KR101524729B1 - Copolymer comprised of hydrophillic polymer and drag reduction composition comprising the same - Google Patents

Abstract

(단, 상기 식에서 a, b, c의 중량비는 5~40 : 5~40 : 0.1~30이고, Z는 폴리에틸렌옥사이드, 폴리아크릴아민 또는 폴리사카라이드 중에서 선택되는 어느 하나의 친수성 폴리머이다.)
<화학식 4>

(단, 상기 식에서 w, x, y, z의 중량비는 5~40 : 5~40 : 5~40 : 0.1~30이고, Z는 폴리에틸렌옥사이드, 폴리아크릴아민 또는 폴리사카라이드 중에서 선택되는 어느 하나의 폴리머이다.)The present invention relates to a copolymer containing a hydrophilic polymer in a side chain and a composition for reducing frictional resistance comprising the same.
More specifically, the present invention relates to a polymerizable monomer composition comprising at least one acrylate-based monomer and at least one methacrylate-based monomer in the main chain and represented by the following general formula (1) or (4) Copolymer.
&Lt; Formula 1 >

(Wherein the weight ratio of a, b, and c is 5 to 40: 5 to 40: 0.1 to 30, and Z is any hydrophilic polymer selected from the group consisting of polyethylene oxide, polyacrylamine, and polysaccharide.
&Lt; Formula 4 >

Wherein the weight ratio of w, x, y and z is 5 to 40: 5 to 40: 5 to 40: 0.1 to 30, and Z is any one selected from the group consisting of polyethylene oxide, polyacrylamine and polysaccharide Polymer.)

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymer comprising a hydrophilic polymer and a composition for reducing frictional resistance comprising the same. BACKGROUND ART [0002]

The present invention relates to a copolymer containing a hydrophilic polymer in a side chain, and more particularly, to a copolymer comprising an acrylate monomer and a methacrylate monomer in a main chain and a composition for reducing frictional resistance comprising the copolymer.

There is a problem that marine creatures such as oysters, mussels, and seaweeds are easily attached to ships, fishing nets, and other underwater structures, thereby causing problems such as efficient operation of vessels being hindered, resulting in waste of fuel, Problems such as clogging, shortened service life, and the like occur. In order to solve these problems, we have applied anti-fouling paint on the outermost surface of hull etc. to prevent the adhesion of marine organisms and reduce frictional resistance and to prevent surface erosion. In particular, TBT material suitable for the regulations of International Maritime Organization Researches are underway to develop coating materials that reduce the frictional resistance and reduce the speed and fuel consumption of ships by reducing the deterioration of the surface of the hull and the surface adhesion of marine organisms.

The method of reducing the frictional resistance includes a passive device that obtains a frictional resistance reduction effect by fabricating an object structure to stabilize the fluid flow and an additive which is added to the fluid to obtain a physical and rheological And the method of reducing the frictional resistance by changing the flow characteristics of the fluid by controlling the rheological characteristics.

The passive method refers to a method of reducing the surface friction by forming the shape of the object such as riblets or coating the material on the surface of the object, and is a method of moving at high speed in air or fluid such as an aircraft, Has been studied to reduce the frictional resistance of an object.

In addition, the method of adding the additives to the fluid means that the frictional resistance is reduced by injecting a very small amount of the additive in the turbulent flow field causing frictional resistance. In this case, frictional resistance is remarkably higher than surface friction, The flow of the fluid can be improved. In this case, the addition of a suitable additive to the solvent in a very small amount of a million parts per million (ppm) in the turbulent flow can achieve up to 80% (Toms, BA, Proc. , 1984). Such friction reducing additives include long chain structure molecules, colloidal soap solutions, microsuspension, insoluble and inelastic particles, macromolecular materials such as synthetic polymers, biopolymers and surfactants, and the like. Has been used. The most frequently used additives among these additives are polymeric materials. Factors influencing the frictional resistance reduction effect of the polymer include polymer type and structure, polymer concentration, polymer molecular weight, solution temperature, Reynolds number, solvent properties, etc. Is known. It is generally accepted that the cause of the decrease in the frictional resistance due to such a polymer additive is related to the viscoelasticity of the polymer solution (Armstrong, R. et al., J. Chem. Phys., 79: 3143, 1983 , Vlassopoulos, D., J. Rheel., 38: 1427, 1994).

