CN107236147B - A kind of method of crystalline plastics high-performance bio degradation - Google Patents
A kind of method of crystalline plastics high-performance bio degradation Download PDFInfo
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- CN107236147B CN107236147B CN201710322634.2A CN201710322634A CN107236147B CN 107236147 B CN107236147 B CN 107236147B CN 201710322634 A CN201710322634 A CN 201710322634A CN 107236147 B CN107236147 B CN 107236147B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The present invention relates to a kind of methods of crystalline plastics high-performance bio degradation, including crystalline plastics are placed in more than or equal to its melting temperature (Tm) under the conditions of carry out melt process；Then it is transferred to progress quenching processing in cold medium rapidly；Enzymolysis processing will be carried out in quenching treated crystalline plastics.The present invention carries out crystalline plastics by physical method to melt-quenching processing, on the basis of not changing chemical molecular structure, realize crystalline plastics condensed state structure from crystal type to unbodied transformation, the crystallinity of plastics is greatly lowered, the probability that enzyme approaches and acts on plastics is improved, to greatly improve crystalline plastics biodegrade efficiency.
Description
Technical field
The present invention relates to a kind of methods of crystalline plastics high-performance bio degradation, belong to biotechnology and environmental project
Technical field.
Background technique
Between 2005-2015, world's plastics annual output has risen to 320,000,000 tons from 230,000,000 tons.Plastics consumption generates
A large amount of plastic wastes, it is most of all to enter in refuse landfill or be simply discarded in environment.Since stable material is special
Property, plastic wastes decompose under field conditions (factors) very slowly, the plastic wastes constantly accumulated seriously polluted the ecosystem.
Using biological enzyme by plastic degradation be synthon or oligomer, and recycle monomer or oligomer as plastics synthesis
Raw material, be gradually fully realized for various reasons be it is a kind of solve plastic wastes new way (PCT, Method for recycling
plastic products,WO 2014/079844A1).Such as polyethylene terephthalate (PET) and poly- terephthaldehyde
Sour butanediol ester (PBT) etc. can be hydrolyzed into monomer or oligomer by cutinase (EC 3.1.1.74).Polycaprolactam/nylon-
6 (PA-6), polyhexamethylene adipamide/nylon -66 (PA-66), polyhexamethylene sebacamide/nylon-610 (PA-610) etc. can be by
Amidase (EC 3.5.1.4) is hydrolyzed into monomer or oligomer.Poly L-lactic acid (PLLA) can be by serine protease (EC
3.4.21.64) or lipase (EC 3.1.1.3) is hydrolyzed into monomer or oligomer.
However, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), polycaprolactam/
Nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66 (PA-66), polyhexamethylene sebacamide/nylon-610 (PA-610) gather
The plastics such as D-lactic acid (PLLA) are usually all existing for crystal type.In the biodegradation process of crystalline plastics, crystal region
The compact texture that is formed of molecular stuffing hinder the close of enzyme and effect so that the biodegradable efficiency of crystalline plastics is very low
Summary of the invention
For the deficiency of existing crystalline plastic biodegrade inefficiency, the purpose of the present invention is to provide a kind of crystallizations
Property plastics high-performance bio degradation method.
The present invention realizes that the technical solution of above-mentioned purpose is as follows:
A kind of method of crystalline plastics high-performance bio degradation, includes the following steps:
1) crystalline plastics are placed in more than or equal to its melting temperature (Tm) under the conditions of carry out melt process；
2) by crystalline plastics in a molten state, it is transferred to progress quenching processing in cold medium rapidly；
3) enzymolysis processing will be carried out in quenching treated crystalline plastics.
Generally, it needs to carry out melt process again after cleaning, drying by crystalline plastics.
The study found that being more conducive to subsequent melt processing and enzymolysis processing after crystalline plastics are sheared or are crushed.Preferably,
Length 5cm or less is sheared or be crushed to crystalline plastics.
The study found that especially when melt process, temperature is higher than crystalline plastics melting temperature (Tm) 10-30 DEG C when, make
Molecule is in amorphous state in the crystalline plastics melted completely, more conducively subsequent quenching processing and enzymolysis processing.Consider section
The about energy, melting operating temperature are higher than crystalline plastics melting temperature (Tm) 10-30 DEG C.
The study found that quenching treatment temperature is necessarily less than the glass transition temperature (T equal to crystalline plastics itselfg)。
Quenching, i.e. quick refrigeration can make the molecule in crystalline plastics in a molten state have little time to crystallize, and keep amorphous
State is simultaneously fixed up.
