KR20190083918A - Polysiloxane-based copolymer which has high heat-resistant and hydrophobic characteristics, and coating composition comprising thereof - Google Patents

Abstract

The present invention is to provide a modified polysiloxane-based polymer having a perfluorinated group and an alkoxy silane reactor, and a coating composition comprising the polymer. A coating composition comprising a modified polysiloxane-based polymer of the present invention has excellent thermal resistance and high hydrophobic characteristics, thereby being capable of being widely used in various fields such as solar cell cover glass, metal pipe coating or painting of a heat exchanger, a coating material, etc.

Description

TECHNICAL FIELD [0001] The present invention relates to a polysiloxane-based polymer for high heat resistance and hydrophobic coating, and a coating composition comprising the polysiloxane-

The present invention relates to a modified polysiloxane-based polymer having perfluorinated and alkoxysilane reactors and a coating composition comprising the polymer. More specifically, the coating composition comprising the modified polysiloxane-based polymer of the present invention has excellent heat resistance and high hydrophobicity, and thus can be applied to various fields such as solar cell cover glass, metal pipe coating agent of heat exchanger, paint, paint and the like.

Recently, it has been known to manufacture various industrial equipment such as desulfurization equipment, power generation facilities, dust collectors, incinerators, boilers or casting equipment, transferring molten metal, or pouring a molten metal into a pouring box or a metal pipe of a heat exchanger Heat-resistant coating agents are widely used.

In particular, industrial facilities in specific fields such as steel, steel, and petrochemical are easily exposed to high-temperature heat in each process, so that it is easy to cause deterioration and heat loss, and there is a risk of industrial accidents due to occurrence of fire. It is essential to protect industrial equipment using In the case of general paints and paints used for indoor construction, when the material is exposed to a high-temperature environment such as a fire, it releases toxic gases and causes human accidents. Therefore, it is preferable to use the heat-resistant coating agent. Paints and paints containing heat-resistant coatings prevent the generation of toxic fumes in the event of a fire, thus minimizing damage to buildings.

Such a heat resistant coating agent used in various fields causes coating film breakage such as discoloration, cracking, softening or peeling to occur below a predetermined standard even when the coating agent is applied to an object having a high temperature of 100 ° C or higher. It is known that aluminum, zinc, graphite, tin, cadmium powder or quartz is used as a pigment used as a heat-resistant coating agent, and silicone resin is used as a binder.

However, the conventional heat-resistant coating agent is not only difficult to cope with the surface change of the substrate depending on the temperature, but also causes serious pollution caused by heavy metal contamination such as generating harmful substances at high temperature due to the organic compound or metal compound added for improving heat resistance . Particularly, the limit of the conventional heat-resistant coating agent has become prominent in the fields of the steel industry and the like. Specifically, due to the limitations of heat-resistant coatings in charcoal L / D, molten steel, charging L / D, petroleum coke, coke oven doors, OLC (Open Ladle Car) And so on.

Therefore, there is an urgent need to develop a coating material having high heat resistance that can be used in various industrial fields to protect internal equipment and components at high temperatures by improving these problems.

On the other hand, the characteristics of the surface of a specific substance can be distinguished by the contact angle of the water drop. (Or water repellency) from 140 ° to 180 ° in general, from 80 ° to 110 ° in hydrophilic (or water repellent), and from 10 ° to 40 ° in hydrophilic, . This property of the material surface may vary depending on whether the surface is coated with a coating material composed of any compound.

The use of coatings that increase hydrophobicity varies widely. For example, it can be applied not only to objects surrounded by the atmosphere but also to objects with frequent contact with water. It can also be applied to walls, container surfaces, cubicles, platforms, posts, or structures with long contact with fresh or salt water . By applying such hydrophobic coatings to various materials such as metals, glass, and plastics, it can be applied to various business fields such as coatings for electronic products such as semiconductors, as well as antifouling paints for ships. As described above, there is an increasing demand for highly utilizable hydrophobic coating materials and coatings having excellent hydrophobic properties. Recently, however, hydrophobic coating materials using hydrocarbons have attracted attention, There is a problem in that the characteristics of the material remarkably deteriorate as the dehydrogenation reaction progresses gradually at a temperature.

