CN109627709A - A kind of degradable biological base master batch and the preparation method and application thereof - Google Patents
A kind of degradable biological base master batch and the preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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Abstract
The present invention relates to a kind of degradable biological base master batches and the preparation method and application thereof, belong to polymer modification field.Degradable biological base master batch of the present invention includes Biodegradable polyester and biologic packing material, and the weight ratio of Biodegradable polyester and biologic packing material is 20-40:60-80；Total organic carbon of the biologic packing material in natural biomass resource, the biologic packing material accounts for 80% or more of total carbon weight in biologic packing material, the partial size D of the biologic packing material50It is 0.5~8 μm；Total organic carbon in the degradable biological base master batch accounts for the 60%-100% of total carbon weight in degradable biological base master batch.Degradable biological base master batch has been made by raw material of biologic packing material in the present invention, simultaneously, biodegradable polyesters composition has been made using the degradable biological base master batch as raw material in the present invention, and the biodegradable polyesters composition biodegradability is good and has excellent engineering properties.
Description
Technical field
The present invention relates to a kind of degradable biological base master batches and the preparation method and application thereof, belong to polymer modification neck
Domain.
Background technique
Biodegradable polyester is a kind of high molecular material using living resources as raw material.Relative to fossil resources be original
The petroleum based high molecular of material, Biodegradable polyester can occur during biology or biological chemistry action or in biotic environment
Degradation is that best one of degradable material is applied in very active and market in current biodegradable plastic research.
Chinese patent CN 102597105A report with aliphatic diacid such as adipic acid, aromatic diacid such as terephthalic acid (TPA) and
Aliphatic diol is that the biodegradable aliphatic-aromatic polyesters that raw material obtains are that document neutralization is known in the market.These polymerizations
The composition monomer of object is non-renewable, and in this way regardless of their biodegradability, they can all cause significant shadow to environment
It rings.
In addition, this kind polyester currently sold on the market has the amount of the aromatic acid less than 48 moles of %, because in the threshold
More than value, the biodegradable percentage of these polyester significantly reduces.This significantly limits polyester height associated with compostability
The purposes of engineering properties, such as the sack for manufacturing collection of organic waste.
Compost is that organic matter is made to return to the process of Life Cycles to reproduce in the form of controlled and acceleration in natural imitation circle
The commercial run of these processes.In nature, (dried leaf, branch, animal are residual for organic matter generated and no longer lived
Bones of the body etc.) microorganism decomposition present in soil, this is returned in Natural Circulation.The component more difficult to degrade left constitutes rotten
Matter is grown, therefore slowly but constantly discharges nutrient (nitrogen, phosphorus, potassium etc.) to ensure the energy of the sustainable fertility in soil in view of it
Power, these humus are the important foodstuffs suppliers of plant.Therefore industrial compost is to reduce and obtain a humic-like substance, i.e. heap
Time necessary to fertilizer and the quality of final product is improved relative to the product that obtains naturally and is provided for spontaneous in nature
The method of the structure of the reasonable management of the microbial activities of generation.
Similarly, family's compost be the organic substance from kitchen and garden food debris is deposited in compost case or
On the ground in the hole excavated, and under conditions of milder than industrial compost aerobic degradation method.Particularly, in family's composting method
Aerobic degradation carried out under room temperature (usual 10 to 45 DEG C).
However, in the prior art, biodegradability preferably and can be used for compost biodegradable polyesters it is less.
Summary of the invention
It is an object of the invention to provide in place of overcome the deficiencies in the prior art a kind of degradable biological base master batch and its
Preparation method and application, the biodegradable polyesters composition containing the master batch have excellent biodegradability and tearing strong
Degree.
To achieve the above object, the technical scheme adopted by the invention is as follows: a kind of degradable biological base master batch comprising biology
The weight ratio of degradation polyester and biologic packing material, Biodegradable polyester and biologic packing material is 20-40:60-80；The biologic packing material comes
80% or more of total carbon weight in biologic packing material is accounted for from the total organic carbon in natural biomass resource, the biologic packing material,
The partial size D of the biologic packing material50It is 0.5~8 μm；
Total organic carbon in the degradable biological base master batch accounts for the 60%- of total carbon weight in degradable biological base master batch
100%.
