CN107418163B - The preparation method of water vapor rejection PBAT complete biodegradable resin combination and film - Google Patents
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- 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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- 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
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08L2201/14—Gas barrier composition
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention provides a kind of water vapor rejection PBAT full-biodegradable films, include 60~99 parts of PBAT, 0.5-10 parts of degradable waterproofing agents, 0.5~20 part of organic modification montmonrillonite, 0~10 part of organics additive, 0~10 part of inorganic additive, wherein waterproofing agent is several combinations in degradable animal class either plant.For gained film of the invention under the conditions of 6 micron thickness, moisture-vapor transmission is less than 700g/m2Day, breaking strength are greater than 25MPa, and elongation at break is greater than 300%, and film and waterproofing agent may be implemented in degradable in natural environment, can be widely applied to agricultural mulching, packaging bag, courier bag, heat shrink films, adhesive tape etc..
Description
Technical field
The present invention relates to the preparation method of a kind of water vapor rejection PBAT complete biodegradable resin combination and film, belong to complete
Degradable material technical field.
Background technique
In recent years, the development of biodegradable plastic is growing day by day, and application range constantly expands, tableware, non-returnable container,
Plastic film for agricultural use and daily necessities field start gradually to replace conventional plastic.Full-biodegradable film is due in natural environment either compost
Under the conditions of can resolve into water, carbon dioxide and organic composition completely, there is no any negative effect to environment, therefore in recent years
Commodity packaging, courier bag, heat shrink films, adhesive tape, in terms of have very big exploitation and application.
Biological degradation plastics due to itself Chemical Physics structure influence, it is poor to the barrier property of steam, prepare
Thin gauge film physical property is poor, limits the popularization and use of full-biodegradable film.Chinese invention patent CN104830035 is mentioned
And a kind of biodegradation compound and its preparation method and application with barrier property, by addition non-degradable mineral wax and
High molecular material is as waterproofing agent, so that the water vapor transmittance of material is less than 800g/m2Day, but since non-degradable blocks water
The presence of agent, product can not be degradable, can generate pollution to environment.Meanwhile although a variety of waterproofing agents are referred in patent
Combination, but can not obviously find these combination for water preventing ability protrusion improvement.In addition, thin involved in the invention
Film has 25 μm of thickness, lacks usability in actual use.Chinese invention patent CN103804879 refers to a kind of high-barrier
Polytrimethylene carbonate composite film material and preparation method thereof, but what it utilized is resistance that poly (propylene carbonate) itself has
Extended every property, be not directed to the modification to the poor material of water preventing ability, while being added to nondegradable polyvinyl alcohol in material
Material, and possessed bad mechanical property.Have the preferable film of water vapor barrier property on the market for the preparation of non-degradable material, or
Person is to be added to the non-degradable material in part, or carry out surface coating or modification to material, or have preferable
Water vapor barrier property, but mechanical performance is poor.
Therefore, it is necessary to promote its water vapor barrier property and guarantor while maintenance full-biodegradable film preferable mechanical performance
Degradability is held to be very necessary.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide a kind of water vapor rejection PBAT complete biodegradable resins
The preparation method of composition and film.
The present invention is achieved by the following technical solutions:
In a first aspect, the present invention provides a kind of water vapor rejection PBAT complete biodegradable resin combinations comprising by weight
Measure the following component of number meter:
Preferably, the degradable waterproofing agent is the mixture of animal class waterproofing agent and plant waterproofing agent.
Preferably, the animal class waterproofing agent is beeswax, butter, insect wax, whale oil, lanocerin, one in spermaceti
Kind is several;The plant waterproofing agent is oleic acid, linolenic acid, haze tallow, rice bran wax, palm wax, peanut oil, castor wax, palm
One or more of acid, soybean oil, epoxidized soybean oil, bayberry wax, Jojoba Oil, hydrogenated vegetable oil.
Two or more waterproofing agent is added for the barrier property of steam compared to the water for adding single waterproofing agent
Vapour barrier property has promotion outstanding, and what is mainly utilized is the mutually separation knot that a variety of waterproofing agents are mixed and formed during cooling
Structure, so that its hydrophobicity further increases.Mixing for a variety of waterproofing agents can be several compound additions in plant,
Several compound additions being also possible in animal class are equally also possible in one or more of plant and animal class
One or more of compound additions.It is preferred that animal class and the compound addition of plant, the content of further preferred animal class is greater than plant
The content of class.Inventor also found that adding a certain proportion of waterproofing agent has preferable help, Ke Yizuo for the uniformity of film
The physicalchemical structure uniformity of film and the dispersion of additive are improved for plasticizer.It should be pointed out that the present invention chooses
All be degradable waterproofing agent, during use either degrade during can decompose completely in nature,
Waterproofing agent does not have an impact environment while playing block-water effect from animal either plant simultaneously.
