KR20040025056A - Polymer Compositions Containing Waste Edible Oil Useful for the Aggregate Binder - Google Patents

Abstract

PURPOSE: Provided is a polymer composition using a waste edible oil for an aggregate binder, which has improved heat resistance, low-temperature elasticity and performance as a paving material compared with a conventional asphalt binder, and shows various colors. CONSTITUTION: The polymer composition using waste edible oil for an aggregate binder comprises 3-40 wt% of a styrene-conjugated diene block copolymer, 0.5-70 wt% of an adhesion-imparting agent and 0.5-60 wt% of waste edible oil. In particular, the styrene-conjugated diene block copolymer is selected from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butadiene-styrene block copolymer and a styrene-butadiene block copolymer and a mixture thereof.

Description

Polymer Compositions Containing Waste Edible Oil Useful for the Aggregate Binder}

The present invention relates to a polymer composition for aggregate binder using waste cooking oil, and more specifically, using a relatively low-cost petroleum resin as a tackifier, and using waste cooking oil as a plasticizer or softener, The present invention relates to a polymer composition for aggregate binders using excellent binder for hot asphalt, hot melt or waste oil for various sealants.

As the asphalt used in the conventional asphalt pavement, straight asphalt is mainly used, but the asphalt pavement using the same has poor physical properties in all aspects such as plastic deformation resistance (ie, tracking resistance) and crack resistance in summer. PG grade asphalt, a polymer modified asphalt (Polymer Modified Asphalt), has been recently introduced and used.

As in the present invention, since the styrene-butadiene-styrene (SBS) block copolymer improves elasticity while giving low temperature flexibility to the composition, the modified asphalt by adding it is well known for a long time. Increasing use of this material has the advantage of excellent crack protection, especially in cold areas.

In addition, by adding various components to the modified asphalt, it is used as joint materials, adhesives, fillers, waterproof materials, sealants, sealants, and sealants in various facilities such as road pavement and expansion joints of bridges. Property improvements are being made in many areas.

As a binder material for color ascone, thermoplastic and thermosetting polymer materials are used without using asphalt to give a desired color using a pigment, and the polymer composition of the present invention is a thermoplastic material melted and used in the same manner as conventional asphalt.

In the case of the binder material for the color asphalt concrete, the penetration of the material itself, the softening point, the original recovery rate, the low temperature tensile properties, the tracking resistance in the aggregate mixture, and the crack resistance are all required to be better than those of the conventional asphalt pavement.

Color pavement is currently used mainly for sidewalks, bicycle roads, parks, parking lots, and sports facilities due to the poor physical properties of pavement.

As a binder material for preparing a conventional color ascone, a composition in which a process oil, a thermoplastic resin, a thermoplastic elastomer, and rubbers is mixed is introduced as disclosed in Korean Patent Laid-Open Publication No. 2002-020243.

This is to provide color asphalt concrete by mixing aggregates and pigments commonly used in asphalt concrete, but due to the constituent requirements, there may be a problem of low heat resistance due to the high content of process oil, and the price is higher than asphalt using expensive resins. There is a high disadvantage.

On the other hand, the waste cooking oil is known as a raw material for the regeneration industry paint as in the Republic of Korea Patent Application No. 2001-8058 or as a fuel oil composition as in the Republic of Korea Patent Application No. 1999-49548, etc. Recycling is being limitedly used due to problems such as physical properties, and the current waste cooking oil is mainly used to make soap.

Therefore, in the present invention, as a result of extensive research to solve the above problems, when using waste cooking oil as a plasticizer or softener, and using a tackifier and thermoplastic rubber styrene-butadiene triblock copolymer, it is excellent in adhesion and heat resistance and It has been found that the excellent elasticity can provide an excellent composition as a road paving binder. In addition, the color of the composition is colorless, so that it is possible to make a pavement with various colors when mixed with pigment and then paved with aggregate. The invention has been completed based on this.

Accordingly, an object of the present invention is to provide a polymer composition for aggregate binder using waste cooking oil, which is more improved than conventional asphalt binder in heat resistance, low temperature elasticity, price ratio performance, etc. when applied as a packaging material, and can implement a variety of colors.

Polymer composition for the aggregate binder using the waste cooking oil of the present invention for achieving the above object comprises 3 to 40% by weight of styrene-conjugated diene block copolymer, 0.5 to 70% by weight tackifier and 0.5 to 60% by weight waste cooking oil do.

Looking at the present invention in more detail as follows.

As described above, the polymer composition for aggregate binder using the waste cooking oil of the present invention comprises 3 to 40% by weight of the styrene-conjugated diene block copolymer, 0.5 to 70% by weight tackifier and 0.5 to 60% by weight waste cooking oil It is excellent in mixing with aggregate, and can realize various colors by using various pigments when mixing and packing with aggregate. It is more improved than existing asphalt binder in terms of heat resistance, low temperature elasticity and price performance when applied to packaging materials.