The content of total organic carbon (TOC) in above-mentioned biologic packing material and degradable biological base master batch is according to ISO16620-2
Standard testing is available.The partial size test method of biologic packing material in degradable biological base master batch of the present invention are as follows:
A) the above-mentioned degradable biological base master batch of 2.0~3.0g is taken to be placed in crucible；
B) will be placed in Muffle furnace equipped with the crucible of degradable biological base master batch, 700 DEG C calcination 30~45 minutes；
C) partial size of the residue after calcination is measured according to " grain size analysis laser diffractometry " method of GB/T 19077.1.
The present invention selects the biologic packing material of appropriate particle size to prepare master batch, and the biology base that can prepare high filling (>=65%) is filled out
Master batch is filled, on the basis of reducing master batch cost, keeps the service performance of master batch, which combines with the formation of other degradable materials
Object has preferable degradation property.
It should be noted that above-mentioned biologic packing material, the partial size the big more not easy to reunite, is conducive in Biodegradable polyester
Dispersion；But work as the partial size D of biologic packing material50When more than 8 μm, since the particle of biologic packing material is excessive, it will affect subsequent thin film etc.
The surface characteristic (roughness) of product, and then affect the performance of product.
As the preferred embodiment of degradable biological base master batch of the present invention, the Biodegradable polyester and biology are filled out
The weight ratio of material is 25-35:65-75.Studies have shown that the weight ratio of Biodegradable polyester and biologic packing material will affect containing described
The biodegradability and tearing strength of the polymer blend of degradable biological base master batch, within the scope of the preferred weight ratio, most
The biodegradability of gained polymer blend and tearing strength are more excellent eventually.
As the preferred embodiment of degradable biological base master batch of the present invention, 2.16kg is used according to ASTM D1238
Weight is simultaneously measured in 190 DEG C of temperature, and the melt index of the Biodegradable polyester is 8-80g/10min；Preferably, the life
The melt index of object degradation polyester is 10-60g/10min；It is highly preferred that the melt index of the Biodegradable polyester is 15-
45g/10min.The biodegradability and tearing strength of polymer blend containing degradable biological base master batch of the present invention also can
It is influenced by Biodegradable polyester melt index in master batch, when the melt index of the Biodegradable polyester is 10-60g/
When 10min, the biodegradability and tearing strength of gained polymer blend are more preferable, especially when its melt index is 15-
When 45g/10min, the biodegradability and tearing strength of gained polymer blend are best.
As the preferred embodiment of degradable biological base master batch of the present invention, the partial size D of the biologic packing material50For
0.8~6 μm；It is highly preferred that the partial size D of the biologic packing material50It is 1~5 μm.
As the preferred embodiment of degradable biological base master batch of the present invention, in following (a)~(b) at least one
:
(a) Biodegradable polyester be polylactic acid, polyhydroxyalkanoates (PHA), polybutylene succinate (PBS),
Poly adipate succinic acid ester is copolymerized succinic acid-butanediol ester (PBSA), polyadipate-mutual-phenenyl two acid bromide two alcohol ester (PBAT), gathers
At least one of succinic acid mutual-phenenyl two acid bromide two alcohol ester (PBST), poly- decanedioic acid mutual-phenenyl two acid bromide two alcohol ester (PBSeT)；
(b) biologic packing material comes from least one of animal bone, eggshell class, coral, shell, oyster, nacre.
As the preferred embodiment of degradable biological base master batch of the present invention, the preparation method of the biologic packing material
Are as follows: it first passes through crushing and screening and obtains partial size D50For 15~50 μm of biologic packing material crude product；Institute is crushed by airslide disintegrating mill again
Biologic packing material crude product is stated, the biologic packing material is obtained；Wherein, the condition of airslide disintegrating mill are as follows: classification wheel speed 3000~
5000rpm, -0.3~-0.1MPa of air-introduced machine pressure；15~32kg/h of feeding capacity.