Therefore, it is necessary to develop a compound which has high heat resistance and maintains hydrophobicity even at a high temperature so that its characteristics are not changed, and a coating composition containing it as an effective ingredient.

Korea registered patent 1,492,251 Korea Patent No. 1,297,368 Korea registered patent 1,582,344

Polymethylhydrosiloxane-based organic-inorganic hybrids for amphiphobic coatings; Saravanan Nagappan etc, Composite Interfaces page 33-43, 2013.

The present invention provides a polysiloxane polymer comprising a fluorine group and an alkoxysilane reactor having high heat resistance and being hydrophobic even at a high temperature in order to solve the problems of conventional heat resistant or hydrophobic coating agents, or a coating composition comprising the same as an active ingredient .

In order to achieve the above object,

There is provided a modified polysiloxane-based polymer having the following general formula (1).

[Formula 1]

In the general formula (1), X is selected from A, B or C,

이고, B는

이며, C는

이고,Here, A is

And B is

And C is

ego,

이고,Wherein R < _{1 &}

ego,

Wherein R ₃ and R ₄ are each independently a branched or unbranched C ₁ -C ₁₀ alkylene,

, -CONH- 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z is

, -CONH-, and -O-, and at least one group selected from the group consisting of

f is 0 or 1,

b is an integer of 1 to 10,

g is 0, 1 or 2,

h is 0, 1 or 2, provided that g + h is 2;

i is 0, 1 or 2,

j is 0, 1, 2 or 3, with the proviso that i + j is 3,

이며, Wherein R < _{2 &}

Lt;

Wherein R ₅ and R ₆ are each independently a branched or unbranched C ₁ -C ₁₀ alkylene,

R ₇ is C ₁ -C ₁₀ alkyl,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z '

, -CONH-, and -O-, and at least one group selected from the group consisting of

k is 0 or 1,

Wherein Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,

In Formula 1, a is an integer of 1 or more, and one of A, B, and C is selected as a increases.

In one embodiment of the present invention, the modified polysiloxane-based polymer may have a weight average molecular weight ranging from 500 to 1,000,000.

이고, In one aspect of the present invention, R ₃ and R ₅ are each independently

ego,

R ₄ is branched or unbranched C ₁ -C ₅ alkylene,

R ₆ is a branched or unbranched C ₂ -C ₅ alkylene,

R ₇ is a C ₁ -C ₅ alkyl,

부분은 Si와 결합하는 부위이고,In the above formula,

The moiety is a moiety bonding to Si,

R ₈ can be a hydrogen atom, or a branched or unbranched C ₁ -C ₅ alkyl.

The present invention also relates to a process for producing a polymer comprising a fluorine-containing polymer represented by the following formula (2) and an alkoxysilane group represented by the following formula (3) in a polysiloxane-based polymer backbone represented by the following formula (1) and a grafted moiety. The present invention also provides a modified polysiloxane-based polymer.

≪ Formula 1 >

(2)

(3)

In the above formulas,

Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R _{3 and} R ₇ are each independently a hydrogen atom, a branched or unbranched C ₁ -C ₅ alkyl group,

R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

R _{5, which} may be the same or different, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,

R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

, -CONH-, 및 -O- 로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z and Z 'are each independently

, -CONH-, and -O-, and at least one group selected from the group consisting of

f and k are each independently 0 or 1,

m is an integer of 1 to 2000, and as m increases, R ₁ and R ₂ are each independently selected from a hydrogen atom or a methyl group,

n is an integer of 1 to 20;

In one aspect of the present invention, the moiety may be represented by the following Formula 4:

≪ Formula 4 >

In the above formulas,

Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R ₃ and R ₇ are each independently a hydrogen atom or a branched or unbranched C ₁ -C ₅ alkyl group,

R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

R _{5, which} may be the same or different, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,

R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z and Z ' may be present or absent and, if present, each independently

, -CONH-, and -O-, and at least one group selected from the group consisting of

n is an integer of 1 to 20,

c, d and e are each an integer of 0 to 2000, provided that c + d + e is 2 to 2000,

The order of each moiety that can be c, d, and e is arbitrary.

