KR20140086814A - Polymethacrylate composition - Google Patents

Abstract

A polymethacrylate composition of the present invention includes polymethacrylate, an antioxidant containing a first compound represented by Formula (I) and a second compound represented by Formula (II). The polymethacrylate has a weight average molecular weight of 50,000-150,000, and includes 92-99 wt% of a methacrylate monomer unit and 1-8 wt% of an acrylate monomer unit. The amount of the antioxidant is equal to or greater than 0.005 to less than 0.3 parts by weight based on 100 parts by weight of the polymethacrylate.

Description

[0001] POLYMETHACRYLATE COMPOSITION [0002]

The present invention relates to a polymethacrylate composition, and more particularly to a polymethacrylate composition comprising an antioxidant.

Polymethacrylates are widely used in many applications, and are excellent in properties such as moldability and physical and mechanical properties. In addition, polymethacrylates are believed to be one of the most outstanding transparent polymers known as "plexiglass " used in molded articles having a higher translucency (92% or less) than glass and requiring a transparent appearance. Polymethacrylates are widely used for the manufacture of various optical elements or consumer goods, such as camera lenses, lenses, tail-lights, billboards and the like.

Although the polymethacrylate has excellent optical properties and moldability as described above, the thermal stability is poor. In order to improve the thermal stability, a method of increasing the molecular weight of polymethacrylate has been proposed. However, the higher the molecular weight of the polymethacrylate, the lower the flowability of the polymethacrylate. When polymethacrylates have a large molecular weight, it is difficult or impossible to process them, and thus a high processing temperature is required. When the poly methacrylate is extruded or injected at a high temperature, the possibility of deterioration of the polymethacrylate is greatly increased. In addition, if the molecular weight of the polymethacrylate is increased in order to improve the thermal stability, the flowability of the polymethacrylate may be lowered, so that subsequent processing may become more difficult.

Optical elements made from a polymethacrylate composition tend to become yellowing after being used for a predetermined period of time due to weather effects and / or prolonged exposure to sunlight. The yellowing of the optical element has a significant impact on transparency and may even result in changes in the color and brightness of the light after passing through the optical element.

As a general solution to the yellowing problem, octadecyl- (3,5-bis-tert-butyl-4-hydroxyphenyl) -propionate, triethylene glycol-bis [3- (3- Methyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (3,5-bis-tert- Methylphenylacrylate, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2, Bis [tert-butyl-4-hydroxyphenyl] -2'-thio-bis (4-methyl- Propionate] and 2,2'-bisoxalylamide-bis [ethyl-3- (3,5-bis-tert-butyl-4-hydroxyphenyl) propionate] A method of adding the silane coupling agent to the silane coupling agent is proposed.

Patent documents EP 0322166 and US 5,045,581 disclose antioxidants for polybutadiene rubber. The antioxidant includes a compound represented by the following formula (I) or an analog thereof:

In the preparation of the polybutadiene rubber, the devolatilizing temperature is generally higher than the solution polymerization temperature. Compounding in an oxygen-free atmosphere can cause yellowing of the polybutadiene rubber. Although the aforementioned yellowing problem of the polybutadiene rubber can be improved by using the compound of the formula (I) as an antioxidant, the problem of yellowing of the polymethacrylate can be solved by only using the compound of the formula (I) It can not be effectively solved.

In view of the above circumstances, there is a long-felt need to provide a polymethacrylate composition having high thermal stability and excellent resistance to yellowing.

It is therefore an object of the present invention to provide a polymethacrylate composition which can overcome the above-mentioned disadvantages associated with the prior art

According to the present invention there is provided a polymethacrylate composition comprising the following components:

Polymethacrylates having a weight average molecular weight in the range of 50,000 to 150,000, containing 92 to 99% by weight of methacrylate monomer units and 1 to 8% by weight of acrylate monomer units; And

An antioxidant comprising a first compound represented by the following formula (I) and a second compound represented by the following formula (II):

,

,

Here, the amount of the antioxidant is 0.005 parts by weight or more and less than 0.3 parts by weight based on 100 parts by weight of polymethacrylate.

According to the present invention, there is provided a polymethacrylate composition having high thermal stability and excellent resistance to yellowing.