In addition, the present invention also provides the preparation methods of above-mentioned degradable biological base master batch comprising following steps: can
Component in degradation biological base master batch is put into double screw extruder after mixing in proportion, is squeezed out, is granulated in 140-220 DEG C, obtains
To the degradable biological base master batch.
In addition, the present invention also provides a kind of biodegradable polyesters compositions comprising following components in parts by weight: rouge
Fat adoption ester or 50~90 parts of aliphatic-aromatic copolyester, 0~35 part of natural polymer, above-mentioned degradable biological
5~40 parts of base master batch, 0~5 part of inorganic filler, 0~4 part of auxiliary agent.
In above-mentioned biodegradable polyesters composition, aromatic monomer such as terephthaldehyde in aliphatic-aromatic copolyester
The presence and acquisition of acid have sufficiently high melting temperature, sufficient crystalline rate, associated mechanical property such as ultimate strength, pierce through energy
It is related that the aliphatic-aromatic copolyester of characteristic can be processed with elasticity modulus and excellent industry.But regardless of biology drop
How is solution ability, and the synthesis source of monomer limits the application of these polyester, such as can significantly reduce the money from non-renewable carbon
A possibility that consumption in source (raw material).
On the other hand, the high-content of the aliphatic monomer of synthesis source such as adipic acid is although to a suitable level of biology is realized
It is desirable for degradability, but the environment for not only improving these polyester in this way influences, its engineering properties is also made to be deteriorated.This
Outside, the high-content of aliphatic monomer significantly reduces the melting temperature of polyester and reduces its crystalline rate at high temperature, thus wants
It asks and uses bigger kilocalorie number and longer cooling time in the industry processes of polyester.These limit the industry to these polyester
Machinability has adverse effect.
Filler is one of common additive of plastics, and addition filler can make polymer blend keep preferable performance, but
Its additive amount just will affect greatly very much the performance of polymer blend, and its excessively high additive amount is difficult to realize.
Aliphatic polyester, aliphatic-aromatic copolyester and the natural polymer that the present invention uses are markets
It is upper known, it is combined according to specific proportion of the present invention, gained biodegradable polyesters composition biodegradability is good
And there is excellent engineering properties.Also, due to its excellent engineering properties and biodegradability, the composition is especially suitable
For manufacturing film and bag film, such as: the sack of food product packing film and collection of organic waste.Studies have shown that using this hair
The longitudinal tear that 12 μm of ± 1 μm of films of open-birth Biodegradable polymer blend preparation are tested according to standard ASTM D-882/88
Intensity >=1100mN, the cross direction tear strength that 12 μm of ± 1 μm of films of preparation are tested according to standard ASTM D-882/88 >=
2800mN。
Even more important to be, biodegradable polyesters composition of the present invention is according to Unificazione Italian UNI 11355:2010 can
Family's compost.
As the preferred embodiment of biodegradable polyesters composition of the present invention, in following (I)~(IV) extremely
Few one kind:
(I) aliphatic polyester is polybutylene succinate (PBS), poly adipate succinic acid ester is copolymerized succinic acid fourth
At least one of diol ester (PBSA), the aliphatic-aromatic copolyester are polyadipate-mutual-phenenyl two acid bromide two alcohol ester
(PBAT), poly- succinic acid mutual-phenenyl two acid bromide two alcohol ester (PBST), in poly- decanedioic acid mutual-phenenyl two acid bromide two alcohol ester (PBSeT)
It is at least one；
(∏) described natural polymer is at least one of starch, polylactic acid；
(III) inorganic filler is selected from talcum powder, montmorillonite, kaolin, graphite, gypsum, conductive black, calcium chloride, oxygen
Change iron, dolomite, silica, wollastonite, titanium dioxide, silicate, mica, glass fibre, at least one in mineral fibres
Kind；
(IV) auxiliary agent is plasticizer, release agent, surfactant, wax, antistatic agent, dyestuff, UV absorbent, UV steady
Determine at least one of agent.