Of the above polymeric materials, those most known to reduce friction most effectively have molecular structures of linear and long chains and are very large in molecular weight. Particularly, linear polyethylene oxide (PEO) satisfying the above conditions is widely used as an additive for reducing frictional resistance in a system using water as a solvent.

However, the method of reducing the frictional resistance by adding the polymer compound is applied as an optimal resistance reduction technique in the case of the tube flow, but the flow control technique for reducing the surface friction is complicated, . This is because, in the internal flow such as the pipe flow, the added polymer remains in the flow and causes resistance reduction, but the continuous polymeric compound injection is required because it is immediately washed out from the boundary layer flow around the vessel.

It is therefore required to reduce the frictional resistance with the liquid by the coating film in terms of reduction in navigation fuel consumption and energy saving of the ship when coating the surface of the object such as a ship where friction with the liquid occurs The present inventors have completed the present invention by producing a copolymer having excellent frictional resistance reduction performance by including a polymer having a frictional resistance reducing performance.

Accordingly, it is an object of the present invention to provide a copolymer containing a hydrophilic polymer.

Another object of the present invention is to provide a composition for reducing frictional resistance comprising the copolymer.

The present invention for solving the above problems is characterized in that it comprises at least one acrylate monomer and at least one methacrylate monomer in the main chain and has a hydrophilic polymer in its side chain, &Lt; / RTI &gt;

&Lt; Formula 1 >

In the above formula, the weight ratio of a, b, and c is 5 to 40: 5 to 40: 0.1 to 30, and Z is any hydrophilic polymer selected from polyethylene oxide, polyacrylamine or polysaccharide.

The present invention also relates to a copolymer comprising at least one acrylate monomer and at least one methacrylate monomer in the main chain and represented by the following general formula (4) and having a hydrophilic polymer in its side chain .

&Lt; Formula 4 >

Wherein the weight ratio of w, x, y and z is in the range of 5 to 40: 5 to 40: 5 to 40: 0.1 to 30, and Z is any polymer selected from polyethylene oxide, polyacrylamine or polysaccharide to be.

In addition, the present invention for solving the above-mentioned problems relates to a composition for reducing frictional resistance comprising the copolymer.

As described above, the copolymer according to the present invention, including the hydrophilic polymer, can remarkably reduce the frictional resistance in the water-soluble solvent system and exhibit excellent frictional resistance reduction performance.

1 shows a representative synthesis procedure of a copolymer according to the present invention.
2 shows the FT-IR spectrum of ZMA synthesized in the present invention.
Figure 3 shows the FT-IR spectrum of a copolymer according to one embodiment of the present invention.
4a-c show the ¹ H-NMR spectrum of the copolymer according to one embodiment of the present invention.
Fig. 5 shows the structure (a) and the photograph (b) of the circulating water tank used in the frictional resistance reduction test according to an embodiment of the present invention.
Figure 6 shows the flow profile for a magnetomechanical resin according to one embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

In one aspect, the present invention relates to a copolymer comprising at least one acrylate monomer and at least one methacrylate monomer in the main chain and having a side chain of a hydrophilic polymer represented by the following formula will be.

&Lt; Formula 1 >

In the above formula, the weight ratio of a, b, and c is 5 to 40: 5 to 40: 0.1 to 30, and Z is any hydrophilic polymer selected from polyethylene oxide, polyacrylamine or polysaccharide.

In the present invention, polyethylene oxide has a molecular structure of linear and long chains and has a large molecular weight, so that the polyethylene oxide has a role of reducing frictional resistance in a system using water as a solvent.

In the present invention, preferably,

Wherein the acrylate monomer is at least one selected from the group consisting of ethyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and butyl acrylate, and the methacrylate monomer is at least one selected from the group consisting of methyl methacrylate, cyclohexyl Methacrylate, and the like. When such monomers are mixed and copolymerized, the desired mechanical properties can be exhibited depending on each monomer.

