KR20120136194A - Plastic composition and biodegradable molded article of the composition - Google Patents
Plastic composition and biodegradable molded article of the composition Download PDFInfo
- Publication number
- KR20120136194A KR20120136194A KR1020110055264A KR20110055264A KR20120136194A KR 20120136194 A KR20120136194 A KR 20120136194A KR 1020110055264 A KR1020110055264 A KR 1020110055264A KR 20110055264 A KR20110055264 A KR 20110055264A KR 20120136194 A KR20120136194 A KR 20120136194A
- Authority
- KR
- South Korea
- Prior art keywords
- cellulose ether
- molded article
- plastic
- biodegradable
- acetylated
- Prior art date
Links
Classifications
-
- 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
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
Abstract
Description
Plastic compositions and biodegradable shaped articles thereof are disclosed. More specifically, plastic compositions comprising non-biodegradable plastics and acetylated cellulose ethers and biodegradable shaped articles thereof are disclosed.
Biodegradable plastics are being investigated as a solution to the increasing problem of disposal of plastic waste. Conventional biodegradable plastics do not have enough mechanical strength, are expensive, and have a short shelf life, making it difficult to be commercialized.
In particular, conventional natural starch (corn starch, potato starch, sweet potato starch, wheat starch, rice starch, tapioca starch, sorghum starch, etc.) having modified biodegradation properties and modified starch are blended with a non-biodegradable plastic substrate. After preparing the composition, the biodegradable plastic product produced by molding the composition has a problem of poor water resistance and very low strength under general storage conditions.
Therefore, there is a growing demand for new plastic products having good water resistance, good mechanical strength and biodegradable properties.
One embodiment of the present invention provides a plastic composition comprising a non-biodegradable plastic and acetylated cellulose ether.
Another embodiment of the present invention provides a biodegradable molded article of the plastic composition.
According to an aspect of the present invention,
Non-biodegradable plastics; And
Provided are plastic compositions comprising acetylated cellulose ethers.
The non-biodegradable plastic may include at least one selected from the group consisting of polyolefin resins, polyester resins and polyamide resins.
The acetylated cellulose ether may have an alkyl group substitution degree (DS) of 1 to 2, a hydroxyalkyl group substitution degree (MS) of 0 to 3, and an acetyl group substitution degree (DS) of 1 to 3.
The acetylated cellulose ether may be formed by acetylation of at least one cellulose ether selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose.
The content of the acetylated cellulose ether may be 5 to 40 parts by weight based on 100 parts by weight of the non-biodegradable plastic.
Another aspect of the invention,
It provides a biodegradable molded article prepared by molding the plastic composition.
The biodegradable molded article may have a tensile strength of 25 Mpa or more, an Izod impact strength of 42 J / m or more measured at 23 ° C., and an Izod impact strength of 20 J / m or more measured at −10 ° C.
The biodegradable molded article may be an automobile interior material, a home appliance case, a mobile phone case, a packaging film, or an envelope.
According to one embodiment of the present invention, a plastic composition comprising a non-biodegradable plastic and an acetylated cellulose ether may be provided.
According to another embodiment of the present invention, a plastic molded article having excellent mechanical strength, water resistance and biodegradability may be provided.
Hereinafter, a plastic composition and a molded article thereof according to an embodiment of the present invention will be described in detail.
The plastic composition includes non-biodegradable plastics and acetylated cellulose ethers.
The non-biodegradable plastic may include at least one selected from the group consisting of polyolefin resins, polyester resins and polyamide resins.
The polyolefin resin may include a polypropylene resin, a polyethylene resin, or a combination thereof.
The polypropylene resin may include a propylene homopolymer, a block copolymer, a random copolymer, a modified polypropylene, or a combination thereof. The polypropylene resin may include at least one of those disclosed in US Pat. No. 7,423,071.
The polyethylene resin may include an ethylene homopolymer, a block copolymer, a random copolymer, a modified polyethylene, or a combination thereof. The polyethylene resin may include at least one of those disclosed in US Patent Publication Nos. 2010/0279087 and 2006/0173123.