Preferably, the time that step 1) molten state crystalline plastics are transferred to the cold medium process of step 2) is less than or equal to
Flexible chain (the t of crystalline plastics itself1/2)。
Preferably, the crystallinity of crystalline plastics is less than or equal to 5% after control melt process, quenching processing, then carries out enzyme
Solution processing.The probability that enzyme approaches and acts on plastics is improved the study found that being more advantageous to this condition, to greatly improve crystallization
The biodegradable efficiency of plastic.
Quenching processing cold medium used can use cold air (0-25 DEG C), water (0-25 DEG C) or liquid nitrogen etc.；Preferably water (0-25
℃)。
For most of crystalline plastics, under normal circumstances, the melt process time can be controlled in 3-10min；By step 1)
The time that molten state crystalline plastics are transferred to the cold medium process of step 2) can be controlled in 10s or less；Quenching handles the time can
Control is in 3-10min；Quenching treatment temperature can be controlled in 0-25 DEG C.
Crystalline plastics of the present invention include but is not limited to polyethylene terephthalate (PET), poly- terephthaldehyde
Sour butanediol ester (PBT), polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66 (PA-66), the poly- last of the ten Heavenly stems two
Acyl hexamethylene diamine/nylon-610 (PA-610), Poly L-lactic acid (PLLA) etc..
Preferably, the melt process temperature of polyethylene terephthalate (PET) is 270 DEG C -300 DEG C, is gathered to benzene two
The melt process temperature of formic acid butanediol ester (PBT) is 230 DEG C -250 DEG C, at the melting of polycaprolactam/nylon-6 (PA-6)
Managing temperature is 220 DEG C -250 DEG C, and the melt process temperature of polyhexamethylene adipamide/nylon -66 (PA-66) is 270 DEG C -300 DEG C,
The melt process temperature of polyhexamethylene sebacamide/nylon-610 (PA-610) is 230 DEG C -250 DEG C, Poly L-lactic acid (PLLA)
Melt process temperature is 170 DEG C -200 DEG C.
Conventional method in that art can be used and carry out enzymolysis processing.
It is preferred that using cutinase (EC 3.1.1.74), amidase (EC 3.5.1.4), serine protease (EC
3.4.21.64) or lipase (EC 3.1.1.3) carries out biodegradable processing.
Preferably, when crystalline plastics are polyethylene terephthalate (PET) or polybutylene terephthalate (PBT)
(PBT) when, it is preferable that hydrolysis result is carried out using cutinase (EC 3.1.1.74)；Phosphate of the pH value for 7.0 especially is being added
Under buffer conditions.
It is further preferred that the enzymatic hydrolysis condition:
In terms of g/mL, quenching treated polyethylene terephthalate (PET) or polybutylene terephthalate (PBT)
It (PBT) is 1:10-1:100 (preferably 1:20) with the ratio of the phosphate buffer；
In terms of g/mL, quenching treated polyethylene terephthalate (PET) or polybutylene terephthalate (PBT)
It (PBT) is 1:0.1-1:1 (preferably 1:0.5) with the ratio of cutinase (EC 3.1.1.74)；
Reaction temperature is 40-60 DEG C, and the reaction time is 12-96h, revolving speed 150r/min.
Enzyme digestion reaction terminates to separate cutinase using molecular film, and taking filtrate is catabolite monomer or oligomer.
Preferably, when crystalline plastics are polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66
(PA-66) or when polyhexamethylene sebacamide/nylon-610 (PA-610) hydrolysis result, is carried out using amidase (EC 3.5.1.4)
Preferably；Especially under the conditions of the phosphate buffer that pH value is 7.0 is added.
It is further preferred that the enzymatic hydrolysis condition:
In terms of g/mL, quenching treated polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66
(PA-66) or the ratio of polyhexamethylene sebacamide/nylon-610 (PA-610) and the phosphate buffer is 1:10-1:100
(preferably 1:20).
In terms of g/mL, quenching treated polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66
(PA-66) or the ratio of polyhexamethylene sebacamide/nylon-610 (PA-610) and amidase (EC 3.5.1.4) are 1:0.1-1:1
(preferably 1:0.5).
Reaction temperature is 40-60 DEG C, and the reaction time is 12-96h, revolving speed 150r/min.
Enzyme digestion reaction terminates using molecular film separating amide enzyme, and taking filtrate is catabolite monomer or oligomer.
Preferably, when crystalline plastics are Poly L-lactic acid (PLLA), using serine protease (EC
3.4.21.64) or lipase (EC 3.1.1.3) progress hydrolysis result is preferable；Phosphate of the pH value for 7.0 especially is being added
Under buffer conditions.
