defined by claims.
Claims (1)
1. a kind of degradable polymer compositionss it is characterised in that
Described degradable polymer compositionss, are prepared via a method which：
Take 10PE27 100g and transition metal salt：Copper stearate 2g, silver stearate 0.5g and zinc chloride 0.5g mono-
Rise and add in double helical mixer, after mixing, the long filament of molten condition is extruded by spinneret, and long filament is cured, and pass through water-cooled
But, it is then cut into particle form；
Or, described degradable polymer compositionss, it is prepared via a method which：
Polyethylene terephthalate 100g and transition metal salt：Manganese oleate 5g and cobalt oleate 3g and 0.05g antioxidant IRGANOX
1010 add in double helical mixer together, and after mixing, the long filament of molten condition is extruded by spinneret, and long filament is cured, and
By water cooling, it is then cut into particle form；
Or, described degradable polymer compositionss, it is prepared via a method which：
Polyphtalamide 100g and transition metal salt：2.5g copper oleate, 0.05g zinc oleate and 0.5g cerium stearate, together plus
Enter in double helical mixer, after mixing, the long filament of molten condition is extruded by spinneret, and long filament is cured, and pass through water cooling, so
After be cut into particle form；
Or, described degradable polymer compositionss, it is prepared via a method which：
Polystyrene 100g and transition metal salt：1.5g cobalt naphthenate and 0.05g zinc naphthenate add double helical mixer together
In, after mixing, the long filament of molten condition is extruded by spinneret, and long filament is cured, and passes through water cooling, is then cut into granule
Form.
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| CN106032422A (en) * | 2015-03-13 | 2016-10-19 | 香港纺织及成衣研发中心有限公司 | Degradable synthetic fiber composition, preparation method thereof and product |
| US20200258362A1 (en) * | 2017-11-03 | 2020-08-13 | Jonathan L. Liss | Smoke detection material, method, apparatus and kit |
| CN110028688A (en) * | 2018-12-19 | 2019-07-19 | 香港生产力促进局 | A kind of preparation method and applications of degradable poly styrene materials |
| CN112030260B (en) * | 2020-08-31 | 2021-06-11 | 江南大学 | Preparation method of easily degradable PET luminescent fiber and product thereof |
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| CN1267681A (en) * | 1999-03-19 | 2000-09-27 | 北京清大亚太科技研究中心 | Degradeable resin composition and its preparation and application |
| CN101665625A (en) * | 2008-09-03 | 2010-03-10 | 王丽红 | Plastic degrading composition, use of same and plastic and product containing same |
| CN102177196A (en) * | 2008-10-08 | 2011-09-07 | 威尔斯塑料有限公司 | Polymer additives |
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| EP0563291A1 (en) * | 1990-12-21 | 1993-10-06 | Ecostar International L.P. | Photodegradable plastic composition |
| US6482872B2 (en) * | 1999-04-01 | 2002-11-19 | Programmable Materials, Inc. | Process for manufacturing a biodegradable polymeric composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1267681A (en) * | 1999-03-19 | 2000-09-27 | 北京清大亚太科技研究中心 | Degradeable resin composition and its preparation and application |
| CN101665625A (en) * | 2008-09-03 | 2010-03-10 | 王丽红 | Plastic degrading composition, use of same and plastic and product containing same |
| CN102177196A (en) * | 2008-10-08 | 2011-09-07 | 威尔斯塑料有限公司 | Polymer additives |
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