The polymethacrylate compositions of the present invention include polymethacrylates and antioxidants.

The antioxidant contains a first compound represented by formula (I) and a second compound represented by formula (II): < EMI ID =

,

,

.

.

The amount of the antioxidant is 0.005 weight part or more and less than 0.3 weight part, preferably 0.005 to 0.07 weight part, more preferably 0.005 to 0.03 weight part, based on 100 weight parts of polymethacrylate.

The polymethacrylate has a weight average molecular weight in the range of 50,000 to 150,000, preferably 60,000 to 120,000, more preferably 65,000 to 75,000, and contains 92 to 99% by weight of methacrylate monomer units and 1 to 8% by weight of acrylic Lt; / RTI > monomer units.

Preferably, the polymethacrylate is prepared by polymerizing 92 to 99% by weight of a methacrylate monomer, 1 to 8% by weight of an acrylate monomer, and optionally 0 to 7% by weight of another copolymerizable monomer.

Examples of methacrylate monomers include, but are not limited to, n-octyl methacrylate, methyl methacrylate, n-butyl methacrylate, and combinations thereof.

Examples of acrylate monomers include, but are not limited to, n-hexyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octadecyl acrylate, and combinations thereof.

Examples of other copolymerizable monomers include, but are not limited to, acrylonitrile, styrene, maleic anhydride, a-methylstyrene, and combinations thereof.

Polymethacrylates prepared by polymerization contain methacrylate monomer units and acrylate monomer units. Here, the term "monomer unit" means a repeating structure contained in the polymethacrylate and derived from the corresponding monomer. Specifically, the methacrylate monomer unit and the acrylate monomer unit contained in the polymethacrylate are derived from a methacrylate monomer and an acrylate monomer, respectively.

The polymethacrylate can be prepared by solution polymerization or bulk polymerization. The polymerization is preferably carried out in the presence of a solvent in order to avoid that the viscosity of the crude polymethacrylate during polymerization exceeds a specific value, making it difficult to control the polymerization.

The level of viscosity depends on the solids content of the polymethacrylate in the solution polymerization process. Therefore, the amount of solvent needs to be controlled appropriately. Preferably, the solids content of the crude polymethacrylate is less than 50 wt%, more preferably less than 40 wt%.

The boiling point of the solvent is preferably close to the boiling point of the monomers used in the polymerization. For example, when the boiling point of the solvent is close to the boiling point of the methacrylate monomer, the boiling point range of the mixture of solvent and methacrylate monomer can be narrowed. Since the recycle mixture of solvent and unreacted monomer is less likely to be contaminated with contaminants, it is not necessary to fractionate the recycle mixture of solvent and unreacted monomer.

The boiling point of the solvent is preferably in the range of 40 to 225 占 폚, more preferably 60 to 150 占 폚. Examples of solvents include, but are not limited to, hexane, heptane, octane, benzene, toluene, xylene, o-xylene, m-xylene, ethylbenzene, cyclohexane, cyclodecane, isooctane, and other hydrocarbons And an aromatic hydrocarbon solvent.

Polymerization of polymethacrylates is initiated by free radical initiators. Examples of free radical initiators include, but are not limited to, the following:

(AIBN), 2,2'-azobis- (2-methylbutyronitrile) [AMBN], and 2,2'-azobis- (isobutyronitrile) (2,4-dimethylvaleronitrile) [ADVN];

(2) diacyl peroxides such as dilauryl peroxide, decanoyl peroxide, and dibenzoyl peroxide [BPO];

(3) dialkyls such as 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, dicumyl peroxide, and 1,3-bis- (t-butylperoxyisopropyl) Peroxides;

(4) peroxyesters such as t-butyl peroxypivalate and 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane;

(5) peroxycarbonate such as t-amylperoxy 2-ethylhexylcarbonate, and tert-butylperoxy 2-ethylhexylcarbonate;

(6) peroxydicarbonates such as di-myristyl peroxydicarbonate and di (4-tert-butylcyclohexyl) peroxydicarbonate;

(7) A process for producing (1) a product obtained by reacting 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2- The same peroxyketals; And

(8) Hydroperoxides such as t-butyl hydroperoxide, and isopropyl cumyl hydroperoxide.