Specifically, methyl methacrylate among the monomers makes it possible to have excellent chemical resistance and strength, and ethyl acrylate and 2-methoxyethyl acrylate can increase flexibility and adherence to a substrate, and butyl acrylate and 2 -Hexylhexyl acrylate improves flexibility and cyclohexyl methacrylate plays a role in improving durability and hardness and it is possible to improve the physical properties by complementing the disadvantages of each monomer due to the copolymerization of the various monomers do.

In the present invention, it is preferable that Z is polyethylene oxide, and the copolymer is represented by the following general formula (2).

(2)

In the above formula, the weight ratio of a, b, and c is 5 to 40: 5 to 40: 0.1 to 30, and n is an integer of 1 to 1,000,000.

In the present invention, preferably, the polysaccharide is selected from chitin, chitosan, gum arabic, alginic acid, carrageenan, agar, xanthan gum, gellan gum, cellulose, xylose, starch, pullulan, pectin, Tran or curdlan. &Lt; / RTI &gt;

In the present invention, it is preferable that the acrylate-based monomer or methacrylate-based monomer includes a silyl group or a metal group. By including a silyl group or a metal group in this way, the copolymer of the present invention can exhibit magnetic wear performance. More preferably, the copolymer is a copolymer represented by the following formula (3).

(3)

In the above formula, the weight ratio of a, b, and c is 5 to 40: 5 to 40: 0.1 to 30, n is an integer of 1 to 1,000,000, and M is Cu, Zn, or Si.

According to another aspect of the present invention, there is provided a copolymer comprising at least one acrylate-based monomer and a methacrylate-based monomer in the main chain and at least one hydrophilic polymer in the side chain, .

&Lt; Formula 4 >

Wherein the weight ratio of w, x, y and z is in the range of 5 to 40: 5 to 40: 5 to 40: 0.1 to 30, and Z is any polymer selected from polyethylene oxide, polyacrylamine or polysaccharide to be.

In the present invention, preferably,

Wherein the acrylate monomer is at least one selected from the group consisting of ethyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and butyl acrylate, and the methacrylate monomer is at least one selected from the group consisting of methyl methacrylate, cyclohexyl Methacrylate, and the like. When such monomers are mixed and copolymerized, the desired mechanical properties can be exhibited depending on each monomer.

In the present invention, it is preferable that Z is polyethylene oxide, more preferably the copolymer is represented by the following general formula (5).

&Lt; Formula 5 >

In the above formula, the weight ratio of w, x, y and z is 5 to 40: 5 to 40: 5 to 40: 0.1 to 30, and n is an integer of 1 to 1,000,000.

In the present invention, polyethylene oxide has a molecular structure of linear and long chains and has a large molecular weight, so that the polyethylene oxide has a role of reducing frictional resistance in a system using water as a solvent.

In the present invention, preferably, the polysaccharide is selected from chitin, chitosan, gum arabic, alginic acid, carrageenan, agar, xanthan gum, gellan gum, cellulose, xylose, starch, pullulan, pectin, Tran or curdlan. &Lt; / RTI &gt;

In the present invention, it is preferable that the acrylate-based monomer or methacrylate-based monomer includes a silyl group or a metal group. By including a silyl group or a metal group in this way, the copolymer of the present invention can exhibit magnetic wear performance. More preferably, the copolymer is a copolymer represented by the following formula (6).

(6)

Wherein the weight ratio of w, x, y and z is 5 to 40: 5 to 40: 5 to 40: 0.1 to 30, n is an integer of 1 to 1,000,000, and M is Cu, Zn or Si.

In addition, the present invention relates to a composition for reducing friction resistance comprising the copolymer, wherein the copolymer of the present invention contains a hydrophilic polymer, thereby reducing the frictional resistance in a system using water as a solvent Can exhibit excellent frictional resistance reduction performance, and can further include magnetic abrasion performance depending on the monomers of the main chain.

Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples. However, the following examples are for the purpose of making the invention more clearly understood, and the invention is not limited to the following examples.

