CN111040276A - Biodegradable composite material resin and preparation method thereof - Google Patents
Biodegradable composite material resin and preparation method thereof Download PDFInfo
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- CN111040276A CN111040276A CN201911328203.2A CN201911328203A CN111040276A CN 111040276 A CN111040276 A CN 111040276A CN 201911328203 A CN201911328203 A CN 201911328203A CN 111040276 A CN111040276 A CN 111040276A
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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
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a biodegradable composite material resin, which is prepared by taking low-density polyethylene and polybutylene succinate as main bodies, epoxidized soybean oil as a liquid plasticizer, polyethylene glycol-4000 as a solid plasticizer and other raw materials as auxiliary materials according to reasonable proportion. The invention has the advantages of cheap and easily obtained raw materials, simple operation of the preparation process and wide market application prospect, and can be used for mass production and market popularization and application.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to biodegradable composite material resin and a preparation method thereof.
Background
Polyethylene is one of five synthetic resins, mainly divided into three categories, namely linear low-density polyethylene, low-density polyethylene and high-density polyethylene, and the high-density polyethylene is a thermoplastic resin with high crystallinity and non-polarity, has good chemical stability, higher rigidity and toughness and good mechanical strength, and can be used in the field of packaging. However, the polymer material is stable in nature, is difficult to degrade and is easy to cause white pollution. These white contaminants remain undegraded and accumulate in the natural environment, affecting the environment on which humans live and the health of people.
The existing copolyesters such as polylactic acid, polycaprolactone, polybutylene succinate and the like which can be biodegraded have been successfully researched and developed, but the raw materials are expensive, have special requirements on processing and forming equipment and complex preparation process, and are not produced in large scale and applied in markets.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the biodegradable composite material resin and the preparation method thereof through reasonable proportioning, and the biodegradable composite material resin has the advantages of cheap and easily-obtained raw materials, simple preparation process and equivalent comprehensive performance to plastic products.
In order to overcome the technical problems, the technical scheme adopted by the invention is as follows:
a biodegradable composite resin comprises the following components in parts by weight: 30-90 parts of low-density polyethylene, 0.01-0.1 part of paraffin, 0.01-10 parts of starch, 0.1-5 parts of carbon-nitrogen double-doped nano titanium dioxide, 2-25 parts of aqueous natural polymer aqueous solution, 2-8 parts of liquid plasticizer, 1-10 parts of solid plasticizer, 10-35 parts of active inorganic filler and 5-80 parts of poly (butylene succinate).
As a further improvement of the above scheme, the biodegradable composite resin comprises, in parts by weight: 30 parts of low-density polyethylene, 0.01 part of paraffin, 0.01 part of starch, 0.1 part of carbon-nitrogen double-doped nano titanium dioxide, 2 parts of aqueous natural high-molecular water solution, 2 parts of liquid plasticizer, 1 part of solid plasticizer, 10 parts of active inorganic filler and 5 parts of polybutylene succinate.
As a further improvement of the above scheme, the biodegradable composite resin comprises, in parts by weight: 90 parts of low-density polyethylene, 0.1 part of paraffin, 10 parts of starch, 5 parts of carbon-nitrogen double-doped nano titanium dioxide, 25 parts of aqueous natural polymer aqueous solution, 8 parts of liquid plasticizer, 10 parts of solid plasticizer, 35 parts of active inorganic filler and 80 parts of poly (butylene succinate).
As a further improvement of the above scheme, the biodegradable composite resin comprises, in parts by weight: 45 parts of low-density polyethylene, 0.05 part of paraffin, 5 parts of starch, 2.5 parts of carbon-nitrogen double-doped nano titanium dioxide, 13 parts of aqueous natural high-molecular water solution, 5 parts of liquid plasticizer, 5 parts of solid plasticizer, 22 parts of active inorganic filler and 40 parts of polybutylene succinate.
As a further improvement of the scheme, the active inorganic filler is calcium carbonate and talcum powder which are activated by a rare earth coupling agent.
As a further improvement of the above scheme, the aqueous natural polymer in the aqueous solution of aqueous natural polymers is selected from at least one of cyclodextrin, polyanionic cellulose, hydroxypropyl cellulose, methyl cellulose, starch, hydroxyethyl cellulose, water-soluble chitin, sodium alginate, hyaluronic acid, lignosulfonate, agarose, and collagen.
As a further improvement of the above aspect, the liquid plasticizer comprises epoxidized soybean oil.
As a further improvement of the above, the solid plasticizer comprises polyethylene glycol-4000.
A preparation method of biodegradable composite resin comprises the following steps: weighing the raw materials according to the formula of the biodegradable composite material resin for later use; drying the poly (butylene succinate) and the low-density polyethylene at 50-120 ℃ for 2-10h, uniformly mixing with other raw materials, adding into a double-screw extruder, and extruding and granulating to obtain the biodegradable composite resin.