Other examples of free radical initiators include 2,3-dimethyl-2,3-diphenyl-butane, potassium persulfate, sodium persulfate, and ammonium persulfate.

Preferably, the free radical initiator is 2,2'-azobis- (isobutyronitrile).

The amount of the free radical initiator used in the polymerization of the polymethacrylate is 0.01 to 1 part by weight, preferably 0.03 to 0.5 part by weight, more preferably 0.03 to 0.5 part by weight, based on 100 parts by weight of the monomer mixture supplied for producing the polymethacrylate Is in the range of 0.07 to 0.1 parts by weight.

In one embodiment, the polymerization is carried out at room temperature. In order to increase the polymerization rate, the polymerization may be carried out at an elevated temperature. Preferably, the polymerization temperature is in the range of 5 to 200 占 폚, more preferably 20 to 130 占 폚, and most preferably 30 to 100 占 폚.

The polymethacrylate compositions of the present invention may optionally comprise suitable additives according to actual requirements. The additives may include plasticizers, processing aids, UV stabilizers, UV absorbers, fillers, enhancers, colorants, lubricants, antistatic agents, flame retardants, flame retardant additives, thermal stabilizers, . The additive may be added during polymerization, after polymerization, before polymerization, or during compounding extrusion, but is not limited thereto.

Examples of lubricants include, but are not limited to, ethylene bis-stearyl amide, methylene bis-stearyl amide, palmitoyl amide, butyl stearate, palmityl stearate, glycerol tristearate, n- , Polyethylene wax, n-octanoic acid wax, carnauba wax, petroleum wax and metal soaps of calcium stearate, magnesium stearate and lithium stearate. Preferably, the lubricant is used in an amount ranging from 0.03 parts by weight to 5.0 parts by weight, based on 100 parts by weight of polymethacrylate.

In order to enhance extrusion moldability and thermoformability of the polymethacrylate composition, a processing aid such as an acrylic compound may be added. Preferably, the acrylic compound is a core-shell processing aid and has a weight average molecular weight greater than 500,000. Examples of ultraviolet absorbers include, but are not limited to, benzotriazole-based compounds, benzophenone-based compounds, and cyanoacrylate-based compounds. Examples of UV stabilizers include, but are not limited to, hindered amine based compounds. Preferably, the above-mentioned additives are each used in an amount ranging from 0.02 parts by weight to 2.0 parts by weight, based on 100 parts by weight of polymethacrylate.

Examples of antistatic agents include, but are not limited to, low molecular weight compounds of tertiary amines or quaternary ammonium salts, and polyamide polyethers such as permanent antistatic polymeric materials (e.g., poly (epichlorohydrin)) . Examples of fillers include, but are not limited to, calcium carbonate, silica, and mica. Examples of reinforcing agents include, but are not limited to, glass fibers, carbon fibers, and various whiskers. Examples of colorants include, but are not limited to, titanium dioxide, iron oxide, graphite, and phthalocyanine dyes. Examples of heat stabilizers include, but are not limited to, dibutyl tin maleate, and aluminum magnesium hydro carbonate bases. A non-limiting example of a thermal discoloration inhibitor is a low molecular weight styrene-maleic anhydride copolymer. Preferably, the above-mentioned additives are each used in an amount ranging from 0.1 to 1.0 part by weight based on 100 parts by weight of polymethacrylate.

The second compound of formula (II) is used in an amount of preferably 0.1 to 10 parts, more preferably 0.15 to 5 parts, and most preferably 0.18 to 3 parts, based on 1,000,000 parts of the polymethacrylate composition .

Preferably, the weight ratio of the first compound of formula (I) to the second compound of formula (II) is 99.615: 0.385.

The preparation of the polymethacrylate composition can be carried out using a kneading apparatus. Examples of kneading apparatus include, but are not limited to, a Brabender plasticizer, a Banbury mixer, a kneading mixer, a roll kneader, a single screw extruder, and a twin screw extruder. After extrusion, the extrudate of the polymethacrylate composition is cooled and pelletized. The kneading step is typically carried out at a temperature in the range of 160 to 280 DEG C, preferably 180 to 250 DEG C.

