KR20120126854A - Preparation method of eco-friendly biomass-elastomer - Google Patents

Preparation method of eco-friendly biomass-elastomer Download PDF

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KR20120126854A
KR20120126854A KR1020110044951A KR20110044951A KR20120126854A KR 20120126854 A KR20120126854 A KR 20120126854A KR 1020110044951 A KR1020110044951 A KR 1020110044951A KR 20110044951 A KR20110044951 A KR 20110044951A KR 20120126854 A KR20120126854 A KR 20120126854A
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diene
biomass
styrene
based polymer
elastomer
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KR1020110044951A
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Korean (ko)
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김진국
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경상대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Abstract

PURPOSE: A manufacturing method of a biomass elastomer is provided to manufacture a resource-circulation type natural material-based environment-friendly biomass elastomer with excellent critical performance by using vegetable oil. CONSTITUTION: A manufacturing method of a biomass elastomer comprises a step of obtaining a terminal of a diene-based polymer by a functional group; a step of obtaining fatty acid by purifying vegetable oil; and a step of manufacturing biomass elastomer by polymerization-reacting the diene based polymer of which terminal is modified by a functional group with aliphatic acid of vegetable oil. The diene-based polymer is selected from a group consisting of styrene butadiene rubber, butadiene rubber, and styrene butadiene styrene.

Description

Preparation method of eco-friendly biomass elastomers {Preparation method of eco-friendly biomass-elastomer}

The present invention relates to a method for producing an eco-friendly biomass elastomer based on vegetable oils.

As a result of the progress of industrial technology and mass consumption of petroleum, which is a fossil resource, the limitations of global warming and dependence on fossil resources are emerging as big problems, and as a means to solve them, recyclable resources The development of technology to convert raw materials to in-biomass is highly demanded in the field of energy materials.

Synthetic polymers used as plastics or elastomers (rubbers) are being used in production materials, building materials, and packaging materials in large quantities, which is a major obstacle to building a continuous circular global environment. Reuse and recycling of synthetic polymers has been attempted, but the reality is that they do not contribute significantly to problem solving. Biodegradable polymers are attracting attention as a realistic countermeasure and commercial production has begun. In addition, attention has been focused on polymers for plastics / elastomers derived from biomass in terms of global warming countermeasures and effective use of resources.

Biopolymers can be classified into two types as eco-friendly materials that enable the sustainable development of society and drive low carbon green growth. Biomass-based plastics produced through chemical or biological processes using biomass, a renewable material such as plant-derived resources, and biodegradable biodegradable materials, which can be completely decomposed by microorganisms under certain conditions Plastics (biodegradable plastics) are included.

Biodegradable plastic polymer is a plastic that can be completely decomposed into water and carbon dioxide by the action of microorganisms such as bacteria, algae, fungi and decomposing enzymes existing in water, nature in a certain condition unlike the widely used refractory plastic materials It is produced from a variety of raw materials (biomass or fossil fuel based compounds). Biodegradable plastics can be used in the same way as ordinary plastic products. After use, they can not only be buried in the ground but are also eco-friendly plastics that do not emit harmful substances such as dioxins due to low calorific value.

Biodegradable plastics are synthesized from various raw materials. First, biodegradable polymers made from natural polymers are derived from plants such as Cellulose, Hemicellulose, Pectin, Lignin, and starch, which is a stored carbohydrate, and include shells of shrimp and crabs. There are animal origins based on chitin. There are also microbial biopolymers produced by microorganisms, such as polyalkanoates such as poly-β-hydroxybutyrate (PHB), poly-β-hydrolyvalerate (PHV), and their copolymers PHB / PHV. . Aliphatic polyesters, polycaprolactone (PCL), and poly- (glycolic acid) (PGA) are biodegradable polymers obtained by chemically synthesizing monomers. Since it is easy to give various functions, it is commercially produced for plastic use.

On the other hand, instead of using the existing fossil fuel, biomass, a renewable plant-derived resource, can be used as a raw material to synthesize a polymer, which is biomass plastic.

Biomass plastics are defined as polymeric materials obtained by chemically or biologically synthesizing a substance derived from renewable organic resources as a raw material.

Biomass plastics are a very useful material in terms of reducing carbon emissions because biomass, a raw material, is produced by photosynthesis, and requires carbon dioxide in the air in this process. On the other hand, biodegradable plastics have the advantage of providing an end-of-life alternative that is convenient for landfill or composting after use. For example, a garbage bag made of biodegradable plastic can be used by composting the contents and bags together after a period of composting.