Example 1 Synthesis of Zinc (Zinc methacrylate)

Zinc oxide (ZnO, 40.7 g) and propylene glycol monomethyl ether (PGM, 85.4 g) were charged into a four-necked flask equipped with a stirrer, a condenser, a thermometer, a dropping funnel and the temperature was raised to 90 ° C. When the temperature was adjusted, a monomer solution containing 43.1 g of methacrylate, 36.1 g of acrylate and 5.0 g of water was added dropwise at a constant rate for 3 hours using a dropping funnel. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then propylene glycol monomethyl ether (PGM, 10.0 g) was added to terminate the reaction to obtain ZMA in a clear mixture solution state.

In addition, FT-IR was used to determine whether or not ZMA was synthesized. FIG. 2 shows the FT-IR spectrum of ZMA synthesized above. The existence of a carboxylate salt was confirmed to confirm the binding of carboxylic acid to Zn. Carboxylic salt asymmetric stretching is strongly appears in the vicinity of 1600cm ^-1, it was found that this combination of measures results ester zinc (zinc ester) present in the vicinity of 1630cm ^-1. Therefore, it was confirmed that the synthesis of ZMA was successfully performed.

Example 2 Preparation of Polyethylene Oxide Grafted Copolymer

2-1 Materials

(1) Monomers

- Poly (ethylene glycol) methacrylate [PEGMA, Mn = 500 g / mol, Aldrich]

- Poly (ethylene glycol) methacrylate [PEGMA, Mn = 360 g / mol, Aldrich]

- Poly (ethylene glycol) methyl ether methacrylate [PEGMEM, Mn = 500 g / mol, Aldrich]

- Ethyl acrylate [EA, Mn = 100.12 g / mol, Aldrich]

- 2-ethylhexyl acrylate [2-EHA, Mn = 184.00 g / mol, Aldrich]

- 2-methoxyethyl acrylate [2-MTA, Mn = 130.14 g / mol, Aldrich]

- butyl acrylate [BA, Mn = 128.00 g / mol, Aldrich]

- Methyl methacrylate [MMA, Mn = 100.12 g / mol, Aldrich]

- cyclohexyl methacrylate [CHMA, Mn = 168.23 g / mol, Aldrich]

- Zinc methacrylate [ZMA, Mn = 221.53 g / mol]

(2) Chain transfer

-4-methyl-1-pentene [MSD, Mn = 236.36 g / mol, Aldrich]

(3) Initiator

-Benzoyl peroxide [BPO, Mn = 242.23 g / mol, Sigma]

(4) Solvent

- propylene glycol monomethyl ether [PGM, Mn = 90.12 g / mol, Aldrich]

-Xylene [Xy, Mn = 106.17 g / mol, DAEJUNG]

2-2 Synthesis of Copolymer

A mixed solution of propylene glycol monomethyl ether (PGM, 32.0 g), xylene (122.3 g) and ethyl acrylate (6.8 g) was placed in a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a stirrer, Lt; / RTI &gt; At this time, the stirring speed was maintained at 200 to 210 RPM.

When the temperature was adjusted, the acrylate monomer and the methacrylate monomer were mixed. The mixing ratio is shown in Table 1 below. A mixed solution of 120.1 g of the mixture solution obtained in Example 1, 20 g of xylene, 12.8 g of benzoyl peroxide as an initiator and 1.0 g of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent was stirred for 4 hours at constant velocity . After completion of the dropwise addition, 1.0 g of t-butyl peroctoate and 15.0 g of xylene were added dropwise for 30 minutes and further stirred for 1 hour and 30 minutes. Then, 10.0 g of xylene was added to terminate the reaction to obtain a copolymer resin solution.

The copolymer synthesized in this Example finally obtained a copolymer resin to which PEO was bonded.

PEGMA and the addition ratio.

In case of SPC 1 copolymer, flexibility was added to the film relative to SPC 2 copolymer by using butyl acrylate. In case of SPC 2 copolymer, cyclohexyl methacrylate was used for hardness, durability and water resistance The difference was made between the two copolymers by strengthening. In this case, a styrene monomer may be used.