Furthermore the present invention also provides the preparation methods of above-mentioned biodegradable polyesters composition comprising following steps:
It is put into single screw rod inflation film manufacturing machine after component in biodegradable polyesters is mixed in proportion, in 120-180 DEG C of blown film, or it is mixed
After even in investment extruder, squeeze out, is granulated in 140-220 DEG C, obtain the biodegradable polyesters.
Finally, the present invention also provides a kind of films or bag film containing above-mentioned biodegradable polyesters composition.This
The biodegradable polyesters composition of invention can be used for preparing film, bag film or other composite materials etc., for example, it can be used for
Manufacture (1) it is mono- and double-alignment films, and the film multiple-layer laminated with other polymeric materials, (2) for agriculture field film,
(3) the attaching film for food and for wrapping up waste, (4) dressing equipment, (5) adhesive, (6) are used for organic waste collection
Sack, (7) hot forming single layer and multilayer food product packaging, (8) using extrusion coating methods obtain coating, containing paper, plastics, aluminium or
The multilayer laminates of the layer of metallized film, (9) be used for manufacture by sintering acquisition part foaming or expandable bead,
(10) foaming and half foamed products, including use pre-expanded beads to be formed foam block, (11) foam piece and for food packaging
The container obtained by them, (12) fruits and vegetables container, (13) containing gelatine, disintegrate and/or it is compound starch, natural
The composite material of starch, flour or plant or inorganic natural stuffing, (14) fiber, core are made of rigid polymer；It is blended
Composite fibre has from circle to the fiber of multi-leaf-shaped different section；Staple fiber, through spin and adhesive-bonded fabric, be used in health protect
Strong product, which neutralizes, to be used in agricultural and garment industry.
Compared with prior art, the invention has the benefit that the present invention has been made degradable using biologic packing material as raw material
Biology base master batch, meanwhile, biodegradable polyesters composition has been made using the degradable biological base master batch as raw material in the present invention, should
Biodegradable polyesters composition biodegradability is good and has excellent engineering properties.It is even more important to be, present invention biology
Degradable polyester composition can family's compost according to Unificazione Italian UNI11355:2010.
Specific embodiment
Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
In following embodiments, the substance being not specifically noted is obtained from commercially available.The melt index of Biodegradable polyester is
It is measured according to ASTM D1238 using 2.16kg weight and in 190 DEG C of temperature, biologic packing material and degradable biological base master batch
In total organic carbon (TOC) content it is available according to ISO 16620-2 standard testing.Degradable biological base master batch in embodiment
The partial size test method of middle biologic packing material are as follows:
A) the above-mentioned degradable biological base master batch of 2.0~3.0g is taken to be placed in crucible；
B) will be placed in Muffle furnace equipped with the crucible of degradable biological base master batch, 700 DEG C calcination 30~45 minutes；
C) partial size of the residue after calcination is measured according to " grain size analysis laser diffractometry " method of GB/T 19077.1.
In following embodiments, PLA indicates that polylactic acid, PHA indicate that polyhydroxyalkanoates, PBS indicate poly- succinic acid butanediol
Ester, PBSA indicate that poly adipate succinic acid ester copolymerization succinic acid-butanediol ester, PBAT indicate polyadipate-terephthalic acid (TPA) fourth two
Alcohol ester, PBST indicate that poly- succinic acid mutual-phenenyl two acid bromide two alcohol ester, PBSeT indicate poly- decanedioic acid mutual-phenenyl two acid bromide two alcohol ester.
Examples 1 to 7
The constituent component of degradable biological base master batch described in Examples 1 to 7 is as shown in table 1.The degradable life of Examples 1 to 7
Object base master batch the preparation method comprises the following steps: the component in degradable biological base master batch is mixed in proportion after put into double screw extruder
In, it squeezes out, be granulated in 140-220 DEG C, obtain the degradable biological base master batch.