The invention has the beneficial effects that: the invention provides a biodegradable composite material resin, which is prepared by taking low-density polyethylene and polybutylene succinate as main bodies, epoxidized soybean oil as a liquid plasticizer, polyethylene glycol-4000 as a solid plasticizer and other raw materials as auxiliary materials according to reasonable proportion. The invention has the advantages of cheap and easily obtained raw materials, simple operation of the preparation process and wide market application prospect, and can be used for mass production and market popularization and application.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercially available products; the process steps or extraction methods not mentioned in detail are all process steps or extraction methods known to the person skilled in the art.
Example 1
A biodegradable composite resin comprises the following components in parts by weight: 30 parts of low-density polyethylene, 0.01 part of paraffin, 0.01 part of starch, 0.1 part of carbon-nitrogen double-doped nano titanium dioxide, 2 parts of hydroxypropyl cellulose aqueous solution, 2 parts of epoxidized soybean oil, 01 parts of polyethylene glycol-40001 parts, 10 parts of active inorganic filler and 5 parts of polybutylene succinate.
A preparation method of biodegradable composite resin comprises the following steps: weighing the raw materials according to the formula of the biodegradable composite material resin for later use; drying the poly (butylene succinate) and the low-density polyethylene at 120 ℃ for 2h, uniformly mixing with other raw materials, adding into a double-screw extruder, and extruding and granulating to obtain the biodegradable composite material resin finished product 1.
Example 2
A biodegradable composite resin comprises the following components in parts by weight: 90 parts of low-density polyethylene, 0.1 part of paraffin, 10 parts of starch, 5 parts of carbon-nitrogen double-doped nano titanium dioxide, 25 parts of sodium alginate aqueous solution, 8 parts of epoxidized soybean oil, 400010 parts of polyethylene glycol-400010 parts, 35 parts of active inorganic filler and 80 parts of polybutylene succinate.
A preparation method of biodegradable composite resin comprises the following steps: weighing the raw materials according to the formula of the biodegradable composite material resin for later use; drying the poly (butylene succinate) and the low-density polyethylene at 50 ℃ for 12h, uniformly mixing with other raw materials, adding into a double-screw extruder, and extruding and granulating to obtain the biodegradable composite material resin finished product 2.
Example 3
A biodegradable composite resin comprises the following components in parts by weight: 45 parts of low-density polyethylene, 0.05 part of paraffin, 5 parts of starch, 2.5 parts of carbon-nitrogen double-doped nano titanium dioxide, 13 parts of sodium alginate aqueous solution, 5 parts of epoxidized soybean oil, 22 parts of polyethylene glycol-40005 parts of active inorganic filler and 40 parts of polybutylene succinate.
A preparation method of biodegradable composite material resin comprises weighing raw materials according to the formula of the biodegradable composite material resin; drying the poly (butylene succinate) and the low-density polyethylene at 80 ℃ for 7h, uniformly mixing with other raw materials, adding into a double-screw extruder, and extruding and granulating to obtain the biodegradable composite resin finished product 3.
Example 4
A biodegradable composite resin comprises the following components in parts by weight: 50 parts of low-density polyethylene, 0.04 part of paraffin, 5 parts of starch, 2.5 parts of carbon-nitrogen double-doped nano titanium dioxide, 10 parts of sodium alginate aqueous solution, 4 parts of epoxidized soybean oil, 20 parts of polyethylene glycol-40005 parts of active inorganic filler and 40 parts of polybutylene succinate.
A preparation method of biodegradable composite resin comprises the following steps: weighing the raw materials according to the formula of the biodegradable composite material resin for later use; drying the poly (butylene succinate) and the low-density polyethylene at 80 ℃ for 6h, uniformly mixing with other raw materials, adding into a double-screw extruder, and extruding and granulating to obtain the biodegradable composite material resin finished product 4.
Comparative example 1
The petroleum resin plastic product purchased in the market is marked as a finished product 1 of a comparative example.
Example 5
The biodegradable composite resin products 1 to 4 prepared in examples 1 to 4 and the comparative example product 1 were subjected to the thermal deformation temperature, tensile strength, tensile elongation at break, degradation rate and other property tests, and the test results are shown in table 1 below. Wherein, the test of tensile strength and tensile breaking elongation is carried out according to GB/T1040, 3-2006 standard, the tensile rate is 50mm/min, and the sensor is 500N.
TABLE 1 Performance test results for biodegradable composite resin end products 1-4 and comparative example end product 1
As can be seen from Table 1, the biodegradable composite resin prepared by the invention has higher thermal deformation temperature, tensile strength, elongation at break and better degradation efficiency, and can completely replace petroleum resin to be used for manufacturing plastic products.
It will be obvious to those skilled in the art that many simple derivations or substitutions can be made without inventive effort without departing from the inventive concept. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.
