CN107400339A - The preparation method of imvite modified fully-degradable polymer material - Google Patents
The preparation method of imvite modified fully-degradable polymer material Download PDFInfo
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention discloses a kind of preparation method of imvite modified fully-degradable polymer material, comprise the following steps：Montmorillonite and monomer A and monomer B are subjected to in-situ polymerization, obtain low-molecular-weight polymeric product；The low-molecular-weight polymeric product and monomer A, monomer B and function additive are subjected to catalytic polymerization, obtain middle-molecular-weihydroxyethyl polymerizate；The middle-molecular-weihydroxyethyl polymerizate and biodegradable polymer and function additive are subjected to double-screw extruding pelletizing, obtain the imvite modified fully-degradable polymer material；Wherein, the number-average molecular weight of the low-molecular weight polymer product is 500~5000, and the number-average molecular weight of the middle-molecular-weihydroxyethyl polymerizate is 10000~50000.The present invention provides a kind of imvite modified high polymer material, it is possible to achieve the preferable intercalation of montmorillonite and is partially stripped, realizes higher production efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of imvite modified fully-degradable polymer material, belongs to high polymer material neck
Domain.
Background technology
High polymer material have light, intensity is high, good endurance, be easy to shaping etc. good characteristics so that it is in daily life
Had a wide range of applications in work.However, due to high polymer material good endurance, steady chemical structure, in natural environment very
It is difficult to natural degradation, causes soil, water body etc. by serious pollution.Therefore degradable high polymer material biological can especially drop
Solution high polymer material has obtained very extensive concern and product development.
The raw material sources of fully bio-degradable high polymer material are extensive, in natural environment certain time can be with degradable
Small-molecule substance, and product is environmentally safe, a variety of biodegradable plastic products have been prepared at present and have obtained one
Determine the application of degree.But due to Biodegradable polymer material generally have mechanical performance not enough, water vapor rejection performance it is poor,
The shortcomings of heat endurance difference, its large-scale use is limited, it is modified with preferable feasibility by inorganic filler.
Montmorillonite can reach enhancing and the effect of toughness reinforcing simultaneously as a kind of flaky inorganic powder for possessing layer structure
Fruit, and laminated structure has huge help to water vapor barrier property, therefore as one kind in the modifying process of high polymer material
Typical additives are widely used.Because montmorillonite source is simple, and to environment and pollution-free, therefore montmorillonite is as biology
The additive of degradation material is also by numerous studies.Because the intercalation and peeling effect of montmorillonite layer structure directly determine it
Action effect, therefore intercalation peels off the emphasis that modification is montmorillonite research.
At present, the intercalation of montmorillonite mainly uses two methods, using macromolecule directly with montmorillonite mixing intercalation and illiteracy
De- soil is in-situ polymerization intercalated.Chinese invention patent CN200510030494.9 is by PLA and montmorillonite melting mixing, by double
Screw Extrusion is granulated to form intercalation configuration, and the active force between PLA and montmorillonite is improved using compatilizer, using greatly enhancing
Footpath than twin-screw enhance scattered and intercalation effect, obtain the PLA montmorillonite material of intercalation.It is special that farsighted chemical industry is expanded in Shanghai
Sharp CN201610795447.1 extrudes PBAT with montmorillonite by twin-screw melting mixing, and both are improved mutually using compatilizer
Active force, montmorillonite intercalation modified PBAT material is obtained, while be prepared for PBAT films, most thin to cause 5 μm, intensity is reachable
20MPa, moisture-vapor transmission 240g/ (m2·24h).Because spacing is minimum between cheating engaging layer, by between modified cheating engaging layer
Spacing contrast high polymer material still very little, cause macromolecule to enter well between cheating engaging layer so that intercalation with
Peeling effect is poor, the modified effect unobvious of montmorillonite.