It is further preferred that the enzymatic hydrolysis condition:
In terms of g/mL, the ratio of quenching treated Poly L-lactic acid (PLLA) and the phosphate buffer is 1:10-
1:100 (preferably 1:20).
In terms of g/mL, quenching treated Poly L-lactic acid (PLLA) and serine protease (EC 3.4.21.64) or rouge
The ratio of fat enzyme (EC 3.1.1.3) is 1:0.1-1:1 (preferably 1:0.5).
Reaction temperature is 40-60 DEG C, and the reaction time is 12-96h, revolving speed 150r/min.
Using molecular film separation serine protease or lipase after enzyme digestion reaction, taking filtrate is catabolite list
Body or oligomer.
Melting temperature (the T of crystalline plastics of the present invention itselfm), glass transition temperature (Tg) and crystallinity
Reference book is measured or consulted by existing conventional method to obtain.
In the specific embodiment of the invention, the melting temperature (T of described crystalline plastics itselfm), glass transition temperature
Spend (Tg) and crystallinity by differential scanning calorimeter (Differential Scanning Calorimetry, DSC) measure.
The present invention carries out crystalline plastics by physical method to melt-quenching processing, is not changing chemical molecular structure
On the basis of, realize that from crystal type to unbodied transformation, the crystallinity of plastics is greatly lowered in crystalline plastics condensed state structure,
The probability that enzyme approaches and acts on plastics is improved, to realize the high-performance bio degradation of crystalline plastics.
Detailed description of the invention
Fig. 1 is DSC (differential scanning calorimetry, the differential scanning of crystalline plastics
Calorimetry) curve graph；Wherein Figure 1A is the DSC curve of plastic raw materials polyethylene terephthalate (PET), is only gone out
Melting peak is showed；Figure 1B is the DSC curve of the polyethylene terephthalate (PET) after melting-quenching, cold crystallization occurs
Peak and melting peak illustrate a large amount of amorphous region occurred；Fig. 1 C is plastic raw materials polybutylene terephthalate (PBT) (PBT's)
Only there is melting peak in DSC curve；Fig. 1 D is the DSC curve of the polybutylene terephthalate (PBT) (PBT) after melting-quenching,
There is cold crystallization peak and melting peak, illustrates a large amount of amorphous region occurred.
Fig. 2 indicates crystalline plastics raw material polyethylene terephthalate (PET), poly- to benzene two after melting-quenching
Formic acid glycol ester (PET), poly- pair after crystalline plastics raw material polybutylene terephthalate (PBT) (PBT) and melting-quenching
Biodegradable efficiency of the benzene dicarboxylic acid butanediol ester (PBT) through enzymatic 96h.
Fig. 3 indicates crystalline plastics raw material polyethylene terephthalate (PET), poly- to benzene two after melting-quenching
Formic acid glycol ester (PET), poly- pair after crystalline plastics raw material polybutylene terephthalate (PBT) (PBT) and melting-quenching
Benzene dicarboxylic acid butanediol ester (PBT) is through surface topography scanning electron microscope (SEM) figure in enzymatic 96h.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
Biodegrade efficiency according to the present invention is calculated as follows:
Biodegradable efficiency %=(plastics weight after plastics weight-degradation before degrading)/preceding plastics weight of degrading ×
100%
Melting temperature (the T of crystalline plastics as described below itselfm), glass transition temperature (Tg) and crystallinity by showing
Difference scanning calorimeter (Differential Scanning Calorimetry, DSC) measurement.
Embodiment 1
A kind of method of crystalline plastics high-performance bio degradation, includes the following steps:
The crystalline plastics be polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT),
Its processing step is as follows:
1) prepared by plastic raw materials: by polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) (PBT)
Etc. cleaning up, shearing to less than 5cm length are dried spare.Measure the melting temperature (T of described crystalline plastics itselfm), glass
Glass transition temperature (Tg) and crystallinity: the melting temperature (T of polyethylene terephthalate (PET)m) it is 270 DEG C, vitrifying
Transition temperature (Tg) it be 69 DEG C and crystallinity is 30%.Melting temperature (the T of polybutylene terephthalate (PBT) (PBT)m) it is 224
DEG C, glass transition temperature (Tg) it be 52 DEG C and crystallinity is 32%.
2) melt process: by above-mentioned crystalline plastics heating melting, the melting work of polyethylene terephthalate (PET)
It is set as 300 DEG C as temperature parameter, the melting operating temperature parameter setting of polybutylene terephthalate (PBT) (PBT) is 250 DEG C,
The melting working time of above-mentioned plastics is set as 3min.