The polymethacrylate composition may be shaped to form a product having a desired shape, such as a pressing plate and a thin sheet. The flowability and thermal stability of the polymethacrylate compositions can be adjusted according to actual requirements. Methods for molding a polymethacrylate composition include, but are not limited to, film molding, injection molding, compression molding, extrusion molding, blow molding, thermoforming, and vacuum molding.

The following examples are provided to illustrate preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention.

Chemicals used in the following examples:

1. Antioxidant (AO-1): The first compound of formula (I) described above and the second compound of formula (II) described above are contained at a weight ratio of 99.615: 0.385.

2. Antioxidant (AO-2): Containing 99.9% by weight of the first compound of formula (I) and not containing the second compound of formula (II).

3. Octadecyl- (3,5-bis-tert-butyl-4-hydroxyphenyl) -propionate: available from Yi Yi Industrial Co., Ltd., trade name "I1076".

4. 2-t-Butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, available from Yi Yi Industrial Co., -246 ".

(Preparation of polymethacrylate)

Preparation Example 1:

93.5 parts by weight of methyl methacrylate, 6.5 parts by weight of methyl acrylate, 0.43 part by weight of n-dodecyl mercaptan, 0.085 part by weight of 2,2'-azo-bis-iso-butyronitrile and 66 parts by weight of toluene were mixed To form a preliminary mixture. The preliminary mixture was fed to a jacketed reactor in which thermal oil was circulated and a continuous solution polymerization reaction was carried out.

The reaction was carried out at a temperature of about 100 DEG C under a pressure of 600 torr. The premix was stirred in the reactor until the premix became a homogeneously mixed polymer solution. After the polymerization was completed, the polymer solution was heated to 265 DEG C and devolatilized under reduced pressure in a continuous-type devolatilizer to form a polymer product. The polymer product was extruded through a extruder to be a strip, and then cooled and pelletized to obtain a pellet of polymethacrylate (P-1).

The thus formed polymethacrylate (P-1) contains 95.5% by weight of methacrylate monomer units and 4.5% by weight of acrylate monomer units, and has a weight average molecular weight of 75,000 and a melt flow index (MI) of 9.0 I have.

Preparation Example 2:

The operation conditions for the production of the polymethacrylate (P-2) were 93 parts by weight of methyl methacrylate, 7 parts by weight of methyl acrylate, 0.4 part by weight of n-dodecyl mercaptan, (P-1) were prepared in the same manner as in Example 1 except that 0.08 part by weight of 2,2'-iso-butyronitrile and 66 parts by weight of toluene were mixed to form a premixture.

The thus formed polymethacrylate (P-2) contains 95% by weight of methacrylate monomer units and 5% by weight of acrylate monomer units and has a weight average molecular weight of 110,000 and a melt flow index (MI) of 1.8 I have.

Preparation Example 3:

The operation conditions for the production of the polymethacrylate (P-3) were 93.5 parts by weight of methyl methacrylate, 6.5 parts by weight of methyl acrylate, 0.4 parts by weight of n-dodecyl mercaptan, (P-1) were prepared in the same manner as in Example 1 except that 0.08 part by weight of 2,2'-iso-butyronitrile and 66 parts by weight of toluene were mixed to form a premixture.

The thus formed polymethacrylate (P-3) contained 95.5% by weight of methacrylate monomer units and 4.5% by weight of acrylate monomer units and had a weight average molecular weight of 72,000 and a melt flow index (MI) of 9.5 I have.

Preparation Example 4:

The operating conditions for the production of the polymethacrylate (P-4) were 93 parts by weight of methyl methacrylate, 7 parts by weight of methyl acrylate, 0.45 part by weight of n-dodecyl mercaptan, (P-1) were prepared in the same manner as in Example 1, except that 0.09 part by weight of 2,2'-iso-butyronitrile and 66 parts by weight of toluene were mixed to form a premix.

The thus formed polymethacrylate (P-4) contained 95% by weight of methacrylate monomer units and 5% by weight of acrylate monomer units, and had a weight average molecular weight of 74,000 and a melt flow index (MI) of 10 I have.