It is blended in Chinese patent CN200510023647.7 using lactide and montmorillonite, due to the less molecule of lactide
Amount and molecular volume, it is easy into montmorillonite interlayer spacings, be then catalyzed lactide in-situ polymerization and obtain PLA, obtain
Montmorillonite obtains the structure being partially stripped completely by PLA intercalation, and the montmorillonite content that this method prepares product is low, efficiency
It is relatively low, it is impossible to adapt to large-scale production.Chinese patent CN201210044664.9 refers to a kind of hydroxy-functionalized polyesters/montmorillonite
The preparation method of nano composite material, it is modified using a variety of carboxylic acids, diepoxy thing and organic modification montmonrillonite in-situ polymerization
High polymer material, but this method is a polymerisation, reacts more difficult control, and it is poor to obtain product mechanical performance.
The content of the invention
For in the prior art the defects of, it is an object of the invention to provide a kind of imvite modified fully-degradable polymer material
Preparation method.
The present invention is achieved by the following technical solutions：
The invention provides a kind of preparation method of imvite modified fully-degradable polymer material, it comprises the following steps：
Montmorillonite and monomer A and monomer B are subjected to in-situ polymerization, obtain low-molecular-weight polymeric product；
The low-molecular-weight polymeric product and monomer A, monomer B and function additive are subjected to polymer, obtain middle-molecular-weihydroxyethyl
Polymerizate；
The middle-molecular-weihydroxyethyl polymerizate and biodegradable polymer and function additive are subjected to twin-screw extrusion
It is granulated, obtains the imvite modified fully-degradable polymer material；
Wherein, the number-average molecular weight of the low-molecular weight polymer product is 500~5000, the middle-molecular-weihydroxyethyl polymerization production
The number-average molecular weight of thing is 10000~50000.
Preferably, the montmorillonite is selected from sodium-based montmorillonite, calcium-base montmorillonite, was modified by organic modifiers
At least one of montmorillonite.
Because organic modifiers can enter the interlayer of montmorillonite, pre- intercalation is carried out to montmorillonite, makes cheating engaging layer spacing
Become big, therefore it is preferred that the montmorillonite of organically-modified mistake.Organic modifiers are ammonium salt, and the ammonium salt can be octadecyltrimethylammonium
Salt, octadecyl ammonium salt, double octadecyl ammonium salts, triethoxy propyl-siloxane ammonium salt, cetyltrimethyl ammonium salt, 14
One or more in alkylammonium salt, tetramethyl ammonium and 4-butyl ammonium, it is preferred that the ammonium salt be octadecyl ammonium salt,
One or more in cetyltrimethyl ammonium salt, triethoxy propyl-siloxane ammonium salt.
Preferably, the organic modifiers are selected from octadecyltrimethylammonium salt, octadecyl ammonium salt, double 18
Alkylammonium salt, triethoxy propyl-siloxane ammonium salt, cetyltrimethyl ammonium salt, myristyl ammonium salt, tetramethyl ammonium, four
One or more in butylammonium salts.
Preferably, the monomer A is the one or more in lactide, lactic acid, low molecular weight, described
Monomer B is butanediol, adipic acid, dimethyl terephthalate (DMT), low molecule amount tetramethylene adipate, low molecule amount terephthaldehyde
One or more in sour butanediol ester.
One or more in montmorillonite and monomer A, monomer B are stirred 4~12h at 60~90 DEG C, make montmorillonite
In monomer sufficiently mixing swelling so that compositing monomer polymerization after can in montmorillonite more preferable intercalation.Abundant
After being stirred, whole reaction system is vacuumized, lifting temperature catalyst amount 0.1~1%, is reacted to 110~160 DEG C
During carry out continuous mechanical agitation so that reaction uniformly carry out.The whole reaction time is controlled to prepare the poly- of lower molecular weight
Close product, molecular weight control between 500~5000, between more preferably 500~2000, appropriate molecular weight and
Molecular weight distribution can make the low-molecular-weight polymeric product have more preferable effect in the reaction of next step, and molecular weight is too low,
Polymerizate can not be fixed between cheating engaging layer well, further have impact on after strand improves and struts effect to montmorillonite
Fruit；Molecular weight is too high, and polymer can be caused directly to envelope whole montmorillonite, have a strong impact on montmorillonite the later stage intercalation and
Peel off, can further influence modified effect of the montmorillonite for high polymer material.