3) quenching is handled: by above-mentioned crystalline plastics in a molten state, being transferred to rapidly in cold medium and is carried out quenching, turns
Shift time is less than 10s, and the quenching time is set as 3min.Quenching media temperature parameter is set as 0 DEG C, and cold medium is water.
4) biodegradable: by the polyethylene terephthalate (PET) or poly terephthalic acid after the above-mentioned quenching of 1.00g
The phosphate buffer and cutinase (EC 3.1.1.74) that pH value is 7.0 is added in butanediol ester (PBT), to poly terephthalic acid
Glycol ester (PET) or polybutylene terephthalate (PBT) (PBT) carry out biodegrade.Poly terephthalic acid second two after quenching
The solid-to-liquid ratio of alcohol ester (PET) or polybutylene terephthalate (PBT) (PBT) and phosphate buffer is 1:20g/mL, after quenching
The solid-to-liquid ratio of polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) (PBT) and cutinase is 1:0.5g/
ML, reaction temperature are 60 DEG C, reaction time 96h, revolving speed 150r/min.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: using method provided by the invention, and melt process-quenching processing makes polyethylene terephthalate
(PET) crystallinity is reduced to 3.6% by 30%, is reduced to the crystallinity of polybutylene terephthalate (PBT) (PBT) by 32%
5.0% (as shown in Figure 1).In 96h, the biodegradable efficiency of polyethylene terephthalate (PET) reaches 75.2%, and poly- pair
The biodegradable efficiency of benzene dicarboxylic acid butanediol ester (PBT) reaches 71.4% (as shown in Figure 2).In 96h, pass through scanning electron
Microscope (SEM) observes that the sample surfaces of the method for the present invention degradation occur very significantly corroding (as shown in Figure 3).
Comparative example 1-1
A kind of biodegradable method of crystalline plastics, the difference with embodiment 1 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, directly using enzyme to crystalline plastics raw material polyethylene terephthalate
(PET) (crystallinity 30%) and polybutylene terephthalate (PBT) (PBT) (crystallinity 32%) carry out biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: method provided by the invention is not used, directly using enzyme to the poly- terephthaldehyde of crystalline plastics raw material
Sour glycol ester (PET) (crystallinity 30%) and crystalline plastics raw material polybutylene terephthalate (PBT) (PBT) (crystallinity
32%) it carries out biodegradable (as shown in Figure 1).In 96h, the biodegradable efficiency of polyethylene terephthalate (PET) is only
It is 0.16%, it is 470 times lower than the degradation efficiency (75.2%) that method provided by the invention generates；Polybutylene terephthalate (PBT)
(PBT) biodegradable efficiency is only 0.25%, 286 times lower than the degradation efficiency (71.4%) that method provided by the invention generates
(as shown in Figure 2).In 96h, observes that plastic raw materials sample surfaces are very smooth by scanning electron microscope (SEM), do not have
There is the significant erosion (as shown in Figure 3) generated such as method provided by the invention.
Comparative example 1-2
A kind of biodegradable method of crystalline plastics, the difference with embodiment 1 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, and only carries out melt process, then natural cooling.Using enzyme to melting-nature
Cooling crystalline plastics polyethylene terephthalate (PET) (crystallinity 15%) and polybutylene terephthalate (PBT)
(PBT) (crystallinity 19%) carries out biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: it to crystalline plastics raw material without melting provided by the invention-quenching processing, and is only melted
It handles, then natural cooling.Recrystallization process occurs for natural cooling process.Poly terephthalic acid second after melting-natural cooling
The crystallinity of diol ester (PET) is 15%, and the crystallinity of polybutylene terephthalate (PBT) (PBT) is 19%.In 96h, melting-
The biodegradable efficiency of polyethylene terephthalate (PET) is only 0.18% after natural cooling, than side provided by the invention
The degradation efficiency (75.2%) that method generates is 417 times low；The biodegradable efficiency of polybutylene terephthalate (PBT) (PBT) is only
0.22%, it is 325 times lower than the degradation efficiency (71.4%) that method provided by the invention generates.