Here, the meaning of the order of each moiety to be c, d, and e is arbitrary is as shown in the following example.

For example, if c is 1, d is 1, and e is 1, then the following six cases (CDE, CED, DCE, DEC, ECD, EDC) are all possible:

case 1)

case 2)

case 3)

case 4)

case 5)

case 6)

It will be appreciated by those skilled in the art that the order may be arbitrarily arranged in various cases when c is 0, d is 1, e is 1, c is 1, d is 0, and e is 1 .

In one embodiment of the present invention, the fluorine-containing polymer may be a compound of the following formula:

≪ Formula 5 >

Wherein R ₃ is a hydrogen atom, a branched or unbranched C ₁ -C ₅ alkyl group,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이며,Z is

, -CONH-, and -O-,

f is 0 or 1,

and n is an integer of 4 to 10.

In one embodiment of the present invention, the polymer comprising the alkoxysilane group may be a compound of the following formula:

(6)

In the above formula

R ₃ is a hydrogen atom, a branched or unbranched C ₁ -C ₅ alkyl group,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이며,Z '

, -CONH-, and -O-,

k is 0 or 1;

In one aspect of the present invention, the metal catalyst may be a platinum catalyst or a Karstedt catalyst.

The present invention also provides a coating composition comprising the modified polysiloxane-based polymer.

In one embodiment of the present invention, the coating composition may further include at least one additive selected from a curing agent, a releasing agent, a surfactant, an antioxidant, metal particles, oxide particles and nitride particles.

In addition,

1) mixing a polysiloxane-based polymer of the following formula 1 with a polymer containing fluorine of the following formula 2 and an alkoxysilane-containing polymer of the following formula 3;

2) introducing the metal catalyst into the 1) mixture; And

3) stirring the mixture of the above 2) to obtain a modified polysiloxane-based polymer having a moiety of the following formula (4).

≪ Formula 1 >

(2)

(3)

≪ Formula 4 >

In the above formulas,

Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R ₃ and R ₇ are each independently a hydrogen atom, a branched or unbranched C ₁ -C ₅ alkyl group,

R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

R ₅ may be the same or different from each other, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,

R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z and Z 'are each independently

, -CONH-, and -O-, and at least one group selected from the group consisting of

f and k are each independently 0 or 1,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이며,In the above formula (4), Z and Z 'may or may not be present, and when present, each independently

, -CONH-, and -O-,

m is an integer of 1 to 2000, and as m increases, R ₁ and R ₂ are each independently selected from a hydrogen atom or a methyl group,

n is an integer of 1 to 20,

c, d and e are each an integer of 0 to 2000, provided that c + d + e is 2 to 2000,

The order of each moiety that can be c, d, and e is arbitrary.

In one embodiment of the present invention, the metal catalyst of step 2) may be at least one of a platinum catalyst or a Karstedt catalyst.

The modified polysiloxane polymer containing a fluorine group and the coating composition containing the fluorine group as an effective ingredient of the present invention have excellent hydrophobicity and high heat resistance and can be utilized in various industrial fields such as solar cell cover glass , heat exchanger metal pipe, paint, paint and the like.

Fig. 1 shows the result of measurement of the contact angle between water and a glass surface coated with the modified fluoropolymer-modified polysiloxane-based polymer.
Fig. 2 shows the results of thermal decomposition behavior analysis of the synthesized fluorine-containing modified polysiloxane-based polymer.

Hereinafter, the present invention will be described in more detail.

The present invention provides a modified polysiloxane-based polymer having the following general formula (1).