After low-molecular-weight polymeric product is obtained, by low-molecular-weight polymeric product and monomer A, monomer B and function additive
Carry out the polymerizate that further polymerization obtains middle-molecular-weihydroxyethyl.In continuous mechanical agitation process, whole reactant is controlled
It is vacuum, and lifts temperature to 110~180 DEG C, for the molecular weight of further lifting product, preferable reaction temperature is 140~180
DEG C, the molecular weight of product of acquisition is between 10000~50000.By the step for the middle-molecular-weihydroxyethyl polymerizate that obtains be into
The preparation that one step obtains imvite modified high polymer material provides important support, and molecular weight is too low, in the process further prepared
In influence whether the uniformity of final product, further influence the properties of product；Molecular weight is too high, increases the difficulty of preparation
Degree, while the stripping of montmorillonite is have impact on, further strutted using power caused by energy caused by polymerization and strand increase
The interlamellar spacing of montmorillonite, it is set further to disperse and peel off.
Research is found, is had the obvious disadvantage that using the biodegradable polymer of single component, and is worked as and used two
During kind or more composition, the performance of product can improve significantly, and when the use of PBAT being that twin-screw is granulated principal component, addition is certain
The PLA of ratio, material on the one hand can be made to keep certain elongation at break, while the intensity of material can be greatly improved again；When
The use of PBAT is that twin-screw is granulated principal component, adds PHA, the barrier property of material can be increased substantially, at the same still maintain compared with
Good mechanical performance；When the use of PBAT being that twin-screw is granulated principal component, PLA, PHA are added, the combination property of product can be made have more
Good lifting.
Preferably, the biodegradable polymer be PBAT, PLA, PPC, PBS, PHA in one kind or
It is several.
Preferably, the function additive includes one in crosslinking agent, crosslinking catalyst, chain extender, nano-powder
Kind is several.
The crosslinking agent be the compound with carbodiimides functional group, the compound with epoxy-functional, with
One or more in the compound of isocyanate functional group, it is however preferred to have the compound of epoxy-functional has carbonization
One or more in the compound of diimine functional group.Because middle-molecular-weihydroxyethyl polymer machinery performance is not high, it is therefore desirable to logical
To cross and carry out crosslinking improving performance with higher molecular weight material, on the one hand, crosslinking can improve molecular weight, structure is become stable,
On the other hand, the power provided by crosslinked action can make the further splitting of montmorillonite.
The chain extender is the compound with epoxy-functional, the compound with acid anhydrides, with bisoxazoline function
One or more in dough compound, the compound with isocyanate functional group.The addition of chain extender causes products therefrom
Molecular weight further improves, and can also make to react to each other between macromolecule, obtains stable compound.
The catalyst is metal salts of organic acids, including backbone structure is alkane, aromatic hydrocarbon, the unitary or polyacid of alkene
One or more in the acylate formed with potassium, calcium, sodium, magnesium, aluminium, zinc, iron, tin, barium metal ion.It is preferably stearic
The acylate that acid, oleic acid, citric acid are formed with above-mentioned metal ion, more preferably zinc stearate, zinc citrate, tristearin
One or more in sour barium.
The nano-powder is nanomete talc powder, nano-calcium carbonate, nanometer dibenzal sorbitol, nanometer 3, and 4- dimethyl is sub-
One or more in benzyl sorbitol, sorbierite sodium benzoate, nanometer whiting, adding proportion account for the 0.1% of overall product
Between~20%, content is too small, and the effect that nanometer powder rises is limited, does not act on significantly；Content is too big, to macromolecule material
The mechanical performance of material itself influences very big.
Preferably, the temperature of the extruding pelletization is 120~200 DEG C.