Comparative example 1-3
A kind of biodegradable method of crystalline plastics, the difference with embodiment 1 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, and only carries out quenching processing.Only quenching is handled using enzyme poly- pair of crystal type
Ethylene terephthalate (PET) (crystallinity 30%) and polybutylene terephthalate (PBT) (PBT) (crystallinity 32%) carry out
Biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: to crystalline plastics raw material without melting provided by the invention-quenching processing, and quenching is only carried out
Processing.Plastics polyethylene terephthalate (PET) crystallinity after the processing of quenching is still 30% and poly- terephthaldehyde
The crystallinity of sour butanediol ester (PBT) is still 32%.In 96h, the rear polyethylene terephthalate (PET) of quenching processing
Biodegradable efficiency be only 0.16%, than method provided by the invention generate degradation efficiency (75.2%) it is 470 times low；Poly- pair
The biodegradable efficiency of benzene dicarboxylic acid butanediol ester (PBT) is only 0.25%, the degradation effect generated than method provided by the invention
Rate (71.4%) is 286 times low.
In conclusion these results suggest that, method provided by the invention can be to polyethylene terephthalate (PET)
Or polybutylene terephthalate (PBT) (PBT) carries out high-performance bio degradation.
Embodiment 2
A kind of method of crystalline plastics high-performance bio degradation, includes the following steps:
The crystalline plastics are polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66 (PA-
66), polyhexamethylene sebacamide/nylon-610 (PA-610)；
1) prepared by plastic raw materials: by polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66 (PA-
66), polyhexamethylene sebacamide/nylon-610 (PA-610) cleans up, and shearing to less than 5cm length are dried spare.Measurement knot
Melting temperature (the T of crystal form plastics itselfm), glass transition temperature (Tg) and crystallinity: polycaprolactam/nylon-6 (PA-6)
Melting temperature (Tm) it is 220 DEG C, glass transition temperature (Tg) it be 55 DEG C and crystallinity is 35%.Polyhexamethylene adipamide/Buddhist nun
Melting temperature (the T of -66 (PA-66) of dragonm) it is 267 DEG C, glass transition temperature (Tg) it be 57 DEG C and crystallinity is 32%.The poly- last of the ten Heavenly stems
Two acyl hexamethylene diamines/nylon-610 (PA-610) melting temperature (Tm) it is 228 DEG C, glass transition temperature (Tg) it is 50 DEG C and knot
Brilliant degree is 32%.
2) melt process: by above-mentioned crystalline plastics heating melting, the melting work of polycaprolactam/nylon-6 (PA-6)
Temperature parameter is set as 250 DEG C, and the melting operating temperature parameter setting of polyhexamethylene adipamide/nylon -66 (PA-66) is 300
DEG C, the melting operating temperature parameter setting of polyhexamethylene sebacamide/nylon-610 (PA-610) is 250 DEG C, and above-mentioned plastics melt
Melting the working time is set as 3min.
3) quenching is handled: by above-mentioned crystalline plastics in a molten state, being transferred to rapidly in cold medium and is carried out quenching, turns
Shift time is less than 10s, and the quenching time is set as 3min.Quenching media temperature parameter is set as 0 DEG C, and cold medium is water.
4) biodegradable: by polycaprolactam/nylon-6 (PA-6) after the above-mentioned quenching of 1.00g, polyhexamethylene adipamide/
Nylon -66 (PA-66), be added in polyhexamethylene sebacamide/nylon-610 (PA-610) phosphate buffer that pH value is 7.0 and
Amidase (EC 3.5.1.4), to polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66 (PA-66) gathers
Hexamethylene sebacamide/nylon-610 (PA-610) carries out biodegrade.Polycaprolactam/nylon-6 (PA-6) after quenching gathers
Hexamethylene adipamide/nylon -66 (PA-66), polyhexamethylene sebacamide/nylon-610 (PA-610) are consolidated with phosphate buffer
Liquor ratio is 1:20g/mL, polycaprolactam/nylon-6 (PA-6) after quenching, polyhexamethylene adipamide/nylon -66 (PA-66),
The solid-to-liquid ratio of polyhexamethylene sebacamide/nylon-610 (PA-610) and amidase is 1:0.5g/mL, and reaction temperature is 40 DEG C, instead
It is 96h, revolving speed 150r/min between seasonable.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: using method provided by the invention, and melt process-quenching processing makes polycaprolactam/nylon-6
(PA-6) crystallinity is reduced to 4.2% by 35%, makes the crystallinity of polyhexamethylene adipamide/nylon -66 (PA-66) by 32% drop
It is 5.0%, the crystallinity of polyhexamethylene sebacamide/nylon-610 (PA-610) is made to be reduced to 3.1% by 32%.In 96h, gather in oneself
The biodegradable efficiency of amide/nylon-6 (PA-6) reaches 71.4%, the biology of polyhexamethylene adipamide/nylon -66 (PA-66)
Degradation efficiency reaches 73.2%, and the biodegradable efficiency of polyhexamethylene sebacamide/nylon-610 (PA-610) reaches 70.5%.