The water vapor barrier property of PBAT full-biodegradable film can be promoted by being added to suitable montmorillonite, be mainly utilized
The lamellar structure of montmorillonite and the staggered floor effect of complexity penetrate the change in path to steam from film.By by montmorillonite with
The water vapor rejection performance of the collective effect of waterproofing agent, film is also promoted, on the one hand, montmorillonite and waterproofing agent are provided with steam
On the other hand barrier property, two kinds of synergistic effects, have blocking water for thermal fluidity so that the water vapor barrier property of film is strengthened
Agent can be flowed into during product is processed between the cheating engaging layer that staggered floor is held or near montmorillonite, further prevent steam
The path penetrated from film.Simultaneously because waterproofing agent enters between cheating engaging layer or near montmorillonite, so that waterproofing agent exists
Presence in film is more stable, reduces the precipitation of waterproofing agent in placement or use process.
Preferably, the organic modification montmonrillonite is ammonium salt modified montmorillonoid, in organic-silicon-modified montmorillonite
It is one or two kinds of.Montmorillonite has lamellar structure, can make its interlaminar separation, preparation cashier by modified and screw rod shearing
The imvite modified PBAT material of the sheet of meter level.On the one hand, it is processed due to montmorillonite and uniform nanometer is presented in the film
Rank dispersion, has obtained good enhancing to the mechanical performance of film itself;Simultaneously as its laminated structure, to the machine of film
Tool performance plays the role of unique improvement, can make have biggish extension at break by the film that blow molding is prepared
Rate has preferable improvement simultaneously for thin film strength size and direction;The third aspect, the interlaminar separation of montmorillonite is for thin
Film water vapor rejection has preferable improvement effect.Montmorillonite according to the present invention can be modified by organic ammonium salt, can also be with
It is modified by organosiloxane, the montmorillonite dispersion effect obtained by different modifications has certain otherness, this hair
Modified material of the bright montmorillonite modified preferably through ammonium salt as film.It is good that montmorillonite realizes that interlaminar separation has later
Nucleating effect can be very good that PBAT material is promoted to form fine and uniformly distributed crystal grain, for the water vapor barrier property of film
Promotion has very big help, and the different nucleating effect of montmorillonite may be implemented by different processing methods, and then makes gained
The water vapor rejection effect of film changes.
Preferably, the organics additive selects PLA, PPC, PBSA, PHA, PEF, PCF, ADR, maleic acid
One or more of acid anhydride, sorbierite and its derivative.
By a certain proportion of organics additive, having special performance to film has help well, for example, disconnected
Resistance to spalling, water vapor barrier property, transparency etc..Due to different organics additives have the effect of it is different, it is therefore desirable to according to
Actual use situation is compounded, for example, adding certain PLA, PBSA, ADR etc. can be improved thin film strength;Addition PPC,
Processing stability and water vapor barrier property can be improved in one or more of PHA, further for the water vapor barrier property of film
It is promoted helpful;The transparency of film can be improved by one or more of addition PEF, PCF, PPC etc..It needs especially
, it is noted that the organic matter of addition can not only promote the performance of film, the chemical structure of film itself is also changed.
Preferably, the inorganic additive be selected from calcium carbonate, talcum powder, calcium oxide, titanium dioxide, carbon black,
One or more of mica, whiting, inorganic pigment, aromatic radical phosphates, metal carboxylate, stearates.
On the one hand the addition of inorganic additive makes performance of the film with preferable mechanical performance and other additions, simultaneously
The cost of material of film can be reduced again, and since inorganic additive is to the adsorptivity of waterproofing agent, can make waterproofing agent more
Stable exists in the film.
Second aspect, the present invention also provides a kind of water vapor rejection PBAT complete biodegradable resin combinations as the aforementioned
Preparation method comprising following steps:
By PBAT, degradable waterproofing agent, organic modification montmonrillonite, organics additive, inorganic additive 150~
After carrying out first time extruding pelletization at 170 DEG C, then second of extruding pelletization is carried out at 150~170 DEG C, it is complete to obtain the PBAT
Biodegradable resin composition.