Claims (9)
1. A biodegradable composite resin is characterized by comprising the following components in parts by weight: 30-90 parts of low-density polyethylene, 0.01-0.1 part of paraffin, 0.01-10 parts of starch, 0.1-5 parts of carbon-nitrogen double-doped nano titanium dioxide, 2-25 parts of aqueous natural polymer aqueous solution, 2-8 parts of liquid plasticizer, 1-10 parts of solid plasticizer, 10-35 parts of active inorganic filler and 5-80 parts of poly (butylene succinate).
2. The biodegradable composite resin according to claim 1, characterized in that it comprises, in parts by weight: 30 parts of low-density polyethylene, 0.01 part of paraffin, 0.01 part of starch, 0.1 part of carbon-nitrogen double-doped nano titanium dioxide, 2 parts of aqueous natural high-molecular water solution, 2 parts of liquid plasticizer, 1 part of solid plasticizer, 10 parts of active inorganic filler and 5 parts of polybutylene succinate.
3. The biodegradable composite resin according to claim 1, characterized in that it comprises, in parts by weight: 90 parts of low-density polyethylene, 0.1 part of paraffin, 10 parts of starch, 5 parts of carbon-nitrogen double-doped nano titanium dioxide, 25 parts of aqueous natural polymer aqueous solution, 8 parts of liquid plasticizer, 10 parts of solid plasticizer, 35 parts of active inorganic filler and 80 parts of poly (butylene succinate).
4. The biodegradable composite resin according to claim 1, characterized in that it comprises, in parts by weight: 45 parts of low-density polyethylene, 0.05 part of paraffin, 5 parts of starch, 2.5 parts of carbon-nitrogen double-doped nano titanium dioxide, 13 parts of aqueous natural high-molecular water solution, 5 parts of liquid plasticizer, 5 parts of solid plasticizer, 22 parts of active inorganic filler and 40 parts of polybutylene succinate.
5. The biodegradable composite resin according to claim 1, characterized in that said active inorganic filler is calcium carbonate and talc activated by rare earth coupling agent.
6. The biodegradable composite resin according to claim 1, wherein the aqueous natural polymer in the aqueous solution of aqueous natural polymer is at least one selected from cyclodextrin, polyanionic cellulose, hydroxypropyl cellulose, methyl cellulose, starch, hydroxyethyl cellulose, water-soluble chitin, sodium alginate, hyaluronic acid, lignosulfonate, agarose, collagen.
7. The biodegradable composite resin according to claim 1, wherein said liquid plasticizer comprises epoxidized soybean oil.
8. The biodegradable composite resin according to claim 1, wherein said solid plasticizer comprises polyethylene glycol-4000.
9. A preparation method of biodegradable composite resin is characterized by comprising the following steps: weighing the raw materials according to the formula of the biodegradable composite resin as defined in any one of claims 1 to 8 for later use; drying the poly (butylene succinate) and the low-density polyethylene at 50-120 ℃ for 2-10h, uniformly mixing with other raw materials, adding into a double-screw extruder, and extruding and granulating to obtain the biodegradable composite resin.
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| CN201911328203.2A CN111040276B (en) | 2019-12-20 | 2019-12-20 | Biodegradable composite material resin and preparation method thereof |
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| CN201911328203.2A CN111040276B (en) | 2019-12-20 | 2019-12-20 | Biodegradable composite material resin and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103987523A (en) * | 2011-09-26 | 2014-08-13 | Ｋｒｈ株式会社 | Stretch film product |
| CN104387657A (en) * | 2014-12-02 | 2015-03-04 | 国家电网公司 | Degradable packaging plastic for electric power systems |
| CN104557323A (en) * | 2015-01-27 | 2015-04-29 | 北京富特来复合肥料有限公司 | Degradable resin coating material and application thereof |
| KR20170075052A (en) * | 2015-12-22 | 2017-07-03 | 롯데정밀화학 주식회사 | Resin composition for mulching film and biodegradable mulching film using the same |
| KR20190067320A (en) * | 2017-12-07 | 2019-06-17 | 전상민 | Eco-friendly biedegradable thermo plastic polymer resin composition and it's manufacturing film |
-
2019
- 2019-12-20 CN CN201911328203.2A patent/CN111040276B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103987523A (en) * | 2011-09-26 | 2014-08-13 | Ｋｒｈ株式会社 | Stretch film product |
| CN104387657A (en) * | 2014-12-02 | 2015-03-04 | 国家电网公司 | Degradable packaging plastic for electric power systems |
| CN104557323A (en) * | 2015-01-27 | 2015-04-29 | 北京富特来复合肥料有限公司 | Degradable resin coating material and application thereof |
| KR20170075052A (en) * | 2015-12-22 | 2017-07-03 | 롯데정밀화학 주식회사 | Resin composition for mulching film and biodegradable mulching film using the same |
| KR20190067320A (en) * | 2017-12-07 | 2019-06-17 | 전상민 | Eco-friendly biedegradable thermo plastic polymer resin composition and it's manufacturing film |
Non-Patent Citations (3)
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| 唐见茂 编著: "《绿色复合材料》", 31 December 2016, 中国铁道出版社 * |
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