Comparative example 2-1
A kind of biodegradable method of crystalline plastics, the difference with embodiment 2 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, directly using enzyme to crystalline plastics raw material polycaprolactam/nylon-6 (PA-
6) (crystallinity 35%), polyhexamethylene adipamide/nylon -66 (PA-66) (crystallinity 32%) and polyhexamethylene sebacamide/Buddhist nun
Imperial -610 (PA-610) (crystallinity 32%) carry out biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: do not use method provided by the invention, directly utilize enzyme to crystalline plastics raw material polycaprolactam/
Nylon-6 (PA-6) (crystallinity 35%), polyhexamethylene adipamide/nylon -66 (PA-66) (crystallinity 32%) and poly- decanedioyl
Hexamethylene diamine/nylon-610 (PA-610) (crystallinity 32%) carries out biodegrade.In 96h, polycaprolactam/nylon-6 (PA-6)
Biodegradable efficiency be only 0.17%, than method provided by the invention generate degradation efficiency (71.4%) it is 420 times low；Gather oneself
The biodegradable efficiency of two acyl hexamethylene diamines/nylon -66 (PA-66) is only 0.22%, the drop generated than method provided by the invention
It is 333 times low to solve efficiency (73.2%).The biodegradable efficiency of polyhexamethylene sebacamide/nylon-610 (PA-610) is only
0.23%, it is 307 times lower than the degradation efficiency (70.5%) that method provided by the invention generates.
Comparative example 2-2
A kind of biodegradable method of crystalline plastics, the difference with embodiment 2 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, and only carries out melt process, then natural cooling.Using enzyme to melting-nature
Cooling crystalline plastics polycaprolactam/nylon-6 (PA-6) (crystallinity 19%), polyhexamethylene adipamide/nylon -66
(PA-66) (crystallinity 17%) and polyhexamethylene sebacamide/nylon-610 (PA-610) (crystallinity 18%) carry out biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: it to crystalline plastics raw material without melting provided by the invention-quenching processing, and is only melted
It handles, then natural cooling.Recrystallization process occurs for natural cooling process.Polycaprolactam/Buddhist nun after melting-natural cooling
The crystallinity of -6 (PA-6) of dragon is 19%, and the crystallinity of polyhexamethylene adipamide/nylon -66 (PA-66) is 17% and the poly- last of the ten Heavenly stems two
Acyl hexamethylene diamine/nylon-610 (PA-610) crystallinity is 18%.In 96h, polycaprolactam/nylon-after melting-natural cooling
The biodegradable efficiency of 6 (PA-6) is only 0.16%, lower by 446 than the degradation efficiency (71.4%) that method provided by the invention generates
Times；The biodegradable efficiency of polyhexamethylene adipamide/nylon -66 (PA-66) is only 0.21%, is produced than method provided by the invention
Raw degradation efficiency (73.2%) is 349 times low.The biodegradable efficiency of polyhexamethylene sebacamide/nylon-610 (PA-610) is only
0.19%, it is 371 times lower than the degradation efficiency (70.5%) that method provided by the invention generates.
Comparative example 2-3
A kind of biodegradable method of crystalline plastics, the difference with embodiment 2 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, and only carries out quenching processing.Gather oneself using the crystal type that enzyme handles only quenching
Lactams/nylon-6 (PA-6) (crystallinity 35%), polyhexamethylene adipamide/nylon -66 (PA-66) (crystallinity 32%) and poly-
Hexamethylene sebacamide/nylon-610 (PA-610) (crystallinity 32%) carries out biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: to crystalline plastics raw material without melting provided by the invention-quenching processing, and quenching is only carried out
Processing.Plastics polycaprolactam/nylon-6 (PA-6) crystallinity after the processing of quenching is still 35%, poly hexamethylene adipamide oneself two
The crystallinity of amine/nylon -66 (PA-66) be still 32% and polyhexamethylene sebacamide/nylon-610 (PA-610) crystallinity still
It is 32%.In 96h, the biodegradable efficiency of rear polycaprolactam/nylon-6 (PA-6) of quenching processing is only 0.17%, than
The degradation efficiency (71.4%) that method provided by the invention generates is 420 times low；Polyhexamethylene adipamide/nylon -66 (PA-66)
Biodegradable efficiency is only 0.22%, 333 times lower than the degradation efficiency (73.2%) that method provided by the invention generates.The poly- last of the ten Heavenly stems two
The biodegradable efficiency of acyl hexamethylene diamine/nylon-610 (PA-610) is only 0.23%, the drop generated than method provided by the invention
It is 307 times low to solve efficiency (70.5%).