Extruding pelletization process is operated in double screw extruder, passes through the shear action that twin-screw is strong, one side
So that different component is reacted at high temperature, the progress of further induced chemical reaction is sheared；On the other hand, twin-screw is passed through
Physical shear effect, realize the dispersed of montmorillonite, and montmorillonite is realized splitting, reach preferably separation effect
Fruit, and inventor has found, is processed further by twin-screw, realizes the scattered peeling effect of unexpected mixing, this is right
In from now on be machined with good reference function.
Temperature when twin-screw is granulated is between 120~200 DEG C, and temperature is too low, and macromolecule can not melt well, a side
Face prevents montmorillonite from disperseing well, meanwhile, machine can be also lost in larger frictional force between screw rod and macromolecule, and can make
Macromolecule issues sub- chain break estranged in huge shearing force, also, relatively low temperature is not appropriate for chemical reaction
Further carry out, have impact on the reaction between middle-molecular-weihydroxyethyl product and Biodegradable polymer material；Temperature is too high, can cause
Macromolecular chain occurs fracture and decomposed.Material time in twin-screw is 3~8 minutes, and the time is too short, can cause the scattered of montmorillonite
Uniformity is inadequate, can also make the degree of chemical reaction inadequate；And overlong time, it can equally cause macromolecular chain that fracture point occurs
Solution.
Compared with prior art, the present invention has following beneficial effect：
The imvite modified high polymer material that the present invention obtains can realize the separation and intercalation and stripping of montmorillonite, cover
De- soil layer spacing gradually expands and last test is less than interlamellar spacing, and high polymer material has good physical property and later stage
Processing characteristics, it is widely used when preparing the products such as packaging bag, agricultural film, automotive trim, packaging in the later stage.Present invention system
Standby modified polymer material can be added among other Biodegradable polymer materials as master batch, while can also be single
Solely use and prepare final finished product.
Brief description of the drawings
The detailed description made by reading with reference to the following drawings to non-limiting example, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the small angle x-ray diffraction (SAXD) collection of illustrative plates for the product that embodiment 2 is prepared in each step.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
The present invention tests montmorillonite by small angle X-ray diffraction, and is calculated by formula 2dsin θ=λ between cheating engaging layer
Away from d, wherein λ is that 0.154, θ is abscissa numerical value.
Molecular weight is tested by viscosimetry, and by the intrinsic viscosity of dilute solution and the relation of molecular weight, backstepping goes out relatively
Molecular mass.
Embodiment 1
1st, by 10 parts of ammonium salt modified montmorillonoids (Zhejiang Feng Hong DK4, interlamellar spacing 3.8nm) and 30 parts of lactides, 13 parts of fourths two
Alcohol, 10 parts of terephthalic acid (TPA)s, 12 parts of tetramethylene adipates, after 0.3 part of stannous octoate, 70 DEG C of vacuum mix 5h, temperature carries
135 DEG C are risen to, continues to stir 2h, prepares low molecular weight product A, cheating engaging layer spacing is 4.5nm, product relative molecular weight
2500；
2nd, by 10 parts of low molecular weight product A and 20 parts of butanediols, 8 parts of adipic acids, 7 parts of dimethyl terephthalate (DMT)s, 0.1 part
Stannous octoate is stirred, and is warming up to 155 DEG C, is stirred under vacuum reaction 4h, is prepared middle-molecular-weihydroxyethyl product B, 80 DEG C of drying after washing
4h, cheating engaging layer spacing are 6.2nm, product relative molecular weight 28500；
3rd, added after 10 parts of middle-molecular-weihydroxyethyl product B are well mixed with 50 parts of PBAT, 1 part of ADR, 0.1 part of zinc stearate double
Screw rod, it is 165 DEG C to control extrusion temperature, screw slenderness ratio 60, prepares imvite modified degradable PBAT materials, now sees
Cheating engaging layer spacing is not detected, shows to realize splitting substantially.
Embodiment 2
1st, it is 10 parts of organic-silicon-modified montmorillonites and 15 parts of butanediols, 10 parts of adipic acids, 0.1 part of stannous octoate is true at 65 DEG C
After sky is stirred 4h, temperature is promoted to 130 DEG C of stirring reaction 2h, prepares low molecular weight product A, and cheating engaging layer spacing is
4.2nm, product relative molecular weight 3250, small angle x-ray diffraction (SAXD) spectrogram is as shown in the curve 1 in Fig. 1.