The styrene-conjugated diene block copolymer used in the present invention is used in an amount of 3 to 40% by weight based on the total composition, preferably 10 to 30% by weight. At this time, when the amount of the block copolymer is less than 3% by weight, there is almost no effect of addition, and when the amount of the block copolymer exceeds 40% by weight, the viscosity tends to be too large, making processing difficult.

The styrene-conjugated diene block copolymer is selected from styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-ethylene-butadiene-styrene (SEBS), and styrene-butadiene (SB) block copolymers. One or more species can be used, and two or more kinds of products having different molecular weight and styrene content can be used simultaneously.

Among these, styrene-butadiene-styrene triblock copolymer is most preferred, and the copolymer preferably has a styrene content of 20 to 60 mol%, more preferably 25 to 35 mol%.

The form of the block copolymer can be either linear or branched, and the molecular weight of the block copolymer can be used from 5,000 to 1,000,000, preferably between 10,000 and 300,000.

SBS triblock copolymer is a thermoplastic rubber that is provided in pellet, plaque, and powder form. KOSYN KTR-101, 101P, 201, 401, 401P, etc., which are manufactured by Kumho Petrochemical Co., Ltd. can be used. Shell's Creton products are available. The product form is preferred because the powder form has a shorter dissolution time than the flakes.

Styrene-butadiene-styrene block copolymers, one of thermoplastic rubbers, are fully dispersed in the asphalt matrix by high-speed mixing at high temperatures (between 150 ° C and 200 ° C) by means of high shear mixers or ordinary impeller mixers. Forming a network structure of the form and its content increases as the elasticity and mechanical strength increases, but there is a disadvantage that is relatively expensive compared to asphalt.

The tackifier may be a tackifying agent that is commonly used, and may include petroleum resins such as aromatic petroleum resins, coumarone indene resins, aliphatic petroleum resins, and hydrogenated dicyclopentadiene hydrocarbon resins. (hydrocarbon resin or petroleum resin) or rosin, modified rosin, copal, shellac, fatty acid, polyamide resin, polyester resin can be selected at least one. In particular, it is most preferable to use the hydrogenated dicyclopentadiene type resin which is excellent in adhesive force and low brittleness.

Such tackifiers, in particular, enable the polymer composition to function as a binder by improving adhesion to aggregates even at cold temperatures. The content of the tackifier is 0.5 to 70% by weight, more preferably 10 to 60% by weight.

At this time, if the amount of the tackifier is less than 0.5% by weight, there is almost no effect of addition, and if it exceeds 70% by weight, brittleness increases and there is a problem of easily breaking.

The waste cooking oil used in the present invention can be directly used when food is less contaminated with waste cooking oil that has not been used after cooking or manufacturing, but is generally used in cotton wool, glass wool, quartz wool, It is preferable to use various filter materials such as filter paper or filter cloth to remove suspended matter, food dregs, and carbonized materials at room temperature or below 60 ° C., and a filtration device using a pressurized or pumped method may be used.

In addition, waste cooking oil includes both vegetable and vegetable wastes discarded after use, such as various vegetable oils obtained from soybeans, castors, sesame seeds, cotton, palms, corn, and various animal oils such as various kinds of tallow, pork and fish oils. In special cases, cooking oil may be used instead of waste cooking oil.

The amount of the waste cooking oil used is 0.5 to 60% by weight, preferably 10 to 30% by weight. If the amount is less than 0.5% by weight, there is almost no effect of addition, and if the amount is more than 60% by weight, plasticization of the polymer composition is severe and is not preferable.

On the other hand, the polymer composition of the present invention may include within 50 parts by weight of the waste tire rubber powder with respect to 100 parts by weight of the polymer composition in the range that the color does not change in order to improve the hardness, softening point and the original recovery rate.

The waste tire rubber powder is a powder obtained by crushing the discarded tire at room temperature or low temperature, and includes styrene-butadiene rubber (SBR) and / or natural rubber and carbon black.

The average particle size of the waste tire rubber powder is preferably 200 mesh or less, more preferably between 10 and 80 mesh. The finer the waste tire rubber powder is, the better the physical properties such as elongation and adhesiveness are used. Therefore, it is preferable to use as fine a powder as possible.

By using the waste tire rubber powder in the polymer composition of the present invention, the manufacturing cost can be further lowered, and the problem of environmental pollution due to waste tire disposal and incineration can be solved.