The polyester resin may be poly (ethylene terephthalate), poly (ethylene terephthalate-isophthalate) copolymer, poly (ethylene-1,4-cyclohexanedimethylene terephthalate) copolymer, poly (ethylene-2,6 Naphthalenedicarboxylate), poly (ethylene-2,6-naphthalenedicarboxylate-terephthalate) copolymer, poly (ethylene terephthalate-4,4′-non-phenyldicarboxylate) copolymer, Or combinations thereof.
The polyamide-based resins are nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, m-xylylene adipamide, hexamethylenediamine-terephthalic acid polymer, hexamethylenediamine-terephthalic acid and adipic Acid polymers, hexamethylenediamine-terephthalic acid and ε-caprolactam copolymers, trimethylhexamethylenediamine-terephthalic acid, or combinations thereof.
The acetylated cellulose ether may have 1 to 2 alkyl group substitution degree (DS), 0 to 3 hydroxyalkyl group substitution degree (MS) and 1 to 3 acetyl group substitution degree (DS).
The acetylated cellulose ether may be formed by acetylation of a cellulose ether having an alkyl group substitution degree (DS) of 1 to 2 and a hydroxyalkyl group substitution degree (MS) of 0 to 3. The alkyl group and the hydroxyalkyl group may each have 1 to 16 carbon atoms. Cellulose may be used as starting material in the preparation of the acetylated cellulose ether.
By acetylating the cellulose ether having the alkyl group substitution degree (DS) range and the hydroxyalkyl group substitution degree (MS) range, an acetylated cellulose ether having excellent water resistance and high molecular weight and excellent mechanical strength can be obtained. This will be described later.
The acetylated cellulose ether may be formed by acetylation of at least one cellulose ether selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose.
In addition, the viscosity of the solution in which the acetylated cellulose ether was dissolved in acetone (concentration of acetylated cellulose ether: 2% by weight) was measured in a Brookfield viscometer at 5 ° C. and 20 rpm under 5-100,000 cps. Can be. If the viscosity is within the above range, the mechanical strength of the acetylated cellulose ether is excellent.
The acetylated cellulose ether may have a melting point of 180 ~ 250 ℃. When the melting point is within the above range, the acetylated cellulose ether may be applied to melt processing such as injection.
Hereinafter, a method for preparing acetylated cellulose ether according to an embodiment of the present invention will be described in detail.
First, the hydroxyl group of cellulose is etherified to produce cellulose ether. That is, a cellulose ether is formed by blocking a part of hydroxyl groups in a cellulose structure by the etherification reaction of a cellulose, or substituting hydrogen in the said hydroxyl group with another substituent. At this time, the main chain of the cellulose is maintained without being cut, but a high molecular weight water-soluble cellulose ether is produced because the hydrogen bond in the cellulose is broken and the cellulose is converted into an amorphous structure. Thereafter, the hydrogen atom in the hydroxyl group included in the prepared water-soluble cellulose ether is substituted with an acetyl group (CH 3 CO − ) (this substitution reaction is called acetylation) to prepare a water-insoluble acetylated cellulose ether. In the following Chemical Formulas 1 and 2, anhydroglucose, which is a basic repeating unit of cellulose, is sequentially etherified and acetylated to convert a basic repeating unit of an acetylated cellulose ether.
Formula 1 shows a process in which cellulose is etherified to be converted into hydroxyalkylalkyl cellulose, and then the hydroxyalkylalkyl cellulose is acetylated to be converted to acetylated cellulose ether. After conversion to alkyl cellulose, the alkyl cellulose is acetylated to show the process of conversion to acetylated cellulose ether.
In Formula 1, R 1 and R 2 may be, independently of each other, H, CH 3 , CH 2 CH 2 OH or CH 2 CH (CH 3 ) OH, and R 3 may be H or CH 3 .
In Formula 2, R 4 and R 5 are each H or CH 3 , and at least one of R 4 and R 5 is CH 3 .