The constituent component of Examples 1 to 7 biodegradable polyesters composition is as described in Table 2, and Examples 1 to 7 biology can drop
Solve polymer blend the preparation method comprises the following steps: after the component in biodegradable polyesters is mixed in proportion investment single screw rod inflation film manufacturing machine
In, it is put into extruder in 120-180 DEG C of blown film, or after mixing, squeezes out, is granulated in 140-220 DEG C, obtaining the biology can
Degradation polyester.
Meanwhile 12 μm of ± 1 μm of films are respectively prepared in Examples 1 to 7 biodegradable polyesters composition, according to standard
ASTM D-882/88 tests its machine direction tear and cross direction tear strength, tests it 12 weeks according to standard ISO 16929 (2013)
Biological degradation rate afterwards, test result are as shown in table 2.
1 Examples 1 to 7 degradable biological base master batch of table
2 Examples 1 to 7 biodegradable polyesters composition of table
As can be seen from Table 2, being had using biodegradable polyesters composition made from degradable biological base master batch of the present invention excellent
Different biodegradability and tearing strength.
Effect example 1
The weight ratio of Biodegradable polyester and biologic packing material, which will affect, in degradable biological base master batch of the present invention contains the mother
The biodegradability and tearing strength of the biodegradable polyesters composition of grain.It is filled out to investigate Biodegradable polyester with biology
The weight ratio of material is prepared for the biodegradability of biodegradable polyesters composition and the influence of tearing strength, this effect example
The biodegradable polyesters composition of following test groups 1~5 and control group 1~4.The biology of test group 1~5 and control group 1~4
Degradable polyester composition is made of following components in parts by weight: aliphatic polyester or aliphatic-aromatic copolyester 50~90
Part, 0~35 part of natural polymer, 5~40 parts of degradable biological base master batch, 0~5 part of inorganic filler, 0~4 part of auxiliary agent；
The degradable biological base master batch includes Biodegradable polyester and biologic packing material, and the melt index of the Biodegradable polyester is 8-
80g/10min, the melt index of the Biodegradable polyester are according to ASTM D1238 using 2.16kg weight and at 190 DEG C
Temperature measurement；Total organic carbon of the biologic packing material in natural biomass resource, the biologic packing material accounts for biology and fills out
80% or more of total carbon weight, the partial size D of the biologic packing material in material50It is 0.5~8 μm；The Biodegradable polyester and biology
The weight ratio of filler is as described in Table 3, and the total organic carbon in the degradable biological base master batch accounts for degradable biological base master batch
In total carbon weight 60%-100%.In the biodegradable polyesters composition of test group 1~5 and control group 1~4, except biology
Except polyester of degrading is different with the weight ratio of biologic packing material, all other is identical.
This effect example tests test according further to the test method of Examples 1 to 7 biodegradable polyesters composition properties
The biological degradation rate and tearing strength of the biodegradable polyesters composition of group 1~5 and control group 1~4, test result such as table 3
It is shown.
Table 3
Seen from table 3, the weight ratio of Biodegradable polyester and biologic packing material within the scope of the present invention when, obtained biology can
The biodegradability and tearing strength of degradation polymer blend are more preferable, the weight especially when Biodegradable polyester and biologic packing material
When amount is than being 25-35:65-75, the biodegradability and tearing strength of gained polymer blend are especially excellent.