The polymer composition according to the present invention may further include an inorganic filler within 200 parts by weight based on 100 parts by weight of the polymer composition in order to increase the softening point. As inorganic fillers, talc (talc), silica, dolomite, magnesium hydroxide, alumina hydroxide, kaolin (white clay), mica, barium sulfate, calcium carbonate, asbestos, aggregate, stone powder, steel slag, etc. can be used alone or in combination. Can be.

Among the inorganic fillers, talc calcium carbonate or silica is most preferably used alone, and two or more of talc calcium carbonate or silica may be used in combination depending on the intended use. The smaller the average particle size of talc calcium carbonate or silica is, the better, but it is suitably between 20 and 2,000 mesh.

In the polymer composition according to the present invention, a plasticizer or a softener may be further added in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the polymer composition in order to further increase the penetration of the composition, low temperature adhesiveness and low temperature elongation.

As the plasticizer or softener, heavy oil (bunker A, B, C oil), lubricating oil, various process oils (paraffinic, naphthenic, aromatic), phthalate plasticizers (DOP, DINP, DBP, DIBP, DHP, etc.), aromatic Carbonic acid ester plasticizer (TOTM, DEDB, etc.), aliphatic dibasic acid ester plasticizer (DOS, DOA, DIDA, DOZ, etc.), phosphate (phosphate ester) plasticizer (TCP, TOF, TPP, etc.), epoxy plasticizer (epoxidized soy bean oil) Or epoxidized linseed oil, chlorinated paraffin, phosphorus-chlorine-containing plasticizer (TCPP, TCEP, etc.) may be used alone or in combination thereof.

Plasticizers mainly used in asphalt compositions include bunker-C oil, dioctylphthalate (DOP), tricresil phosphate (TCP), naphthene or aromatic process oils. Among these, it is particularly preferable to use aromatic and naphthenic process oils alone or in parallel.

The addition of process oil greatly increases the elongation of the composition but slightly reduces the softening point, slightly increases the penetration and results in very good low temperature flexibility and adhesion. Therefore, it is especially suitable to add a plasticizer together in cold districts.

Antioxidants, light stabilizers (ultraviolet absorbers or HALS light stabilizers), thermal stabilizers, and the like may be further added to the polymer composition of the present invention, and colorants such as dyes and pigments, antimicrobial agents, and slips may be added depending on the application. An inhibitor, an antiwear agent, etc. can also be added.

In addition, it may contain various reinforcing agents such as glass fibers, glass flakes, carbon fibers and silicon carbide fibers, and may contain rubber or polymers such as polyethylene, ethylene-based copolymers and plastics such as polypropylene, or wastes discarded using these. .

As the polymer, ethylene polymers (LDPE, LLDPE, VLDPE, etc.) and ethylene copolymers (EVA, EEA, EMA, etc.) are most suitable. Examples of the polymer wastes include various crushed rubber products, polyethylene wastes such as agricultural waste vinyl, and styrene waste plastics (for example, yogurt bottles or styrofoams of high impact polystyrene).

The polymer composition for aggregate binder using the waste cooking oil of the present invention can be produced regardless of the type and mixing order of the mixer, such as an impeller mixer, a high shear mixer. It is preferable here to use high shear or high viscosity mixers in order to obtain a more uniformly dispersed composition and to mix in less time.

The polymer composition for the aggregate binder using the waste cooking oil of the present invention uses a variety of manufacturing equipment and construction equipment alone for hot melt coating, lane for the construction and construction of various pavement, buildings, bridges and structures according to various construction methods Paints, crack repair agents, joints, expansion joint sealers or fillers, sealants, waterproofing materials, waterproofing membranes, waterproof membranes, geomembranes, intermediate layers of shock absorbing membranes, topcoats for roofing membrane structures, underbody coatings for military vehicles and equipment, packaging It is used as a water-repellent film, dustproof material, and the like, and is used as a binder to be mixed with various aggregates, to be used for sidewalks, bicycle-only roads, and general road pavement.

In addition to the above uses, further development of the use is being made so that it can be used as a material raw material and secondary applications in the future.

Hereinafter, the polymer composition for aggregate binder using waste cooking oil of the present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

Examples 1-4

KOSYN KTR-101P from Kumho Petrochemical as a styrene-conjugated diene copolymer in the amounts shown in Table 1, and the waste cooking oil was filtered through glass cloth to be used in the preparation of frying at a snack shop, and the tackifier is sold by Kolon Oil. P-110S, an aromatic petroleum resin, and talc (manufactured by Hanzhong Talc) were used as the inorganic filler.

As a basic stabilizer, 0.5 wt% of Song Knox 21B of Songwon Industrial Co., Ltd. was used as an antioxidant, and 0.5 wt% of a HALS (Hindered Amine Light Stabilizer) stabilizer and an ultraviolet absorber were used as the light stabilizer.

Comparative Example 1

AP-5 sold by LG Caltex Oil was used.