By extruding pelletization twice, inorganic matter being dispersed in PBAT resin matrix more evenly can be made, while in screw rod
Under the action of shearing force, better layered effect is may be implemented in montmorillonite, so that its water-resisting ability is strengthened.In addition, twice
It is preferably compatible in PBAT resin that extruding pelletization can also make inorganic matter preferably absorb waterproofing agent and waterproofing agent.
It preferably, is that PBAT complete biodegradable resin combination above-mentioned is carried out blow molding to be either cast
Molding, obtains the water vapor rejection PBAT full-biodegradable film.
The temperature of the blow molding is 160~180 DEG C, controls blow-up ratio between 2.5:1~6:1, further preferred 3.5:1
Between~5:1, when draw-down rate is drawn between 0.5mm~2.5mm, by adjusting suitable in the mouth mold gap of inflation film manufacturing machine,
Prepare the film of required thickness.
The temperature of the curtain coating be 150~190 DEG C, casting head die lip width between 0.8mm~2mm, by adjusting
The film of suitable Screw Extrusion rate and windup rate preparation required thickness.
It is preferred that drying 3~6h in 70 DEG C of vacuum dryings either rotary drum before being blow molded and being cast.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, the film that the present invention obtains can be greater than 35MPa in the breaking strength under 6 μ m thicks, and elongation at break is greater than
600%, water vapor transmittance is less than 300g/m2·day;
2, waterproofing agent may be implemented degradable in the natural environment, and no pollution to the environment;
3, agricultural mulching, packaging bag, courier bag, heat shrink films, in terms of have very big application prospect.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
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 scope.
Embodiment and material used in comparative example are as follows:
(A-1) PBAT resin: BASF Corp. of Germany's system, the specification trade mark: ecoflex C1200;
(A-2) PBAT resin: Guangzhou golden hair scientific & technical corporation system, the trade mark: 8215;
(B-1) palm wax: Shanghai five cereals International Trading Company Ltd, the specification trade mark: three tree No.1 pieces;
(B-2) epoxidized soybean oil: the macro benefit of Qingzhou City reaches Trade Co., Ltd.;
(B-3) lanocerin: Guangzhou Chong Te Chemical Co., Ltd.;
(B-4) butter: along auspicious leather and fur products Co., Ltd;
(C-1) organic modification montmonrillonite: Zhejiang Fenghong New Material Co., Ltd.'s system, the specification trade mark: DK4;
(C-2) organic modification montmonrillonite: U.S.'s Nanocor system, the specification trade mark: 1.31PS;
(D-1) PLA: the positive system in Zhejiang sea, the specification trade mark: REVODE 101L;
(D-2) PHA: Shandong Yi Keman, EM20010;
(E-1) nanometer calcium carbonate: Jiande City, Zhejiang Province Zheng Fa calcium carbonate Co., Ltd;
(E-2) talcum powder: poly- thousand Chemical Co., Ltd. in Shanghai, MY-4000.
Raw material, the composition of acquisition, product sample used in embodiment and comparative example are according to following standard testings
Method is tested for the property:
Thickness: using weight method, measure 100 square metres of areas, claim to obtain quality, calculates thickness, test three according to density
It is secondary, it is averaged.The average thickness of embodiment and comparative example is 6 microns.
Breaking strength and elongation at break: longitudinal direction (MD) and transverse direction at 25 DEG C, by GB1040.3-2006 testing film
(TD) breaking strength and elongation at break, and the average value for obtaining vertically and horizontally numerical value is stretched as the breaking strength of film and fracture
Long rate.
Water vapour permeability: using the water vapor transmittance of weight method measurement film, the anhydrous chlorine of 150g is packed into round bottle
Change calcium, film is cut into the disk of diameter 6cm and is covered on round bottle, be put into 25 DEG C, 24 hours in 90% humidity environment, claims
It is of poor quality before and after weighing and calculating, calculate water vapor transmittance.
Raw material is mixed by table through double-screw extruding pelletizing, extrusion temperature is 150~170 DEG C, and gained particle is carried out
Second of granulation, extrusion temperature are 150~170 DEG C.Embodiment 1~17 by single screw rod blow molding, blow temperatures are 160~
180 DEG C, embodiment 18~19 is by tape casting, and specific raw material proportioning is referring to table 1-1, table 1-2 and table 1-3;Then to film
It is tested for the property, is as a result listed in table 2-1, table 2-2 and table 2-3.