In conclusion these results suggest that, method provided by the invention can to polycaprolactam/nylon-6 (PA-6),
Polyhexamethylene adipamide/nylon -66 (PA-66) and polyhexamethylene sebacamide/nylon-610 (PA-610) carry out high-performance bio drop
Solution.
Embodiment 3
A kind of method of crystalline plastics high-performance bio degradation, includes the following steps:
The method of the biodegradable efficiency of the crystalline plastics Poly L-lactic acid (PLLA), processing step are as follows:
1) prepared by plastic raw materials: Poly L-lactic acid (PLLA) etc. being cleaned up, shearing to less than 5cm length are dried standby
With.Measure the melting temperature (T of crystalline plastics itselfm), glass transition temperature (Tg) and crystallinity: Poly L-lactic acid
(PLLA) melting temperature (Tm) it is 175 DEG C, glass transition temperature (Tg) it be 55 DEG C and crystallinity is 20%.
2) melt process: the melting operating temperature of above-mentioned crystalline plastics heating melting, Poly L-lactic acid (PLLA) is joined
Number is set as 200 DEG C, and the melting working time of above-mentioned plastics is set as 3min.
3) quenching is handled: by above-mentioned crystalline plastics in a molten state, being transferred to rapidly in cold medium and is carried out quenching, turns
Shift time is less than 10s, and the quenching time is set as 3min.Quenching media temperature parameter is set as 0 DEG C, and cold medium is water.
4) biodegradable: the phosphate buffer and silk that pH value is 7.0 is added in the Poly L-lactic acid (PLLA) after quenching
Serine protease (EC 3.4.21.64) or lipase (EC 3.1.1.3) carry out biodegrade to Poly L-lactic acid (PLLA).
The solid-to-liquid ratio of Poly L-lactic acid (PLLA) and phosphate buffer after quenching is 1:20g/mL, smashed Poly L-lactic acid
It (PLLA) is 1:0.5g/mL with the solid-to-liquid ratio of serine protease or lipase, reaction temperature is 40 DEG C, reaction time 96h,
Revolving speed is 150r/min.
After reaction using molecular film separation serine protease or lipase, take filtrate be catabolite monomer or
Oligomer.
Experimental result: using method provided by the invention, and melt process-quenching processing makes Poly L-lactic acid (PLLA)
Crystallinity is reduced to 3.2% by 20%.In 96h, the biodegradable efficiency of Poly L-lactic acid (PLLA) reaches 75.4% by comparative example.
Comparative example 3-1
A kind of biodegradable method of crystalline plastics, the difference with embodiment 3 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, directly using enzyme to crystalline plastics raw material Poly L-lactic acid (PLLA) (crystallization
20%) degree carries out biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: method provided by the invention is not used, directly using enzyme to crystalline plastics raw material Poly L-lactic acid
(PLLA) (crystallinity 20%) carries out biodegrade.In 96h, the biodegrade effect of Poly L-lactic acid (PLLA) (crystallinity 20%)
Rate is only 0.16%, 471 times lower than the degradation efficiency (75.4%) that method provided by the invention generates.
Comparative example 3-2
A kind of biodegradable method of crystalline plastics, the difference with embodiment 3 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, and only carries out melt process, then natural cooling.Using enzyme to melting-nature
Cooling crystalline plastics Poly L-lactic acid (PLLA) (crystallinity 16%) carries out biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: it to crystalline plastics raw material without melting provided by the invention-quenching processing, and is only melted
It handles, then natural cooling.Recrystallization process occurs for natural cooling process.Plastics Poly L-lactic acid after melting-natural cooling
(PLLA) crystallinity is 16%.In 96h, the biodegradable efficiency of Poly L-lactic acid (PLLA) is only after melting-natural cooling
0.17%, it is 443 times lower than the degradation efficiency (75.4%) that method provided by the invention generates.
Comparative example 3-3
A kind of biodegradable method of crystalline plastics, the difference with embodiment 3 be only that, not to crystalline plastics raw material
Melting provided by the invention-quenching processing is carried out, and only carries out quenching processing.The crystalline plastics that only quenching is handled using enzyme
Poly L-lactic acid (PLLA) (crystallinity 20%) carries out biodegrade.
Molecule UF membrane is utilized after reaction, measures the complete plastics dry weight of unreacted, calculates biodegradable efficiency.
