KR100780477B1 - Reforming Method of Petroleum Resin with Improved Dynamic Properties and Elongation Characteristics - Google Patents

Abstract

The present invention relates to a method for reforming a petroleum resin with improved dynamic properties and elongation characteristics, and more particularly, in a method for reforming a petroleum resin with a styrenic block copolymer, in which the process oil, sulfur, and specific sulfur donation are provided. When the substance and the vulcanization accelerator are used, the petroleum resin composition obtained by reforming has a stability against temperature change as well as dynamic physical properties and elongation characteristics, and relates to a petroleum resin reforming method useful for color packaging binders and waterproof sheets.

Description

Reforming method of petroleum resin compositions improved dynamic properties and ductility

The present invention relates to a method for reforming a petroleum resin with improved dynamic properties and elongation characteristics, and more particularly, in a method for reforming a petroleum resin with a styrenic block copolymer, in which the process oil, sulfur, and specific sulfur donation are provided. When the substance and the vulcanization accelerator are used, the petroleum resin composition obtained by reforming has a stability against temperature change as well as dynamic physical properties and elongation characteristics, and relates to a petroleum resin reforming method useful for color packaging binders and waterproof sheets.

In general, petroleum resin is widely used as an adhesive tackifier, and various kinds of petroleum resins are used according to the type of polymer used. On the other hand, as another application field of petroleum resin as a binder for reforming used in dark brown color asphalt or color concrete, the demand is high and related technologies are also being developed. In general, color asphalt and color concrete are used for sidewalks, trails, stadium tracks, bicycle paths and roads in front of schools, bus stops, and the like.

Like ordinary asphalt compositions, binders used for color asphalt or colored concrete also behave very sensitive to temperature during road pavement or waterproofing sheet production, if not modified, and plastic deformation is likely to occur due to temperature or load at high temperatures. At low temperatures, crack fracture from the top occurs due to fatigue cracking from the bottom due to cyclic loading and repeated stretching due to rapid temperature changes. In addition, there is a problem that the resistance to plastic deformation, temperature sensitivity, fatigue cracking, low temperature cracking, etc., as well as color discoloration problem is sharply inferior.

In order to improve the problems of the binder, a modified color binder modified by adding a polymer to a petroleum resin, which is a basic binder, is used. Specifically, for example, low density polyethylene, polypropylene, ethylene vinyl acetate, and amorphous polypropylene By mixing polymers such as thermoplastic resins such as thermoplastic resins, styrene-butadiene rubber, butyl rubber or styrene-butadiene block copolymers, the resistance to plastic deformation due to softening at high temperatures is improved, and due to repeated loads at low temperatures. Research on modified asphalt showing excellent effect in suppressing impact cracking due to external stress and repeated shrinkage is underway, and it is gradually increasing in the case of applying to road in actual industrial field.

In the known literature, US Pat. No. 3,853,779 discloses a method for preparing a composition in which ethylene-propylene diene rubber, sulfur and polyethylene are added to improve the penetration and thermal properties of bitumen (natural hydrocarbon). U.S. Patent No. 3,992,341 discloses a method for preparing a composition for use as insulation or carpet flooring by adding polypropylene or copolymer fibers or filaments to bitumen and melt spinning.

In addition, Korean Patent Application Publication No. 95-3393 discloses a method for preparing a composition in which a modified polyolefin having a carboxyl group or a derivative and a modified polyolefin metal composite which is a transition metal product are combined with asphalt to increase resistance to low temperature ductility and plastic deformation at high temperatures. Suggesting. Korean Unexamined Patent Publication No. 94-7121 discloses a method for preparing a bitumen composition exhibiting storage stability, flexibility, permeability and softening properties at low temperatures by adding propylene-based or ethylene-based homopolymers or copolymers. .

In addition, Korean Patent Laid-Open Publication No. 02-23743 discloses a binder composition for color ascon which is capable of improving plastic deformation resistance at high and low temperatures and preventing discoloration by mixing process oil, thermoplastic resin, thermoplastic elastomer, and general rubber. Korean Patent Laid-Open Publication No. 04-28877 proposes a method for preparing a binder composition for color packaging having melt and process oil, thermoplastic resin and petroleum resin having excellent transparency, resistance to plastic deformation and low temperature cracking.

Accordingly, the present inventors have tried to develop a petroleum resin modified with a block copolymer having improved physical properties such as dynamic and elongation even after high temperature and low temperature as well as heat aging. As a result, when styrene-based block copolymers are used to modify the petroleum resin, process oils and sulfur, certain sulfur donating agents or mixtures thereof, and vulcanization accelerators are added in an amount. The petroleum resin obtained after the reforming by acting as a crosslinking agent between the petroleum resin and the styrene-based block copolymer was found to have excellent dynamic properties and elongation characteristics and stability against temperature changes, thereby completing the present invention.