Comparative Example 2

AP-3 sold by LG Caltex Oil was used.

Comparative Example 3

A domestic binder for color ascone was used.

The physical property measurement results of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Composition of Composition (wt%) SBS KTR-101 15 21 25 29 - - - Waste Cooking Oil 20 26 30 33 - - - P-110S 54 45 40 36.5 - - - Talc 9.5 6.5 3.5 - - - - stabilizator One One One One - - - Antioxidant 0.5 0.5 0.5 0.5 Properties Breakthrough (dmm) ¹⁾ 55 86 110 92 70 86 180 Softening Point (℃) ²⁾ 70 77 67 69 48 42 55 Elongation (cm) ³⁾ 100 120 More than 150 More than 150 More than 150 More than 150 68 Recovery rate (%) ⁴⁾ 57 62 68 70 - - 45 Tensile Adhesion Length (mm) ⁵⁾ 12 17 20 18 0.3 0.6 10

The final physical properties of the asphalt compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the methods given below.

1) Penetration Degree: KS M 2252 (Load 150g)

2) Softening point: KS M 2250

3) Shinto: KS F 4052

4) Recovery rate of normalization: KS F 2368

5) Tensile adhesion length: KS F 2368 (However, the measurement temperature is measured by using a low temperature chamber at -20 ℃, not room temperature)

As can be seen in Table 1, the asphalt composition according to the embodiment was all excellent in low temperature flexibility and adhesion, the tensile adhesion length measured at -20 ℃ was very large. It is expected that the plastic deformation resistance is high because the softening point showing excellent heat resistance and high heat resistance is high.

The penetration and elongation of the asphalt composition according to the examples showed similar values to the asphalt compositions according to the comparative example.

In addition, it can be seen that the original recovery rate of the compositions according to the embodiment is relatively large and is a very excellent binder material.

Asphalt composition according to an embodiment of the present invention can be produced at a relatively low cost environmentally friendly and economical by containing a large amount of waste cooking oil. In addition, the compositions made of Examples 1 to 4 show excellent physical properties that satisfy the US standard ASTM D-3405, the standard for melt-injected concrete joint sealants.

Claims (8)

A polymer composition for an aggregate binder using waste cooking oil, comprising 3 to 40% by weight of a styrene-conjugated diene block copolymer, 0.5 to 70% by weight of a tackifier, and 0.5 to 60% by weight of waste cooking oil. The method of claim 1, wherein the styrene-conjugated diene block copolymer is a styrene-butadiene-styrene (SBS) block copolymer, a styrene-isoprene-styrene (SIS) block copolymer, a styrene-ethylene-butadiene-styrene (SEBS) block Polymer composition for an aggregate binder using waste cooking oil, characterized in that one or more selected from the group consisting of a copolymer and a styrene-butadiene (SB) block copolymer. The polymer composition for aggregate binder using waste cooking oil according to claim 1 or 2, wherein the amount of the styrene-conjugated diene block copolymer is 10 to 30% by weight. The tackifier of claim 1, wherein the tackifier is an aromatic petroleum resin, coumarone indene resin, aliphatic petroleum resin, hydrogenated dicyclopentadiene petroleum resin, phenol resin, rosin, hydrogenated rosin, modified rosin, coumarone- Polymer composition for an aggregate binder using waste cooking oil, characterized in that one or more selected from the group consisting of indene resin, shellac, copal, fatty acid, polyamide resin and polyester resin. The composition of claim 1, wherein the composition is a heavy oil, a lubricating oil, a process oil, a phthalate plasticizer, an aromatic carbonic acid ester plasticizer, an aliphatic dibasic acid ester plasticizer, a phosphate (phosphate ester) plasticizer, an epoxy plasticizer, a chlorine-containing plasticizer and a phosphorus-chlorine. Polymer composition for an aggregate binder using waste cooking oil, characterized in that it further comprises one or more plasticizers or softeners selected from the group consisting of containing plasticizers. The method of claim 1, wherein the composition is one or more inorganic fillers from the group consisting of talc, silica, calcium carbonate, magnesium hydroxide, kaolin, mica, barium sulfate, asbestos, asbestos, aggregate, glass fiber, carbon fiber and SiC fiber Polymer composition for an aggregate binder using waste cooking oil, characterized in that it further comprises. The method of claim 1, wherein the composition further comprises any one or more components selected from the group consisting of one or more polymers, rubbers or their waste selected from the group consisting of polyethylene, ethylene-based copolymers and polypropylene. Polymer composition for aggregate binder using waste cooking oil. The aggregate using waste cooking oil according to claim 1, wherein the composition further comprises one or more additives selected from the group consisting of light stabilizers, heat stabilizers, antioxidants, reinforcing agents, preservatives, colorants, lubricants and anti-wear agents. Polymer composition for binders.