[Formula 1]

In the general formula (1), X is selected from A, B or C,

이고, B는

이며, C는

이고,here. A is

And B is

And C is

ego,

이고 여기서 R₃ 및 R₄는 각각 독립적으로 분지 또는 비분지된 C₁-C₁₀ 알킬렌이며,Wherein R < _{1 &}

Wherein R ₃ and R ₄ are each independently a branched or unbranched C ₁ -C ₁₀ alkylene,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z is

, -CONH-, and -O-, and at least one group selected from the group consisting of

f is 0 or 1,

b is an integer of 1 to 10,

g is 0, 1 or 2,

h is 0, 1 or 2, provided that g + h is 2;

i is 0, 1 or 2,

j is 0, 1, 2 or 3, with the proviso that i + j is 3,

이며, Wherein R < _{2 &}

Lt;

Wherein R ₅ and R ₆ are each independently a branched or unbranched C ₁ -C ₁₀ alkylene,

R ₇ is C ₁ - ₁₀ alkyl, and,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z '

, -CONH-, and -O-, and at least one group selected from the group consisting of

k is 0 or 1,

Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,

In the general formula (1), a is an integer of 1 or more, and one of A, B, and C is selected as a increases.

More specifically, the definition that one of A, B, or C is selected with increasing a means that the A, B, or C structure can be randomly generated without specific rules as the number of X units increases , Meaning that in many cases a number of polymers having a structure that satisfies the above definition can be produced. The structures of possible compounds satisfying the above definition are shown below by way of example. However, the scope of the present invention is not limited to the following examples.

Example 1: _{(CH 3) 3 Si-O-} [ABABABABA ....] a -Si (CH 3) 3

Example 2: (CH ₃ ) ₃ Si-O- [AABAABAABA ....] _a -Si (CH ₃ ) ₃

Example _{3: (CH 3) 3 Si} -O- [ABBABBABB ....] a -Si (CH 3) 3

Example _{4: (CH 3) 3 Si} -O- [AABBAABBA ....] a -Si (CH 3) 3

Example _{5: (CH 3) 3 Si} -O- [ABAABBABBA ....] a -Si (CH 3) 3

Example _{6: (CH 3) 3 Si} -O- [ABCAACBBACBBA ....] a -Si (CH 3) 3

Example _{7: (CH 3) 3 Si} -O- [ACBACBACB ....] a -Si (CH 3) 3

Example 8: (CH ₃ ) ₃ Si-O- [CABCABCAB ....] _a -Si (CH ₃ ) ₃

Example _{9: (CH 3) 3 Si} -O- [BACBCABAC ....] a -Si (CH 3) 3

Example _{10: (CH 3) 3 Si} -O- [CCABCABC ....] a -Si (CH 3) 3

In one embodiment of the present invention, the modified polysiloxane-based polymer may have a weight average molecular weight of 500 to 1,000,000.

이고, In one aspect of the present invention, R ₃ and R ₅ are each independently

ego,

R ₄ is branched or unbranched C ₁ -C ₅ alkylene,

R ₆ is a branched or unbranched C ₂ -C ₅ alkylene,

R ₇ is a C ₁ -C ₅ alkyl,

부분은 Si와 결합하는 부위이고,In the above formula,

The moiety is a moiety bonding to Si,

R ₈ can be a hydrogen atom, or a branched or unbranched C ₁ -C ₅ alkyl.

The present invention also relates to a process for producing a polymer comprising a fluorine-containing polymer represented by the following formula (2) and an alkoxysilane group represented by the following formula (3) in a polysiloxane-based polymer backbone represented by the following formula (1) and a grafted moiety. The present invention also provides a modified polysiloxane-based polymer.

≪ Formula 1 >

(2)

(3)

In the above formulas,

Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R ₃ and R ₇ are each independently a hydrogen atom or a branched or unbranched C ₁ -C ₅ alkyl group,

R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

R ₅ may be the same or different from each other, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,

R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

, -CONH-, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z and Z 'are each independently

, -CONH-, and -O-, and at least one group selected from the group consisting of

f and k are each independently 0 or 1,

m is an integer of 1 to 2000, and as m increases, R ₁ and R ₂ are each independently selected from a hydrogen atom or a methyl group,

n is an integer of 1 to 20;

On the other hand, the moiety is characterized by being represented by the following formula (4).