Effect example 2
The melt index of Biodegradable polyester will affect the biology containing the master batch in degradable biological base master batch of the present invention
The biodegradability and tearing strength of degradable polyester composition.In order to investigate the melt index of Biodegradable polyester to biology
The biodegradability of degradable polyester composition and the influence of tearing strength, this effect example are prepared for following 1~7 Hes of test group
The biodegradable polyesters composition of control group 1~4.The biodegradable polyesters composition of test group 1~7 and control group 1~4
It is made of following components in parts by weight: aliphatic polyester or 50~90 parts of aliphatic-aromatic copolyester, natural polymerization
0~35 part of object, 5~40 parts of degradable biological base master batch, 0~5 part of inorganic filler, 0~4 part of auxiliary agent；The degradable biological base
Master batch includes Biodegradable polyester and biologic packing material, and the melt index of the Biodegradable polyester is as shown in table 4, and the biology is filled out
Expect total organic carbon in natural biomass resource, the biologic packing material account for 80% of total carbon weight in biologic packing material with
On, the partial size D of the biologic packing material50It is 0.5~8 μm；The weight ratio of the Biodegradable polyester and biologic packing material is 20-40:
60-80；Total organic carbon in the degradable biological base master batch accounts for the 60%- of total carbon weight in degradable biological base master batch
100%.In the biodegradable polyesters composition of test group 1~7 and control group 1~4, except the melt index of Biodegradable polyester
Except difference, all other is identical.
This effect example tests test according further to the test method of Examples 1 to 7 biodegradable polyesters composition properties
The biological degradation rate and tearing strength of the biodegradable polyesters composition of group 1~7 and control group 1~4, test result such as table 4
It is shown.
Table 4
By table 4 as it can be seen that when the melt index of Biodegradable polyester in degradable biological base master batch is 10-60g/10min,
The biodegradability and tearing strength of gained biodegradable polyesters composition are more preferable, especially when its melt index is
When 15-45g/10min, the biodegradability and tearing strength of gained polymer blend are best.
Effect example 3
The biodegradable polyesters of the master batch are contained in the grain diameter influence of biologic packing material in degradable biological base master batch of the present invention
The tearing strength of composition.In order to investigate the partial size of biologic packing material to the shadow of the tearing strength of biodegradable polyesters composition
It rings, this effect example is prepared for the biodegradable polyesters composition of following test groups 1~7 and control group 1~4.Test group 1~7
It is made of with the biodegradable polyesters composition of control group 1~4 following components in parts by weight: aliphatic polyester or aliphatic-
50~90 parts of aromatic copolyester, 0~35 part of natural polymer, 5~40 parts of degradable biological base master batch, inorganic filler
0~5 part, 0~4 part of auxiliary agent；The degradable biological base master batch includes Biodegradable polyester and biologic packing material, the biodegrade
The melt index of polyester is 8-80g/10min, and the melt index of the Biodegradable polyester is used according to ASTM D1238
2.16kg weight is simultaneously measured in 190 DEG C of temperature；The biologic packing material is from natural biomass resource, the biologic packing material
In total organic carbon account for 80% or more of total carbon weight in biologic packing material, the partial size D of the biologic packing material50As shown in table 5；It is described
The weight ratio of Biodegradable polyester and biologic packing material is 20-40:60-80；Total organic carbon in the degradable biological base master batch
Account for the 60%-100% of total carbon weight in degradable biological base master batch.
In the biodegradable polyesters composition of test group 1~7 and control group 1~4, except the partial size difference of biologic packing material
Outside, all other is identical.
This effect example tests test according further to the test method of Examples 1 to 7 biodegradable polyesters composition properties
The tearing strength of the biodegradable polyesters composition of group 1~7 and control group 1~4, test result are as shown in table 5.
Table 5
By table 5 as it can be seen that working as the partial size D of biologic packing material in degradable biological base master batch50When being 0.8~6 μm, gained biology can
The tearing strength of degradation polymer blend is more preferable, especially as the partial size D of biologic packing material50When being 1~5 μm, the combination of gained polyester
The tearing strength of object is best.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of degradable biological base master batch, which is characterized in that including Biodegradable polyester and biologic packing material, Biodegradable polyester
Weight ratio with biologic packing material is 20-40:60-80；The biologic packing material is filled out from natural biomass resource, the biology
Total organic carbon in material accounts for 80% or more of total carbon weight in biologic packing material, the partial size D of the biologic packing material50It is 0.5~8 μm；
Total organic carbon in the degradable biological base master batch accounts for the 60%-100% of total carbon weight in degradable biological base master batch.