2nd, the PBT for being 1000 or so by 10 parts of low molecular weight product B and 25 parts of self-control weight average molecular weight, 15 parts of butanediols,
0.1 part of stannous octoate is stirred, and is warming up to 165 DEG C of reaction 5h, is dried 4h at 80 DEG C after washing, prepare middle-molecular-weihydroxyethyl product B,
Cheating engaging layer spacing is 6.1nm, product relative molecular weight 22800, small angle x-ray diffraction (SAXD) spectrogram such as the institute of curve 2 in Fig. 1
Show.
3rd, by 10 parts of middle-molecular-weihydroxyethyl product B and 50 parts of PBAT, 5 parts of PLA, 1 part of ADR, 0.1 part of zinc stearate, 1 part of talcum
Powder, 1 part of nano-calcium carbonate are sufficiently mixed stirring, add double-screw extruding pelletizing, prepare imvite modified fully-degradable polymer material
Material, extrusion temperature are 170 DEG C, and screw slenderness ratio 60, cheating engaging layer spacing is 7.2nm, and small angle x-ray diffraction (SAXD) spectrogram is as schemed
Shown in curve 3 in 1.
Embodiment 3
1st, by 10 parts of ammonium salt modified montmorillonoids (Zhejiang Feng Hong DK4, interlamellar spacing 3.8nm) and 30 parts of lactides, 13 parts of fourths two
Alcohol, 10 parts of terephthalic acid (TPA)s, after 0.3 part of stannous octoate, 70 DEG C of vacuum mix 5h, temperature is promoted to 135 DEG C, continues to stir
2h, prepares low molecular weight product A, and cheating engaging layer spacing is 4.9nm, product relative molecular weight 1350；
2nd, it is 10 parts of low molecular weight product A and 40 parts of butanediols, 20 parts of adipic acids, 10 parts of lactic acid monomers, 0.1 part of octanoic acid are sub-
Tin is stirred, and is warming up to 160 DEG C, is stirred under vacuum reaction 4h, is prepared middle-molecular-weihydroxyethyl product B, 80 DEG C of drying 4h after washing, is covered de-
Soil layer spacing is 7.5nm, product relative molecular weight 23100；
3rd, by 10 parts of middle-molecular-weihydroxyethyl product B and 20 parts of PLA, 1 part of ADR, 0.1 part of zinc stearate, 1 part of talcum powder, 1 part of nanometer
Calcium carbonate is sufficiently mixed stirring, adds double-screw extruding pelletizing, prepares imvite modified PLA high polymer material, extrusion temperature
For 180 DEG C, screw slenderness ratio 60, cheating engaging layer spacing is not observed now, show to realize splitting substantially.
Comparative example 1
1st, 10 parts of ammonium salt modified montmorillonoids (Zhejiang Feng Hong DK4, interlamellar spacing 3.8nm) and 100 parts of PBAT are passed through into twin-screw
Extruding pelletization, prepares imvite modified degradable PBAT high-molecular material As, and cheating engaging layer spacing is 4.1nm；
2nd, 10 parts of high-molecular material As and 50 parts of PBAT are passed through into double-screw extruding pelletizing, prepares imvite modified degradable
PBAT high polymer material B, cheating engaging layer spacing are 5.2nm.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (8)
1. a kind of preparation method of imvite modified fully-degradable polymer material, it is characterised in that comprise the following steps：
S1：Montmorillonite and monomer A and monomer B are subjected to in-situ polymerization, obtain low-molecular-weight polymeric product；
S2：The low-molecular-weight polymeric product and monomer A, monomer B and function additive are subjected to catalytic polymerization, obtain middle-molecular-weihydroxyethyl
Polymerizate；
S3：The middle-molecular-weihydroxyethyl polymerizate is carried out into twin-screw extrusion with biodegradable polymer and function additive to make
Grain, obtains the imvite modified fully-degradable polymer material；
Wherein, the number-average molecular weight of the low-molecular weight polymer product is 500~5000, the middle-molecular-weihydroxyethyl polymerizate
Number-average molecular weight is 10000~50000.