In the present specification, the degree of substitution (DS) means an average number of hydroxyl groups substituted with an alkyl group per anhydroglucose unit. Since there are up to three hydroxyl groups per anhydroglucose unit, the theoretical maximum degree of substitution (DS) when substituted with monofunctional substituents is three. However, since the polyfunctional or polymerizable substituent reacts not only with the hydrogen of the hydroxyl group contained in the anhydroglucose unit but also with itself, the degree of substitution (DS) is not limited to 3. In addition, in the present specification, degree of molar substitution (MS) refers to the number of moles of the polyfunctional or polymerizable substituent per anhydroglucose unit. There is no theoretical maximum of this degree of substitution MS.
The acetylated cellulose ether may be one in which hydrogen in most of the hydroxyl groups present in the cellulose ether is substituted with an acetyl group which is a hydrophobic group. Accordingly, the acetylated cellulose ether is insoluble in water and thus has water resistance, but dissolves in organic solvents.
The content of the acetylated cellulose ether may be 5 to 40 parts by weight based on 100 parts by weight of the non-biodegradable plastic. When the content of the acetylated cellulose ether is within the above range, the biodegradable molded article made of the plastic composition may have excellent water resistance and mechanical strength.
On the other hand, the biodegradable molded article according to an embodiment of the present invention is manufactured by molding the plastic composition.
In addition, an injection machine, a twin screw extruder, a batch kneader or a mixing roll may be used for the molding. In particular, when molding the plastic composition using an injection machine, a compound (ie, a plastic composition) is introduced into a hopper and the front end of the inlet is heated to 180 to 220 ° C. with electric heat or high pressure steam to make the plastic composition molten. It is molded by injection into the mold through the piston mounted to the injection machine. In addition, a lubricant may be used during molding for smooth molding.
Since the acetylated cellulose ether included in the plastic composition is biodegradable and can be well mixed with non-biodegradable plastics, the molded article manufactured by molding the plastic composition is biodegradable. That is, the acetylated cellulose ether uniformly dispersed in the molded article can be decomposed by the microorganism, and thus, the non-biodegradable plastic contained in the molded article is also low molecular weight and eventually decomposed by the microorganism.
The biodegradable molded article has a tensile strength of at least 25 MPa, for example, 25-40 MPa; An Izod impact strength measured at 23 ° C. is at least 42 J / m, eg, 42-55 J / m; Izod impact strength measured at -10 ° C may be 20 J / m or more, for example, 20 ~ 30 J / m. When the tensile strength and the Izod impact strength are within the above ranges, the biodegradable molded article may be applied to automobile interior materials, home appliance cases, storage cases, and mobile phone cases.
The biodegradable molded article may be, for example, an automobile interior material, a home appliance case, a storage case, a mobile phone case, a packaging film, or an envelope.
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these embodiments.
Example
Example 1-5
Manufacturing example One: Acetylation Preparation of Cellulose Ether
Into a 3L reactor equipped with a stirrer, 200 g of cellulose ether, 1400 g of acetic acid, 300 g of sodium acetate, and 600 g of acetic anhydride were added, followed by reaction at 85 ° C. for 8 hours with stirring at 200 rpm to prepare acetylated cellulose ether. At this time, acetic acid was used as a solvent and sodium acetate was used as a catalyst. The reactor contents were then coagulated by spraying into an 18L coagulating bath, washed five times with clean water and dried. The molar ratio of acetic anhydride used per methyl anhydride degree (DS), hydroxypropyl group substitution degree (MS), hydroxyethyl group substitution degree (MS), and anhydroglucose unit contained in each cellulose ether used in each example It is shown in Table 1 below.
Degree of substitution
DS
)
* In Table 1, the cellulose ethers used in Examples 1 to 5 are commercialized specifications produced by Samsung Fine Chemicals.
Manufacturing example 2: Preparation of Plastic Composition
87 parts by weight of polypropylene block copolymer (BASELL, Moplen EP548P), 3 parts by weight of modified polypropylene (Polyphenco, DYNALON PP) and 10 parts by weight of each acetylated cellulose ether prepared in Preparation Example 1 Plastic compositions were prepared.