Accordingly, an object of the present invention is to provide a method for reforming a petroleum resin modified with a styrenic block copolymer having excellent dynamic properties, elongation characteristics, and stability to temperature changes.

In the method of modifying petroleum resin with styrene block copolymer,

The reforming is characterized by a process for reforming petroleum resins which is carried out in the presence of process oil, using sulfur, sulfur donating agents represented by the following formula (1) or mixtures thereof and vulcanization accelerators.

(C ₂ H ₅ O) ₃ -Si- (CH ₂ ) _3- (S) _4- (CH ₂ ) ₃ -Si- (OC ₂ H ₅ ) ₃

Hereinafter, the present invention will be described in detail.

The present invention relates to a process for reforming a petroleum resin using a styrenic block copolymer to improve the physical properties of the petroleum resin, wherein the process oil and sulfur, a specific sulfur donating agent or a mixture thereof and When a certain amount of vulcanization accelerator is added, the petroleum resin composition obtained after the reforming is performed by the sulfur or sulfur donor material acting as a crosslinking agent between the petroleum resin and the styrenic block copolymer, and has excellent dynamic and elongation characteristics and stability against temperature changes. Do.

Looking at the method of modifying the petroleum resin with the styrene-based block copolymer of the present invention in more detail as follows.

Petroleum resin used as the base resin in the present invention is generally used in the art, but is not particularly limited, but is not limited to aliphatic (C5) petroleum resin, aromatic (C9) petroleum resin, copolymerized petroleum resin, dicyclopentadiene (DCPD) ) Resins, hydrogenated resins, and the like, and more preferably, hydrogenated resins are preferable in terms of heat resistance and color of the composition.

Styrene-based block copolymers used to modify the petroleum resin are generally used in the art, but are not particularly limited, but have a number average molecular weight in the range of 20,000 to 1,000,000, for example, styrene-butadiene-styrene block copolymers. , Styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and the like can be used. When the number average molecular weight is less than 20,000, it is not easy to express mechanical application properties, and when the number average molecular weight exceeds 1,000,000, workability tends to be lowered.

The styrene-based block copolymer can be used in the range of 5 to 40 parts by weight, preferably 5 to 25 parts by weight with respect to 100 parts by weight of the total petroleum resin composition, and the concentration of the polymer is too high if the amount is less than 5 parts by weight. As it is low, it is difficult to express the performance of the polymer as a modifier, and when it exceeds 40 parts by weight, it causes excessive high viscosity, lowering the dispersibility and flowability of the modified petroleum resin composition, and delaying the dispersion time to thermal decomposition and shear stress of the binder. Mechanical decomposition phenomenon occurs.

The present invention is selected from sulfur, sulfur donating agent represented by the formula (1) and mixtures thereof in order to obtain the dynamic properties, elongation characteristics and stability of temperature change of petroleum resin modified with styrene-based block copolymer The use of one kind or a mixture of two or more kinds has technical features.

The sulfur, a sulfur donating agent represented by Chemical Formula 1, and a mixture thereof are in the range of 1 to 30 parts by weight, preferably 2.5 to 20 parts by weight, based on 100 parts by weight of the styrenic block copolymer. When used, if the amount is less than 1 part by weight negatively affects the dynamic properties and elongation properties of the composition, and if it exceeds 30 parts by weight, the composition is hardened due to excessive hardening and problems of discoloration are maintained. It is preferable. In addition, when using it alone, it is good to use it in 0.5-10 weight part with respect to 100 weight part of styrene-type block copolymers, More preferably, it is 0.7-5 weight part. In the case of using the sulfur donor alone, it is preferable to use 1 to 20 parts by weight, more preferably 2 to 10 parts by weight based on 100 parts by weight of the styrenic block copolymer. In addition, when mixing sulfur and a sulfur donor substance, it is good to maintain the range of 1-5 weight ratio with respect to 1 weight of sulfur.

In addition, the present invention uses a vulcanization accelerator for activating the action of sulfur and sulfur donor material with the sulfur and the specific sulfur donor material, the vulcanization accelerator is generally used in the art, but is not particularly limited -tert-butyl-2-benzothiazole sulfenamide (TBBS), dicyclohexyl sulfenamide (DZ), diphenylguanidine (DPG), dibenzothiazyl disulfide (DM) and the like can be used.

The vulcanization accelerator is used in an amount of 0.2 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the styrenic block copolymer. If this becomes weak, the manufacturing process time of the composition is delayed, the improvement of the dynamic properties and the elongation characteristics is poor, and when it exceeds 5 parts by weight, there is a problem of local curing.