Table 1-1
Table 1-2
Table 1-3
Table 2-1
Table 2-2
Table 2-3
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to 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 substantive content of the invention.
Claims (6)
1. a kind of water vapor rejection PBAT complete biodegradable resin combination, which is characterized in that as follows including according to parts by weight
Component:
The degradable waterproofing agent is the mixture of animal class waterproofing agent and plant waterproofing agent, and the animal class waterproofing agent is bee
One or more of wax, butter, insect wax, whale oil, lanocerin, spermaceti;The plant waterproofing agent is oleic acid, linolenic acid, wood
Wax, rice bran wax, palm wax, peanut oil, castor wax, palmitinic acid, soybean oil, epoxidized soybean oil, bayberry wax, Jojoba Oil, hydrogenation
One or more of vegetable oil.
2. water vapor rejection PBAT complete biodegradable resin combination as described in claim 1, which is characterized in that described organic to change
Property montmorillonite be one or both of organic ammonium salt modified montmorillonoid, organic siloxane modified montmorillonite.
3. water vapor rejection PBAT complete biodegradable resin combination as described in claim 1, which is characterized in that the organic matter
Additive selects one of PLA, PPC, PBSA, PHA, PEF, PCF, ADR, maleic anhydride, sorbierite and its derivative or several
Kind.
4. water vapor rejection PBAT complete biodegradable resin combination as described in claim 1, which is characterized in that the inorganic matter
Additive is selected from one or more of calcium carbonate, talcum powder, calcium oxide, titanium dioxide, carbon black, mica, whiting.
5. a kind of preparation of the water vapor rejection PBAT complete biodegradable resin combination as described in Claims 1 to 4 any one
Method, which comprises the steps of:
By PBAT, degradable waterproofing agent, organic modification montmonrillonite, organics additive, inorganic additive at 150~170 DEG C
After lower progress first time extruding pelletization, then second of extruding pelletization is carried out at 150~170 DEG C, it is entirely biological to obtain the PBAT
Degradable resin composition.
6. a kind of preparation method of water vapor rejection PBAT full-biodegradable film, which is characterized in that being will be described in claim 1
PBAT complete biodegradable resin combination carries out blow molding or tape casting, obtains the full biology drop of the water vapor rejection PBAT
Degrading film.
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CN108547390A (en) * | 2018-04-25 | 2018-09-18 | 温州正城建设有限公司 | A kind of building energy conservation formula house |
CN110016216B (en) * | 2019-04-28 | 2021-08-27 | 睿泊(中国)环保科技有限公司 | Fully-degradable polyglycolic acid composite packaging material and preparation method thereof |
CN110028770B (en) * | 2019-04-28 | 2024-08-20 | 广州知旺科技有限公司 | Fully degradable composite film and preparation method thereof |
CN110055021A (en) * | 2019-05-18 | 2019-07-26 | 福建省昌德胶业科技有限公司 | A kind of high water vapor rejection composition epoxy resin and its application in lithium-ion-power cell |
CN110330773A (en) * | 2019-07-19 | 2019-10-15 | 深圳利琒环保材料有限公司 | A kind of controllable full-biodegradable mulch and preparation method thereof |
CN110452507B (en) * | 2019-08-30 | 2021-09-21 | 中国农业科学院农业环境与可持续发展研究所 | High-barrier-property high-strength ultrathin full-biodegradable mulching film and preparation method thereof |
CN112358657A (en) * | 2020-11-26 | 2021-02-12 | 重庆和泰润佳股份有限公司 | Non-air-permeable biodegradable film and preparation method thereof |
CN112708247A (en) * | 2020-12-28 | 2021-04-27 | 生刚 | Resin modification for producing winding film by biodegradable material and preparation method thereof |
JP7094590B1 (en) | 2021-12-17 | 2022-07-04 | 株式会社Tbm | Resin composition and molded product |
CN114539734A (en) * | 2022-03-11 | 2022-05-27 | 佛山清粤新材料科技有限公司 | Fully-degradable composite dielectric material and preparation method thereof |
CN115260711B (en) * | 2022-08-12 | 2024-01-05 | 横店集团得邦工程塑料有限公司 | Hydrolysis-resistant high-barrier biodegradable film and preparation method thereof |
CN115710412B (en) * | 2022-10-31 | 2023-10-13 | 安徽金田高新材料股份有限公司 | High-barrier biaxially oriented degradable polyester film and preparation method thereof |
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