Examples of such biomass plastics include starch-based plastics using starch and poly (lactic acid) and PLA produced through conversion from corn to glucose, lactic acid and lactide, which are biomass plastics and at the same time biodegradable. Indicates. Research into the use of non-edible crops other than corn as raw materials, and research and development to manufacture general-purpose resins such as polyamides and polyolefins from biomass raw materials.

Biomass plastics obtained by chemical synthesis include polyesters such as polylactic acid and polytrimethylene terephthalate. They are molded and processed into films and fibers, and their use is being developed mainly in the field of general plastics. On the other hand, in the field of engineering plastics requiring heat resistance, there are polyamides such as polyamide 11 (melting point 187 ° C) and polyamide 610 (melting point 215 ° C), which are made from castor oil ricinol acid, and polyamide 4 (melting point 260 ° C). R & D is progressing with the goal of practical application in high value-added applications requiring high performance properties.

However, these biomass plastics have low physical properties such as flame retardancy, impact resistance, heat resistance, and moldability, compared to conventional plastics based on petroleum. Therefore, these biomass plastics are currently used in a limited number of products such as food containers and packaging materials. .

Therefore, there is a need for the production of biomass plastics with improved properties while reusing resources.

On the other hand, diene polymer is a polymer material having remarkable elasticity as rubbers, such as polybutadiene rubber (BR), styrene-butadiene rubber (SBR), carboxyl terminated polybutadiene (CTPB), and hydroxyl terminated polybutadiene (HTPB). ).

The properties of the diene-based polymer vary greatly depending on the microstructure showing the position and stereochemical properties of the -C = C- double bond in the repeating unit of the polymer chain and the macrostructure indicating branching, molecular weight and molecular weight distribution.

Since the diene-based polymer has various microstructures and copolymer types in terms of molecular structure, it is possible to make an elastomer having various physical properties, and thus has a wide range of uses.

For example, currently used carboxyl terminal polybutadiene (CTPB) is used as a rocket propellant binder, and is also widely used in the coating industry, and hydroxyl terminal polybutadiene (HTPB) is a binder of a solid propellant, an adhesive, an electric wire coating, and the like. Used.

In addition, styrene-butadiene rubber (SBR) is a copolymer made by low-temperature emulsion polymerization of butadiene and styrene.It is the most commonly used general purpose rubber among synthetic rubbers, and has excellent abrasion resistance, heat resistance, and vulcanization with stable vulcanization compared to natural rubber. It has a wide range of physical properties such as scorching and easy processing, and is used in most rubber products such as tires, shoes, rubber hoses, and belts.

However, an example of producing biomass elastomer by introducing biomass into such diene-based polymer has not been reported.

Therefore, the inventors of the present invention while researching to produce a new biopolymer with improved properties while reusing resources, polymerizing high molecular weight diene-based polymer and modifying the end of the diene-based polymer with a functional group and then vegetable The present invention has been completed by confirming that a biomass elastomer can be prepared by combining a diene with fatty acids in vegetable oil by reacting with fatty acids of oil.

An object of the present invention is to provide a method for producing an eco-friendly biomass elastomer using a vegetable oil.

In order to achieve the above object, the present invention comprises the steps of modifying the end of the diene polymer with a functional group (step 1); Purifying the vegetable oil to obtain a fatty acid (step 2); And it provides a method for producing an eco-friendly biomass elastomer comprising a step (step 3) of polymerizing the diene-based polymer modified at the end of the functional group with a fatty acid of the vegetable oil in step 2.

The biomass elastomer of the present invention is a biomass, which is a renewable organic resource, as a raw material, and grafted with a high molecular weight diene-based polymer. Since it can be manufactured, it can be widely applied to a variety of industries, such as medical, footwear materials, automotive component material and electrical and electronic component material industry.

1 is a 1 H-NMR spectrum of a waste vegetable oil.
2 is an FT-IR analysis spectrum of waste vegetable oil.
Figure 3 is a 1 H-NMR spectrum of the fatty acid obtained by separating waste vegetable oil.
4 is an FT-IR analysis spectrum of fatty acids obtained by separating waste vegetable oil.
5 is a 1 H-NMR spectrum of the eco-friendly elastomer according to an embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention

Modifying the end of the diene-based polymer with a functional group (step 1);

Purifying the vegetable oil to obtain a fatty acid (step 2); And

It provides a method for producing an eco-friendly biomass elastomer comprising the step (step 3) of producing a biomass elastomer by polymerizing the diene-based polymer modified at the end of the functional group with the fatty acid of the vegetable oil.