Manufacturing example 3: manufacture of molded articles
The plastic composition prepared in Preparation Example 2 was molded using an injection machine (FANUC ROBOSHOT 2000i-50B). In the molding, the temperature of the outlet of the injection machine was 220 ℃, the injection speed is 150mm / s, the holding pressure was 500Kgf / cm 2 .
Comparative example One
Except that 97 parts by weight of polypropylene block copolymer (Moplen EP548P, BASELL Co., Ltd.) and 3 parts by weight of modified polypropylene (Polyphenco, DYNALON PP) were used, and no acetylated cellulose ether was used. The molded article was manufactured by the same method as 1-5.
Comparative example 2
A molded article was manufactured in the same manner as in Examples 1 to 5, except that 10 parts by weight of starch ether (Samyang, General Starch) was used instead of 10 parts by weight of acetylated cellulose ether.
Evaluation example
Evaluation example : Acetylation Evaluation of Physical Properties of Cellulose Ethers and Molded Products
The acetyl group substitution degree and molecular weight of each acetylated cellulose ether sample prepared in Examples 1 to 5, the molecular weight of the starch ether sample used in Comparative Example 2, and in Examples 1 to 5 and Comparative Examples 1 to 2 Tensile strength, flexural strength, flexural modulus, Izod impact strength, and biodegradation rate of each manufactured molded product sample were measured by the following method, and the results are shown in Table 2 below.
(Measurement of acetyl group substitution degree)
Free acetic acid formed by saponification of each of the acetylated cellulose ether samples was titrated with alkali, and the degree of acetyl group substitution (DS) of each of the samples was measured (ASTM D871-96).
(Measurement of molecular weight)
The weight average molecular weight (Mw) of each of the acetylated cellulose ether samples was measured using size exclusion chromatography (Agilent, HP 1100). Specifically, 0.1 g of each sample was dissolved in 100 g of dimethylformamide (HPLC grade), and then measured under conditions of a temperature of 25 ° C. and a flow rate of 10 ml / min using dimethylformamide as a mobile phase.
(Measurement of tensile strength)
The tensile strength of each molded article was measured according to ASTM D638.
(Measurement of Flexural Strength and Flexural Modulus)
Flexural strength and flexural modulus of each molded article were measured according to ASTM D790.
(Measurement of Izod impact strength)
The Izod impact strength of each molded article was measured at 23 ° C. and −10 ° C. according to ASTM D256, respectively.
(Measurement of biodegradation rate)
The biodegradation rate of each of the molded articles was measured 50 and 150 days after the production of each of the molded articles, respectively, according to the method defined in ISO 14855-99.
(DS)
(kDa)
burglar
(MPa)
burglar
(MPa)
Elastic modulus
(MPa)
(J / m)
Biodegradation rate
(%)
Referring to Table 2, each of the acetylated cellulose ether prepared in Examples 1 to 5 was found to have a very high molecular weight compared to the starch ether used in Comparative Example 2. In addition, each of the molded articles prepared in Examples 1 to 5 was found to meet the requirements of ISO 14855 (biodegradation rate> 90% within 180 days) for the ISO biodegradable products, while having a relatively good mechanical strength. In addition, each molded article prepared in Examples 1 to 5 naturally have water resistance because it includes plastic having water resistance and acetylated cellulose ether. On the other hand, the molded article prepared in Comparative Example 1 was found to have a relatively good mechanical strength but a biodegradation rate of nearly 0%. In addition, the molded article prepared in Comparative Example 2 was found to have a high biodegradation rate but very low mechanical strength.
Although the present invention has been described with reference to the examples, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.
Claims (7)
Plastic composition comprising acetylated cellulose ether.
The acetylated cellulose ether is a plastic composition having an alkyl group substitution degree (DS) of 1 to 2, a hydroxyalkyl group substitution degree (MS) of 0 to 3, and an acetyl group substitution degree (DS) of 1-3.
The acetylated cellulose ether is a plastic composition formed by acetylating at least one cellulose ether selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose.
The content of the acetylated cellulose ether is 5 to 40 parts by weight based on 100 parts by weight of the non-biodegradable plastic.