[ Polymethacrylate  Preparation of the composition]

Example 1:

10 kg of polymethacrylate (P-1) and an antioxidant (AO-1) (see Table 1 for the content) were mixed and extruded at 230 ° C in an extruder (available from Continent Machinery Industries Co., Ltd., Model CM -PRA35), and then pelletized to obtain a pellet of a polymethacrylate composition. The polymethacrylate composition was molded through an injection molding machine (available from Chen Hsong Holdings Limited, Model SM-90) to form molded samples. The shaped sample thus formed has a length of 22 cm, a width of 2 cm, and a thickness of 3 mm.

Examples 2 to 7:

The polymethacrylate compositions of Examples 2 to 7 were prepared under the same conditions as those used in Example 1, except for the content of the polymethacrylate composition. The polymethacrylate compositions of Examples 2 to 7 are listed in Table 1. Molded samples of Examples 2 to 7 were prepared under the same conditions as those used in Example 1.

Example 8:

The polymethacrylate composition of Example 8 was prepared under the same conditions as those used in Example 1, except for the content of the polymethacrylate composition. The polymethacrylate composition of Example 8 contained an antioxidant containing a second compound of Formula (II) in an amount of 3.08 parts based on 1,000,000 parts of the polymethacrylate composition (Polymethacrylate P-4) 0.08 part by weight of AO-1).

A test was conducted to measure the temperature at which the thermal weight loss of the polymethacrylate composition of Example 8 was 3%. The test was performed by raising the temperature from 100 DEG C to 600 DEG C at a heating rate of 20 DEG C / min under a nitrogen atmosphere. The temperature at which the weight loss of Example 8 was 3% was 338 占 폚.

Comparative Example 1:

The polymethacrylate composition of Comparative Example 1 was produced under the same conditions as in Example 1 except for the content of the polymethacrylate composition. The polymethacrylate composition of Comparative Example 1 contains no antioxidant. A molded sample of Comparative Example 1 was produced under the same conditions as in Example 1.

Comparative Examples 2 to 9:

The polymethacrylate compositions of Comparative Examples 2 to 9 were prepared under the same conditions as in Example 1 except for the content of the polymethacrylate composition. Each of Comparative Examples 2 to 9 contained 0.05 part by weight of stearyl alcohol. The polymethacrylate compositions of Comparative Examples 2 to 9 are listed in Table 1. The molded samples of Comparative Examples 2 to 9 were produced under the same conditions as in Example 1. [

Comparative Example 2 contains only 0.03 parts by weight of the first compound of Formula (I) and does not contain the second compound of Formula (II). The antioxidant of Comparative Example 3 is I1076. The antioxidant of Comparative Examples 4 to 8 is HW-246. The antioxidant of Comparative Example 9 was 0.3 parts by weight of (AO-1).

Comparative Example 10:

A polymethacrylate composition of Comparative Example 10 was prepared under the same conditions as in Example 1, except for the content of the polymethacrylate composition. The polymethacrylate composition of Comparative Example 10 contains polymethacrylate (P-4) and 0.033 part by weight of antioxidant (I1076).

A test was conducted to measure the temperature at which the thermal weight loss of the polymethacrylate composition of Comparative Example 10 was 3%. The test was performed by raising the temperature from 100 DEG C to 600 DEG C at a heating rate of 20 DEG C / min under a nitrogen atmosphere. The temperature at which the weight loss of Comparative Example 10 was 3% was 302 占 폚.

<Physical property test>

The following tests were conducted on the molded samples of Examples 1 to 7 and Comparative Examples 1 to 9. The test results are shown in Table 1.

1. Relative yellowness index:

To measure the yellowing index, each of the molded samples of Examples 1 to 7 and Comparative Examples 1 to 9 was tested according to ASTM D1925 using a spectrometer (available from Nippon, Model ASA-1).

The yellowing index of the molded sample of Comparative Example 1 is represented by YI ₁ , and the yellowing index of each of the molded samples of Examples 1 to 7 and Comparative Examples 2 to 9 is represented by YI _x . The relative yellowing index was calculated according to the following equation:

Relative Yellowing Index (%) = YI _x / YI ₁ x 100%

2. Weight loss at 5% Temperature:

A sample (0.5 g) of each of the molded samples of Examples 1 to 7 and Comparative Examples 2 to 9 was placed in a thermogravimetric analysis (TGA) apparatus and heated at a heating rate of 20 캜 / min in a nitrogen atmosphere from 100 캜 to 600 캜 The temperature was measured at 5% weight loss by heating.