<Experimental Example>

Instrument and analysis method

In order to evaluate the applicability of the resin to the resin synthesized in the above examples, nonvolatile (NV), viscosity and the like were measured.

At this time, the analytical equipment and analysis method used are as follows.

1) Nonvolatile Content: Modified ASTM D 1644

2) FT-IR: Nicoler iS10 FT-IR analyzer (range of 4000-400 cm ^-1 )

3) ¹ H-NMR: 600 MHz, Agilent superconducting FT-NMR analyzer system

4) PIV test (Particle image velocimetry test)

Nonvolatile matter

The measurement results of the nonvolatile matter as a basic property of the copolymer synthesized in the above examples are summarized in Table 2 below.

As shown in Table 2, nonvolatile matter (NV) was found to have an appropriate value from 49% to 56% regardless of the type of copolymer, and nonvolatile matter (NV) increased as the content of PEO increased.

FT-IR analysis

3 shows the resin FT-IR spectrum synthesized above.

First, the synthesized resin was compared with the peak of the monomer PEGMA in order to judge whether or not it was synthesized. As a result, it was confirmed that the peaks of the synthesized resin coincided with the PEG monomer. The peaks of the OH bending portion increased gradually with increasing PEO content, indicating that the PEO monomer was properly incorporated into the resin. It can be confirmed that these compounds were quantitatively synthesized when compared with the remaining peaks.

^One H-NMR analysis

4 (a) to 4 (d) show the ¹ H-NMR spectrum of the copolymer synthesized above. Referring to FIGS. 4 b to 4 d, the spectrum of PEGMA exhibits its own peak at about 3.5 ppm, By comparing the relative integra, the quantitative properties of the synthesized resin could be predicted. As the PEO content increased, the relative peaks decreased.

Drag Reduction Test

A circular water channel (CWC) as shown in FIG. 5A was fabricated to measure the unsteady flow field with a real time particle resolved PIV.

The real-time particle image anemometer is composed of an Nd: YAG laser, a high-speed camera (two units), an optical system (optical arm and Scheimpflug mount) and a PC (FIG. 5b). Since the PIV analysis is made by pairing two images, the flow information can obtain 4,000 continuous flow information at a maximum of 1,085 Hz.

Type Circulating water channel Size 0.65 m (W) x 1.55 m (H) x 8.99 m (L) Test section 400 mm (W) x 160 mm (H) x 7000 mm (L) Velocity range 0.1 to 0.6 m / s

Also, in this embodiment, the local friction stress on the wall surface was calculated using a CPM (Computational Preston Tube Method) method in which the average flow velocity distribution measured using PIV was fitted to the velocity distribution of the inner boundary layer layer. This method is a generalization of the Clauser plot method of calculating the wall shear stress by adjusting the slope of the log velocity distribution in the log layer which is a part of the inner layer. In the closure plot method, there is a disadvantage that the slope can be changed depending on whether the measurement data belonging to the log layer is selected. However, since the CPM is based on the velocity distribution from the buffer layer to the log layer as follows, A universal analysis is possible.

Therefore, in this embodiment, vi is constructed to perform the CPM calculation based on the Lab VIEW S / W to calculate the local wall friction resistance τ _w and the friction speed u _τ = (τw / ρ) ^1/2 . From the wall friction resistance τ _w thus calculated, the local friction stress coefficient C _F is obtained as follows.

In addition, the flow rate of the local friction stress coefficient C _F calculated in the CPM method (and the number of Reynolds Re _m = u _m h / ν, u _m is the average flow rate obtained by dividing the flow into the test section cross section, h is the half of the test part sectional height) As shown in FIG. The measurements were made at an average flow rate u _m = 0.53 _m / s. The resistance reduction ratio in each case is summarized in Table 4 below.