First step 1 is a step of modifying the end of the diene-based polymer with a functional group.

The properties of diene-based polymers vary greatly depending on the microstructure showing the position and stereochemical properties of -C = C- double bonds in the repeating units of the polymer chain, and the macrostructure indicating branching, molecular weight and molecular weight distribution.

Since diene-based polymer has various microstructures and copolymer types in terms of molecular structure, it is possible to make elastomers having various physical properties.

In the production method according to the present invention, the diene-based polymer may be used styrene-butadiene rubber (SBR; Styrene Butadiene Rubber), butadiene rubber (BR; Butadiene Rubber) and styrene butadiene styrene (SBS; Styrene Butadiene Styrene) It is preferable to use styrene-butadiene rubber. The diene-based polymer may be prepared by a polymerization method commonly used in the art. For example, when styrene-butadiene rubber is used as the diene-based polymer, the styrene-butadiene is an n-BuLi catalyst for the styrene monomer and the butadiene monomer. May be used to polymerize to a desired molecular weight, but is not limited thereto.

In this case, the styrene-butadiene rubber may include styrene monomer and butadiene monomer in various ratios by weight ratio, but is preferably included in 25:75.

In the production method according to the present invention, the diene polymer is preferably 10,000 or more molecular weight, more preferably 10,000 to 100,000 molecular weight.

In one example, a styrene-butadiene rubber having a molecular weight of 10,000 or more can be prepared by putting a styrene monomer and a butadiene monomer in a 25:75 ratio by weight in a high pressure reactor, and then adding n-BuLi as an initiator and polymerizing the reaction.

In the production method according to the present invention, the terminal of the diene-based polymer may be modified with various functional groups, and the functional group may be preferably an amino group, a hydroxyl group, a carboxyl group, etc., but is not limited thereto.

A method of modifying the end of the diene-based polymer with a functional group may be used in the art, for example, 4-bromo-N, N-bis (trimethylsilyl) aniline using an amino group at the terminal of the polybutadiene Can be modified.

Next, step 2 is to purify the waste vegetable oil to obtain fatty acids.

In this step, the waste vegetable oil may be selected from the group consisting of soybean oil, sunflower oil and palm oil, but is not limited thereto.

As shown in FIGS. 1 and 2, the waste vegetable oil may be composed of triglycerides through 1 H-NMR analysis and FT-IR analysis. As shown in, 1 H-NMR analysis and IR analysis show that the end is composed of carboxyl groups as unsaturated hydrocarbons.

Therefore, the fatty acid can be easily bound to the terminal of the diene-based polymer modified with the functional group.

In the production method according to the present invention, the fatty acid may be obtained from waste vegetable oils, and may be commercially available or synthesized by methods according to the art.

In the production method according to the present invention, the method for purifying the waste vegetable oil may be performed by a method commonly used in the art, but is not limited thereto.

Next, step 3 is a step of preparing a biomass elastomer by polymerizing a diene-based polymer whose end group is modified with a functional group in step 1 with fatty acids of waste vegetable oil.

The reaction may be carried out in a high-temperature reactor in which the reaction temperature is preferably 200 to 250 ° C.

The biomass elastomer of the present invention is a biomass, which is a renewable organic resource, as a raw material, and grafted with a high molecular weight diene-based polymer. Since it can be manufactured, it can be widely applied to a variety of industries, such as medical, footwear materials, automotive component material and electrical and electronic component material industry.

Hereinafter, the present invention will be described in detail with reference to examples. However, these examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

< Example > Waste vegetable  Oil-based eco-friendly Biomass  Preparation of Elastomers

Step 1: Of Styrene-Butadiene Rubber Terminal group  Modification

(1) Polymerization of Styrene-Butadiene Rubber

Figure pat00001

A styrene monomer, butadiene monomer and n-BuLi as an initiator were added to a high pressure reactor, and polymerization was performed. In this case, the styrene monomer and the butadiene monomer were reacted in a weight ratio of 25: 75 to prepare a styrene-butadiene rubber having a molecular weight of 100,000.