As shown in Table 1, Comparative Example 1, which contains polymethacrylate (P-1) and contains no antioxidant, has a temperature of 323.28 ° C at a weight loss of 5%. Examples 1 to 4 are different from each other in the amounts of the first compound of the formula (I) and the second compound of the formula (II) contained in the antioxidant (AO-1). The amount of the second compound in each of Examples 1 to 4 is 0.385% by weight based on the total weight of the antioxidant (AO-1). Comparing Examples 1 to 4 and Comparative Example 1, each of Examples 1 to 4 has a much lower relative yellowing index than Comparative Example 1, and the temperature at 5% weight loss is higher than Comparative Example 1.

Each of Examples 5 to 7, which contains polymethacrylate (P-2) having a weight average molecular weight larger than that of polymethacrylate (P-1) Lt; RTI ID = 0.0 &gt; 5% &lt; / RTI &gt; higher than Examples 1 to 4 and Comparative Example 1.

Comparative Example 2, which contains only the first compound of formula (I) (i.e., does not contain the second compound of formula (II)), has a relative yellowing index of 115% Temperature, 336.1 [deg.] C. Comparing Examples 5 to 7 with Comparative Example 2, Comparative Example 2 appears to have relatively poor yellowing resistance.

Embodiment 5 to 7 each contain 0.03 part by weight of an antioxidant. Embodiments 5 to 7 are different from each other in the amounts of the first compound of formula (I) and the second compound of formula (II). As a result of the test, it was found that the greater the amount of the second compound of formula (II), the better the yellowing resistance.

Comparing Comparative Example 10 with Example 8, in the test results of the temperature at 3% weight loss, it was found that the poly (aminophenol) having an antioxidant containing both the first compound of Formula (I) and the second compound of Formula (II) The methacrylate composition appears to have good thermal stability compared to polymethacrylate compositions with antioxidants containing only the first compound of formula (I).

Comparative Example 3 containing I1076 as an antioxidant has poor yellowing resistance. Comparative Examples 4 to 8 contain, as antioxidants, HW-246 having a chemical structure similar to that of the first compound of formula (I). Increasing the amount of HW-246 slightly improves relative yellowing index, but yellowing resistance is worse.

Comparative Example 9, which contains 0.3 part by weight of AO-1 containing the second compound of formula (II) in an amount of 11.55 parts based on 1,000,000 parts of the polymethacrylate composition, has poor yellowing resistance.

Taken together, when the first compound of formula (I) and the second compound of formula (II) are all included in the polymethacrylate composition of the present invention, the above-mentioned disadvantages associated with the prior art can be reduced have.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiment, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the most inclusive interpretation, But should be understood to cover the configuration.

Claims (7)

Polymethacrylates having a weight average molecular weight in the range of 50,000 to 150,000, containing 92 to 99% by weight of methacrylate monomer units and 1 to 8% by weight of acrylate monomer units; And
An antioxidant comprising a first compound represented by the following formula (I) and a second compound represented by the following formula (II)
Wherein the amount of the antioxidant is 0.005 parts by weight or more and less than 0.3 parts by weight based on 100 parts by weight of the polymethacrylate.

,

. The method according to claim 1,
Wherein the amount of said second compound ranges from 0.1 to 10 parts, based on 1,000,000 parts of said polymethacrylate composition. 3. The method of claim 2,
Wherein the amount of said second compound ranges from 0.15 parts to 5 parts based on 1,000,000 parts of said polymethacrylate composition. The method according to claim 1,
&Lt; / RTI &gt; further comprising a thiol compound. The method according to claim 1,
Wherein the methacrylate monomer units are selected from the group consisting of n-octyl methacrylate monomer units, methyl methacrylate monomer units, n-butyl methacrylate monomer units, and combinations thereof. The method according to claim 1,
Wherein the acrylate monomer unit is selected from the group consisting of n-hexyl acrylate monomer units, methyl acrylate monomer units, ethyl acrylate monomer units, butyl acrylate monomer units, octadecyl acrylate monomer units, and combinations thereof , A polymethacrylate composition. The method according to claim 1,
Wherein the polymethacrylate has a weight average molecular weight ranging from 65,000 to 75,000.