Substrates and copolymers u _M (m / s) U _T C _F Resistance reduction rate Bare (Glass) 0.53464 0.02527 0.004469197 - PRD1-0 0.53490 0.02512 0.004411522 1.291% PRD1-1 0.53464 0.02505 0.004391398 1.741% PRD1-2 0.53490 0.02496 0.004354925 2.557% PRD1-3 0.53464 0.02526 0.004463986 0.117% PRD2-0 0.53568 0.02462 0.00422371 5.49% PRD2-1 0.53516 0.02419 0.004087681 8.54% PRD2-2 0.53594 0.02366 0.003896455 12.82% PRD2-3 0.53542 0.02328 0.003780138 15.42% PRD3-1 0.53594 0.02323 0.003756863 15.94% PRD3-2 0.53568 0.02342 0.003823921 14.44% PRD3-3 0.53594 0.02403 0.004019699 10.06% PRD4-1 0.53411 0.02518 0.004444090 3.49% PRD4-2 0.53411 0.02534 0.004501890 2.23% PRD4-3 0.53411 0.02534 0.004501890 2.23%

Figure 6 also shows the flow profile for the synthesized copolymer.

As shown in Table 4 and FIG. 6A, the PRD 1 exhibited a very small friction reduction effect, and the PRD 1-3 exhibited less resistance reduction than the PRD 1-0 without PEO. This is presumed to be due to the change in surface roughness as the coating wears out. Also, PRD 2 exhibited a higher resistance reduction rate as the content of PEO increased, whereas the resistance reduction rate of PRD 3 decreased as the content of PEO increased (FIG. 6b). In contrast, PRD 4 showed a resistance reduction of 2 to 3% (FIG. 6C).

From the above results, it was found that when the SPC 2 copolymer was incorporated with PEO, the resistance reduction effect was exhibited, and in particular, PRD 3-1 showed a large resistance reduction effect of 15.94%.

Claims (9)

(1)
Wherein at least one of the acrylate monomer and the methacrylate monomer is contained in the main chain and the hydrophilic polymer is contained in the side chain.
&Lt; Formula 1 >

In the above formula, the weight ratio of a, b, and c is 5 to 40: 5 to 40: 0.1 to 30, and Z is any hydrophilic polymer selected from polyethylene oxide, polyacrylamine or polysaccharide. The method according to claim 1,
Wherein the copolymer is represented by the following formula (2).
(2)

In the above formula, the weight ratio of a, b, and c is 5 to 40: 5 to 40: 0.1 to 30, and n is an integer of 1 to 1,000,000. The method according to claim 1,
Wherein the polysaccharide is selected from the group consisting of chitin, chitosan, gum arabic, alginic acid, carrageenan, agar, xanthan gum, gellan gum, cellulose, xylose, starch, pullulan, pectin, roastbenght, dextran, &Lt; / RTI &gt; The method according to claim 1,
Wherein the copolymer is represented by the following formula (3).
(3)

In the above formula, the weight ratio of a, b, and c is 5 to 40: 5 to 40: 0.1 to 30, n is an integer of 1 to 1,000,000, and M is Cu, Zn, or Si. (4)
Wherein at least one of the acrylate monomer and the methacrylate monomer is contained in the main chain and the hydrophilic polymer is contained in the side chain.
&Lt; Formula 4 >

Wherein the weight ratio of w, x, y and z is in the range of 5 to 40: 5 to 40: 5 to 40: 0.1 to 30, and Z is any polymer selected from polyethylene oxide, polyacrylamine or polysaccharide to be. 6. The method of claim 5,
Wherein the copolymer is represented by the following formula (5).
&Lt; Formula 5 >

In the above formula, the weight ratio of w, x, y and z is 5 to 40: 5 to 40: 5 to 40: 0.1 to 30, and n is an integer of 1 to 1,000,000. 6. The method of claim 5,
Wherein the polysaccharide is selected from the group consisting of chitin, chitosan, gum arabic, alginic acid, carrageenan, agar, xanthan gum, gellan gum, cellulose, xylose, starch, pullulan, pectin, roastbenght, dextran, &Lt; / RTI &gt; 8. The method of claim 7,
Wherein the copolymer is represented by the following formula (6).
(6)

Wherein the weight ratio of w, x, y and z is 5 to 40: 5 to 40: 5 to 40: 0.1 to 30, n is an integer of 1 to 1,000,000, and M is Cu, Zn or Si. A composition for reducing friction resistance comprising a copolymer according to any one of claims 1 to 8.

Images