(2) of styrene-butadiene rubber Terminal group  Modification

Figure pat00002

4-bromo-N, N-bis (trimethylsilyl) aniline was added to the styrene-butadiene rubber prepared in (1), followed by stirring for 3 hours. After 10% HCl / MeOH and 10% NaOH solution was added to replace the terminal bis (trimethylsilyl) with hydrogen (H) and neutralized with NaOH. Thereafter, the reactants were quenched with MeOH in the reactor to remove impurities and precipitate, and the solvents were evaporated in an evaporator at 70 ° C. In the vacuum drying oven, both the moisture and impurities were removed by evaporation under vacuum to modify the terminal group of the styrene-butadiene rubber with NH 2 .

Step 2: Waste vegetable  Fatty Acid Separation from Oil

Fatty acid and waste glycerol were separated after methanol treatment from waste cooking oil. At this time, glycerol (95%) and fatty acid (5%) were separated with waste glycerol. To this end, first, waste glycerol was filled into a beaker at a ratio of 4: 1 to water, and stirred with a stirrer. Then, pH was adjusted by adding HCl 35.0% little by little. I set it up to be. After the precipitation reaction, fatty acids were obtained from the waste vegetable oil.

Step 3: Biomass  Elastomer production

Figure pat00003

The styrene-butadiene rubber in which the end group obtained in step 1 was modified with NH 2 and the fatty acid obtained in step 2 were put in a high pressure reactor to react at 200-250 ° C. for 3 hours to prepare a biomass elastomer.

1 H NMR spectrum of the manufactured eco-friendly biomass elastomer is shown in FIG. 5. As shown in Figure 5, it can be seen that the produced biomass elastomer is well bonded to the styrene-butadiene rubber and fatty acid.

So far I looked at the center of the preferred embodiment for the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (11)

Modifying the end of the diene polymer with a functional group (step 1);
Purifying the vegetable oil to obtain a fatty acid (step 2); And
Method of producing a biomass elastomer comprising a step (step 3) of producing a biomass elastomer by polymerizing the diene-based polymer modified at the end of the functional group with a fatty acid of vegetable oil in step 2. Modifying the end of the diene-based polymer with a functional group (step 1); And
Method of producing a biomass elastomer comprising a step (step 2) of producing a biomass elastomer by polymerizing the diene-based polymer modified at the terminal with a functional group in step 1 with a fatty acid. The method according to claim 1 or 2,
The diene-based polymer of the biomass elastomer, characterized in that selected from the group consisting of styrene-butadiene rubber (SBR; Styrene Butadiene Rubber), butadiene rubber (BR; Butadiene Rubber) and styrene butadiene styrene (SBS) Manufacturing method. The method of claim 3,
The diene-based polymer is a method for producing a biomass elastomer, characterized in that the styrene-butadiene rubber. 5. The method of claim 4,
The styrene-butadiene rubber is a method for producing a biomass elastomer, characterized in that the styrene monomer and the butadiene monomer are contained in a weight ratio of 25: 75. The method according to claim 1 or 2,
The molecular weight of the diene-based polymer is a method for producing a biomass elastomer, characterized in that 10,000 ~ 100,000. The method according to claim 1 or 2,
Wherein the functional group is an amino group, a hydroxyl group or a carboxyl group. The method of claim 7, wherein
The functional group is a method for producing a biomass elastomer, characterized in that the amino group. The method according to claim 1 or 2,
Step 1 is a method for producing a biomass elastomer, characterized in that the end of the diene-based polymer to modify the amino group using 4-bromo-N, N-bis (trimethylsilyl) aniline. The method according to claim 1 or 2,
Method of producing a biomass elastomer, characterized in that the polymerization reaction of the diene-based polymer and the fatty acid whose terminal is modified in the functional group is carried out at 200-250 ℃. A biomass elastomer produced by the method of any one of claims 1 to 3.
KR1020110044951A 2011-05-13 2011-05-13 Preparation method of eco-friendly biomass-elastomer KR20120126854A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592487A (en) * 2015-01-12 2015-05-06 浙江碳谷上希材料科技有限公司 Method for synthesizing biological base rubber by using soybean oil and epoxidized soybean oil as raw materials
WO2022080826A1 (en) * 2020-10-12 2022-04-21 주식회사 엘지화학 Oil-extended modified conjugated diene-based polymer, method for preparing same, and rubber composition comprising same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592487A (en) * 2015-01-12 2015-05-06 浙江碳谷上希材料科技有限公司 Method for synthesizing biological base rubber by using soybean oil and epoxidized soybean oil as raw materials
WO2022080826A1 (en) * 2020-10-12 2022-04-21 주식회사 엘지화학 Oil-extended modified conjugated diene-based polymer, method for preparing same, and rubber composition comprising same

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