A biodegradable molded article having a tensile strength of 25 Mpa or more, an Izod impact strength measured at 23 ° C. of 42 J / m or more, and an Izod impact strength measured at −10 ° C. of 20 J / m or more.
The biodegradable molded article is a car interior material, a home appliance case, a mobile phone case, a storage case, a packaging film or a biodegradable molded article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110055264A KR20120136194A (en) | 2011-06-08 | 2011-06-08 | Plastic composition and biodegradable molded article of the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110055264A KR20120136194A (en) | 2011-06-08 | 2011-06-08 | Plastic composition and biodegradable molded article of the composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20120136194A true KR20120136194A (en) | 2012-12-18 |
Family
ID=47903721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110055264A KR20120136194A (en) | 2011-06-08 | 2011-06-08 | Plastic composition and biodegradable molded article of the composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20120136194A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220114177A (en) | 2021-02-08 | 2022-08-17 | 소니아코리아 주식회사 | Biodegradable cell phone case with antibacterial and antiviral functions |
-
2011
- 2011-06-08 KR KR1020110055264A patent/KR20120136194A/en active Search and Examination
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220114177A (en) | 2021-02-08 | 2022-08-17 | 소니아코리아 주식회사 | Biodegradable cell phone case with antibacterial and antiviral functions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6365079B1 (en) | Process for preparing starch and epoxy-based thermoplastic polymer compositions | |
| EP0711325B1 (en) | A method of preparing biodegradable modified-starch moldable products and films | |
| KR101682466B1 (en) | Acetylated cellulose ether and articles comprising the same | |
| WO2006055505A2 (en) | Starch-polyester biodegradable graft copolymers and a method of preparation thereof | |
| CN110408180B (en) | Lignin-starch combined master batch compounded biodegradable polyester material and preparation method thereof | |
| US20090160095A1 (en) | Biodegradable thermoplasticized starch-polyester reactive blends for thermoforming applications | |
| JP5469322B2 (en) | Environmentally friendly thermoplastic resin composition | |
| CN112552655B (en) | Modified cellulose filled PBAT/PLA composition suitable for preparing film, and preparation and application thereof | |
| Quintana et al. | Compatibilization of co-plasticized cellulose acetate/water soluble polymers blends by reactive extrusion | |
| Wu et al. | Preparation and characterization of acetylated maltodextrin and its blend with poly (butylene adipate-co-terephthalate) | |
| KR19980702713A (en) | Esterized Polyester Graft Polymerized Starch and Alloys thereof | |
| KR101837634B1 (en) | Acetylated cellulose ether, method of preparing the acetylated cellulose ether and articles comprising the same | |
| KR20120136194A (en) | Plastic composition and biodegradable molded article of the composition | |
| EP2930190B1 (en) | Method for preparing acetylated cellulose ethers having improved anti-fouling properties, and acetylated cellulose ethers prepared by same | |
| KR101749620B1 (en) | Acetylated cellulose ether and articles comprising the same | |
| JP6107910B2 (en) | Resin composition and resin molded body | |
| CN107793592B (en) | Biodegradable aliphatic aromatic copolyester toughened thermoplastic polysaccharide blend and preparation method and film thereof | |
| KR101407691B1 (en) | Bioplastic composition and method for preparing the same | |
| KR101750474B1 (en) | Resin composition comprising polyalkylenecarbonate and method for preparation thereof | |
| JP7336870B2 (en) | resin composition | |
| CN107793591B (en) | Biodegradable polyester toughened thermoplastic polysaccharide blend and preparation method and film thereof | |
| KR100257036B1 (en) | A process of preparing for excellent reaction-property thermo elastic starch, its resin composite, its complex materials | |
| CN115505254B (en) | Photo-biodegradable polyketone starch composite material and preparation method thereof | |
| JP2007039513A (en) | Polybutylene succinate resin composition, its production method, molded article comprising the same | |
| JP3372648B2 (en) | Method for producing molded article of thermoplastic cellulose derivative composition having biodegradability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| AMND | Amendment |