2. the preparation method of imvite modified fully-degradable polymer material as claimed in claim 1, it is characterised in that the illiteracy
De- soil is selected from least one of sodium-based montmorillonite, calcium-base montmorillonite, the montmorillonite that was modified by organic modifiers.
3. the preparation method of imvite modified fully-degradable polymer material as claimed in claim 2, it is characterised in that described to have
Machine modifying agent is selected from octadecyltrimethylammonium salt, octadecyl ammonium salt, double octadecyl ammonium salts, triethoxy propyl-siloxane
One or more in ammonium salt, cetyltrimethyl ammonium salt, myristyl ammonium salt, tetramethyl ammonium, 4-butyl ammonium.
4. the preparation method of imvite modified fully-degradable polymer material as claimed in claim 1, it is characterised in that the list
Body A is the one or more in lactide, lactic acid, low molecular weight, and the monomer B is butanediol, adipic acid, to benzene two
One or more in formic acid dimethyl ester, low molecule amount tetramethylene adipate, low molecule amount mutual-phenenyl two acid bromide two alcohol ester.
5. the preparation method of imvite modified fully-degradable polymer material as claimed in claim 1, it is characterised in that step S1
The one kind being selected from catalyst used in S2 in stannous octoate, trialkyl phosphine, triaryl phosphine.
6. the preparation method of imvite modified fully-degradable polymer material as claimed in claim 1, it is characterised in that it is described can
Biodegradated polymer materal is the one or more in PBAT, PLA, PPC, PBS, PHA.
7. the preparation method of imvite modified fully-degradable polymer material as claimed in claim 1, it is characterised in that the work(
Energy auxiliary agent includes the one or more in crosslinking agent, crosslinking catalyst, chain extender, nano-powder.
8. the preparation method of imvite modified fully-degradable polymer material as claimed in claim 1, it is characterised in that described double
The temperature that Screw Extrusion is granulated is 120~200 DEG C.
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| CN108034200A (en) * | 2017-12-11 | 2018-05-15 | 杭州鑫富科技有限公司 | A kind of biodegradable aliphatic-aromatic copolyester master batch and preparation method thereof |
| CN109737158A (en) * | 2018-12-21 | 2019-05-10 | 湖北飞龙摩擦密封材料股份有限公司 | A kind of drum brake lining and preparation method thereof |
| CN112724622A (en) * | 2020-12-24 | 2021-04-30 | 海南赛高新材料有限公司 | Modified PGA material compatibilized by adopting intercalation structure and preparation method thereof |
| CN113214618A (en) * | 2021-04-14 | 2021-08-06 | 何顺伦 | Food-grade heat-resistant PLA (polylactic acid) foam material and preparation method thereof |
| CN113354928A (en) * | 2021-06-29 | 2021-09-07 | 浙江中邦塑胶股份有限公司 | Biological plastic for manufacturing degradable film and preparation method thereof |
| CN114687066A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Degradable oil absorption material and preparation method thereof |
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| CN108034200A (en) * | 2017-12-11 | 2018-05-15 | 杭州鑫富科技有限公司 | A kind of biodegradable aliphatic-aromatic copolyester master batch and preparation method thereof |
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| CN114687066A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Degradable oil absorption material and preparation method thereof |
| CN113214618A (en) * | 2021-04-14 | 2021-08-06 | 何顺伦 | Food-grade heat-resistant PLA (polylactic acid) foam material and preparation method thereof |
| CN113214618B (en) * | 2021-04-14 | 2022-04-22 | 何顺伦 | Food-grade heat-resistant PLA (polylactic acid) foam material and preparation method thereof |
| CN113354928A (en) * | 2021-06-29 | 2021-09-07 | 浙江中邦塑胶股份有限公司 | Biological plastic for manufacturing degradable film and preparation method thereof |
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