In addition to the process oil can be added to improve the efficiency of the production, the process oil is generally used in the art may be used paraffinic oil, naphthenic oil, aromatic oil, polybutene and the like. The process oil is 2 to 20 parts by weight with respect to 100 parts by weight of the total petroleum resin composition, and preferably 5 to 15 parts by weight. If the amount is less than 2 parts by weight, the viscosity increases during the preparation of the composition, resulting in poor processability. When the amount exceeds 20 parts by weight, it is preferable to maintain the above range because a problem occurs that adversely affects the mechanical properties of the composition.

The petroleum resin modified with the styrenic block copolymer obtained by the above method according to the present invention has a dynamic property and a 30% increase in dynamic properties and a 30% increase in comparison with conventional sulfur and sulfur donor materials. It has an increased elongation and temperature stability, especially when a mixture of sulfur and sulfur donating agents is used.

Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

Example 1

20 g of paraffinic oil (white oil 131 (Seojin Chemical)) was added to a 200 mL stainless steel vessel equipped with a stirrer and heated to 180 ° C. Then, 160 g of hydrogenated petroleum resin (Sukorez Su-100, Kolon Emulsion) was added and stirred. While melting. When the hydrogenated petroleum resin is completely melted, 20 g of styrene-butadiene-styrene block copolymer is added to melt it into a completely homogeneous phase. 0.65 g of sulfur and 0.38 g of TBBS were added as a vulcanization accelerator, and the mixture was stirred to be uniformly dispersed throughout, thereby preparing a transparent or translucent composition.

Example  2

20 g of paraffinic oil (white oil 131 (Seojin Chemical)) was added to a 200 mL stainless steel vessel equipped with a stirrer and heated to 180 ° C. Then, 160 g of hydrogenated petroleum resin (Sukorez Su-100, Kolon Emulsion) was added and stirred. While melting. When the hydrogenated petroleum resin was completely melted, 20 g of styrene-butadiene-styrene block copolymer was added thereto, and the molten petroleum resin was melted to be completely homogeneous. To this, 1.5 g of bis- (triethoxysilylpropyl) tetrasulfane as a sulfur donor and 0.38 g of TBBS were added as a vulcanization accelerator, and the mixture was stirred to be evenly dispersed throughout to prepare a transparent or translucent composition.

Example  3

20 g of paraffinic oil (white oil 131, Seojin Chemical) was added to a 200 mL stainless steel vessel equipped with a stirrer, and heated to 180 ° C. Then, 150 g of hydrogenated petroleum resin was added and melted while stirring. When the hydrogenated petroleum resin (Sukorez Su-100, Kolon Emulsification) was completely melted, 20 g of styrene-butadiene-styrene block copolymer was added and melted into a completely uniform phase. To this, 0.65 g of sulfur, 1.5 g of sulfur donor bis- (triethoxysilylpropyl) tetrasulfane, and 0.38 g of TBBS were added as a vulcanization accelerator, and the mixture was stirred to be uniformly dispersed throughout to prepare a transparent or translucent composition.

Comparative example

20 g of paraffinic oil (white oil 131 (Seojin Chemical)) was added to a 200 mL stainless steel vessel equipped with a stirrer and heated to 180 ° C., and then 160 g of hydrogenated petroleum resin was added thereto and stirred. When the hydrogenated petroleum resin (Sukorez Su-100, Kolon Emulsion) was completely melted, 10 g of styrene-butadiene-styrene block copolymer was added thereto, followed by melting and stirring to prepare a transparent or translucent composition.

The petroleum resin modified from the said Examples 1-3 and the comparative example is put together in Table 1.

Classification (g) oil Petroleum resin Block copolymer sulfur Si69 TBBS Example 1 20 160 20 0.65 - 0.38 Example 2 20 160 20 - 1.5 0.38 Example 3 20 160 20 0.65 1.5 0.38 Comparative example 20 160 10 - - -

Experimental Example

The physical properties of the modified petroleum resin obtained in Examples 1 to 3 and Comparative Examples and the physical properties after aging in an oven at 150 ° C. for 5 hours in order to grasp the physical properties after thermal aging, which are important factors in applying color asphalt, were measured and the results are shown in the following table. 2 is shown.

1. Dynamic property analysis

Dynamic property analysis was performed using StressTech rheometer. The measurement was carried out on a 25 mm diameter parallel plate with a gap of 2 mm and a temperature of 40 ° C. to 100 ° C. at a rate of 1 ° C./min. The frequency was fixed at 10 rad / sec and the initial stress was set to 120 Pa before thermal aging and 220 Pa after thermal aging. The measurement was performed to measure the deformation resistance of the prepared composition by measuring the composite modulus of elasticity (G ^* ), phase difference (δ) and dynamic shear stress (G ^* / sinδ) according to temperature.