2. degradable biological base master batch as described in claim 1, which is characterized in that the Biodegradable polyester and biologic packing material
Weight ratio be 25-35:65-75.
3. degradable biological base master batch as described in claim 1, which is characterized in that use 2.16kg weight according to ASTM D1238
It measures and is measured in 190 DEG C of temperature, the melt index of the Biodegradable polyester is 8-80g/10min；Preferably, the biology
The melt index of degradation polyester is 10-60g/10min；It is highly preferred that the melt index of the Biodegradable polyester is 15-45g/
10min。
4. degradable biological base master batch as described in claim 1, which is characterized in that the partial size D of the biologic packing material50It is 0.8
~6 μm；Preferably, the partial size D of the biologic packing material50It is 1~5 μm.
5. such as the described in any item degradable biological base master batches of Claims 1 to 4, which is characterized in that in following (a)~(b)
At least one of:
(a) Biodegradable polyester is polylactic acid, polyhydroxyalkanoates, polybutylene succinate, polybutyleneadipate
Ester be copolymerized succinic acid-butanediol ester, polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly- succinic acid mutual-phenenyl two acid bromide two alcohol ester,
At least one of poly- decanedioic acid mutual-phenenyl two acid bromide two alcohol ester；
(b) biologic packing material comes from least one of animal bone, eggshell class, coral, shell, oyster, nacre.
6. the preparation method of degradable biological base master batch as described in any one of Claims 1 to 5, which is characterized in that including following
Step: putting into double screw extruder after the component in degradable biological base master batch is mixed in proportion, squeezes in 140-220 DEG C
Out, it is granulated, obtains the degradable biological base master batch.
7. a kind of biodegradable polyesters composition, which is characterized in that including following components in parts by weight: aliphatic polyester or rouge
Fat race -50~90 parts of aromatic copolyester, 0~35 part of natural polymer can drop described in any one of Claims 1 to 5
5~40 parts of biology base master batch, 0~5 part of inorganic filler, 0~4 part of auxiliary agent of solution.
8. biodegradable polyesters composition as claimed in claim 7, which is characterized in that in following (I)~(IV) at least
It is a kind of:
(I) aliphatic polyester is polybutylene succinate, poly adipate succinic acid ester is copolymerized in succinic acid-butanediol ester
At least one, the aliphatic-aromatic copolyester is polyadipate mutual-phenenyl two acid bromide two alcohol ester, poly- succinic acid is to benzene two
At least one of formic acid butanediol ester, poly- decanedioic acid mutual-phenenyl two acid bromide two alcohol ester；
(∏) described natural polymer is at least one of starch, polylactic acid；
(III) inorganic filler is selected from talcum powder, montmorillonite, kaolin, graphite, gypsum, conductive black, calcium chloride, oxidation
At least one of iron, dolomite, silica, wollastonite, titanium dioxide, silicate, mica, glass fibre, mineral fibres；
(IV) auxiliary agent is plasticizer, release agent, surfactant, wax, antistatic agent, dyestuff, UV absorbent, UV stabilizer
At least one of.
9. the preparation method of biodegradable polyesters composition as described in claim 7 or 8, which is characterized in that including following step
It is rapid: it is put into single screw rod inflation film manufacturing machine after the component in biodegradable polyesters is mixed in proportion, in 120-180 DEG C of blown film, or
Person puts into extruder after mixing, and squeezes out, is granulated in 140-220 DEG C, obtains the biodegradable polyesters.
10. a kind of film or bag film containing the biodegradable polyesters composition of claim 7 or 8.
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| PCT/CN2019/121836 WO2020134850A1 (en) | 2018-12-25 | 2019-11-29 | Degradable bio-based masterbatch and preparation method therefor and application thereof, |
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| WO2020134850A1 (en) | 2020-07-02 |
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