Experimental result: to crystalline plastics raw material without melting provided by the invention-quenching processing, and quenching is only carried out
Processing.Plastics Poly L-lactic acid (PLLA) crystallinity after the processing of quenching is still 20%.In 96h, after quenching processing
The biodegradable efficiency of Poly L-lactic acid (PLLA) is only 0.16%, the degradation efficiency generated than method provided by the invention
(75.4%) low 471 times.
In conclusion these results suggest that, method provided by the invention can carry out Poly L-lactic acid (PLLA) efficient
Biodegrade.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a kind of method of crystalline plastics high-performance bio degradation, which comprises the steps of:
1) crystalline plastics are placed in more than or equal to its melting temperature (Tm) under the conditions of carry out melt process；
Temperature is higher than crystalline plastics melting temperature (T when the melt processm)10-30℃；
2) by crystalline plastics in a molten state, it is transferred to progress quenching processing in cold medium rapidly；
The quenching treatment temperature is less than or equal to the glass transition temperature (T of crystalline plastics itselfg)；
3) enzymolysis processing will be carried out in quenching treated crystalline plastics.
2. the method according to claim 1, wherein step 1) molten state crystalline plastics are transferred to step 2)
Cold medium process time be less than or equal to crystalline plastics itself flexible chain (t1/2)。
3. method according to claim 1 or 2, which is characterized in that crystalline plastics after control melt process, quenching processing
Crystallinity be less than or equal to 5%, then carry out enzymolysis processing.
4. method according to claim 1 or 2, which is characterized in that the melt process time control is in 3-10min；It will
The time that step 1) molten state crystalline plastics are transferred to the cold medium process of step 2) controls in 10s or less；When quenching processing
Between control in 3-10min；Quenching treatment temperature is controlled at 0-25 DEG C.
5. method according to claim 1 or 2, which is characterized in that the crystalline plastics are selected from poly terephthalic acid second
Diol ester (PET), polybutylene terephthalate (PBT) (PBT), polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/
Nylon -66 (PA-66), polyhexamethylene sebacamide/nylon-610 (PA-610) or Poly L-lactic acid (PLLA).
6. according to the method described in claim 5, it is characterized in that, the melt process of polyethylene terephthalate (PET)
Temperature is 270 DEG C -300 DEG C, and the melt process temperature of polybutylene terephthalate (PBT) (PBT) is 230 DEG C -250 DEG C, is gathered in oneself
The melt process temperature of amide/nylon-6 (PA-6) is 220 DEG C -250 DEG C, polyhexamethylene adipamide/nylon -66 (PA-66)
Melt process temperature is 270 DEG C -300 DEG C, and the melt process temperature of polyhexamethylene sebacamide/nylon-610 (PA-610) is 230
DEG C -250 DEG C, the melt process temperature of Poly L-lactic acid (PLLA) is 170 DEG C -200 DEG C.
7. according to claim 1, method described in 2 or 6, which is characterized in that use cutinase (EC3.1.1.74), amidase
(EC3.5.1.4), serine protease (EC3.4.21.64) or lipase (EC3.1.1.3) carry out biodegradable processing.
8. method according to claim 1 or 2, which is characterized in that when crystalline plastics are polyethylene terephthalate
Ester (PET) or when polybutylene terephthalate (PBT) (PBT), uses under the conditions of the phosphate buffer that pH value is 7.0 is added
Cutinase (EC3.1.1.74) is digested；
When crystalline plastics are polycaprolactam/nylon-6 (PA-6), polyhexamethylene adipamide/nylon -66 (PA-66) or the poly- last of the ten Heavenly stems
When two acyl hexamethylene diamines/nylon-610 (PA-610), amidase is used under the conditions of the phosphate buffer that pH value is 7.0 is added
(EC3.5.1.4) it is digested；
When crystalline plastics are Poly L-lactic acid (PLLA), used under the conditions of the phosphate buffer that pH value is 7.0 is added
Serine protease (EC3.4.21.64) or lipase (EC3.1.1.3) are digested；
The enzymatic hydrolysis condition:
In terms of g/mL, the ratio of quenching treated crystalline plastics and the phosphate buffer is 1:10-1:100；
In terms of g/mL, the ratio of quenching treated crystalline plastics and enzyme is 1:0.1-1:1；
Reaction temperature is 40-60 DEG C, and the reaction time is 12-96h, revolving speed 150r/min.
9. according to the method described in claim 8, it is characterized in that, the enzymatic hydrolysis condition:
In terms of g/mL, the ratio of quenching treated crystalline plastics and the phosphate buffer is 1:20；
In terms of g/mL, the ratio of quenching treated crystalline plastics and enzyme is 1:0.5.
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