2. Tensile Strength Analysis

Tensile strength and elongation were measured using Instron UTM. The specimen was 50 mm long, 3.5 mm wide, and 2 mm thick. The measurement speed was 250 mm / min.

division Example 1 Example 2 Example 3 Comparative example Elongation (%) 70 ℃ 397 357 429 296 Composite modulus (kPa) 65 ℃ 8.60 8.28 8.52 8.26 70 ℃ 6.40 6.29 6.46 6.24 75 ℃ 4.89 4.86 5.02 4.70 Phase angle (δ) 65 ℃ 47.6 44.3 44.9 51.3 70 ℃ 44.5 42.4 41.4 47.6 75 ℃ 47.4 46.3 43.5 48.3 Dynamic shear stress (kPa) 65 ℃ 11.64 11.80 12.07 10.58 70 ℃ 9.13 9.31 9.77 8.48 75 ℃ 6.65 6.72 7.29 6.30 Composite modulus (after aging) 65 ℃ 13.02 10.86 19.24 10.04 70 ℃ 8.58 7.65 13.10 6.45 75 ℃ 5.98 5.71 9.69 4.37 Phase angle (δ, after aging) 65 ℃ 55.5 47.8 49.7 60.5 70 ℃ 50.4 42.1 42.6 55.8 75 ℃ 49.2 40.7 39.4 56.2 Dynamic Shear Stress (kPa, After Aging) 65 ℃ 15.80 14.67 25.23 11.54 70 ℃ 11.14 11.41 19.35 7.80 75 ℃ 7.90 8.75 15.26 5.26

As shown in Table 2, when the petroleum resin is modified with a styrenic block copolymer, an embodiment of the petroleum resin modified with a styrene-based block copolymer to which sulfur or a sulfur donating agent and a vulcanization accelerator are added 1 and 2 have improved dynamic properties and elongation properties and temperature stability compared to the compositions of the comparative examples without addition of conventional sulfur or sulfur donating agents and vulcanization accelerators, in particular sulfur or sulfur donor materials It has been found that a mixture of sulfur donating agents and vulcanization accelerators maintain much improved increased dynamic and elongation properties and temperature stability.

On the other hand, when sulfur and sulfur donating agents are used alone, the sulfur / vulcanization accelerator composition has a high elastic modulus and is highly resistant to deformation, whereas a sulfur donating agent / vulcanization accelerator is used. It was confirmed that the composition had a smaller phase angle and more excellent elasticity. In addition, when both sulfur and sulfur donating agents were used at the same time, the deformation resistance and elasticity were improved at the same time. In particular, the dynamic properties after aging required for the application of color asphalt showed a greater increase.

As described above, when reforming the petroleum resin with the styrenic block copolymer according to the present invention, sulfur or a sulfur donating agent, a mixture thereof and a vulcanization accelerator are obtained under process oil. The modified petroleum resin composition exhibits significantly increased dynamic properties and elongation characteristics and temperature stability compared to conventional styrene-based block copolymer modified petroleum resins. The modified petroleum resin composition is applied to color packaging binders and waterproof sheets. The effect is expected.

Claims (11)

In the method of modifying petroleum resin with styrene block copolymer, The reforming is carried out in the presence of process oil, using sulfur, sulfur donating agent represented by the following formula (1) or a mixture thereof and a vulcanization accelerator. [Formula 1] (C ₂ H ₅ O) ₃ -Si- (CH ₂ ) _3- (S) _4- (CH ₂ ) ₃ -Si- (OC ₂ H ₅ ) ₃ The method of claim 1, wherein the petroleum resin is one or a mixture of two or more selected from aliphatic petroleum resins, copolymerized petroleum resins, and hydrogenated resins. The method of claim 1, wherein the styrenic block copolymer is one or two or more selected from styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and styrene-ethylene-butylene-styrene block copolymers. Reforming method of petroleum resin, characterized in that the mixture.        The method of claim 1, wherein the styrenic block copolymer is used in the range of 5 to 40 parts by weight based on 100 parts by weight of the total component. The method of claim 1, wherein the process oil is used in an amount of 2 to 20 parts by weight based on 100 parts by weight of the total components. The method of claim 1, wherein the sulfur, the sulfur donor material or a mixture thereof is used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the styrenic block copolymer. The method of claim 1, wherein the vulcanization accelerator is used in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of the styrenic block copolymer. The method of claim 1, wherein the mixture is used in an amount of 1 to 5 parts by weight based on 1 part by weight of sulfur. The method of claim 1, wherein the sulfur is used in the range of 0.5 to 10 parts by weight based on 100 parts by weight of the styrenic block copolymer. The method of claim 1, wherein the sulfur donor material is used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the styrenic block copolymer. A binder for color packaging containing a petroleum resin modified with a styrenic block copolymer obtained by any one of claims 1 to 10.