≪ Formula 4 >

In the above formulas,

Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R ₃ and R ₇ are each independently a hydrogen atom or a branched or unbranched C ₁ -C ₅ alkyl group,

R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

R ₅ may be the same or different from each other, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,

R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

, -CONH-. -O-로 구성된 그룹으로부터 선택되는 적어도 1종이고,Z and Z ' may be present or absent and, if present, each independently

, -CONH-. -O- and at least one member selected from the group consisting of -O-,

m is an integer of 1 to 2000, and as m increases, R ₁ and R ₂ are each independently selected from a hydrogen atom or a methyl group,

n is an integer of 1 to 20,

c, d and e are each an integer of 0 to 2000, provided that c + d + e is 2 to 2000,

The order of each moiety that can be c, d, and e is arbitrary.

More specifically, the fluorine-containing polymer may include a compound represented by the following general formula (5). R ₃ , Z, f and n are as defined above.

≪ Formula 5 >

In Formula 5, n may be more specifically an integer of 4 to 15, and more particularly, an integer of 5 to 10.

On the other hand, the polymer containing alkoxysilane group includes a compound (3- (trimethoxysilyl) propyl methacrylate). Wherein Z 'and k are as defined above.

(6)

The metal catalyst may be selected from the group consisting of Pt, Pb, Ir, Rh, Fe, Ni, Co, Ag, Hg and Karstedt, One or more of the Karstedt catalysts may be used.

In the following Examples and Experimental Examples, examples in which a polysiloxane polymer, a fluorine-containing polymer and an alkoxysilane group-containing polymer were mixed at various ratios were presented. In Experimental Examples, The contact angle and% weight loss at 300 캜 were measured to confirm excellent hydrophobicity and heat resistance of the fluorine-containing polysiloxane polymer of the present invention.

Therefore, the modified polysiloxane-based polymer containing a moiety in which the polysiloxane-based polymer, the fluorine-containing polymer and the alkoxy silane group-containing polymer of the present invention are reacted under a metal catalyst has excellent hydrophobicity and heat resistance and is used in various industrial fields .

The present invention also provides a coating composition comprising the modified polysiloxane-based polymer.

The solvent used for preparing the coating composition is not particularly limited as long as it is a solvent capable of dissolving the modified polysiloxane polymer. Examples thereof include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), iso Propyl alcohol (PG), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), or A mixture of two or more of these may be used as a solvent.

In addition, the coating composition may contain at least one additive such as a curing agent, a releasing agent, a surfactant, an antioxidant, metal particles, oxide particles and nitride particles.

On the other hand, the coating compositions can be applied to various fields, and they can be used for improving heat resistance and improving hydrophobicity in metal tubes of heat exchangers, parts of various industrial equipments exposed to high temperatures, paints, paints and the like.

In addition,

1) mixing a polysiloxane-based polymer of the following formula 1 with a polymer containing fluorine of the following formula 2 and an alkoxysilane-containing polymer of the following formula 3;

2) introducing the metal catalyst into the 1) mixture; And

3) stirring the mixture of the above 2) to obtain a modified polysiloxane-based polymer having a moiety of the following formula (4).

≪ Formula 1 >

(2)

(3)

≪ Formula 4 >

In the above formulas,

Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,

R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,

R ₃ and R ₇ are each independently a hydrogen atom or a branched or unbranched C ₁ -C ₅ alkyl group,

R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

R _{5, which} may be the same or different, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,

R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,

, -CONH, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이며,Z and Z 'are each independently

, -CONH, and -O-,

f and k are each independently 0 or 1,

In Formula 4,

, -CONH, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이며,Z and Z ' may be present or absent and, if present, each independently

, -CONH, and -O-,

m is an integer of 1 to 2000, and as m increases, R ₁ and R ₂ are each independently selected from a hydrogen atom or a methyl group,

n is an integer of 1 to 20,

c, d and e are each an integer of 0 to 2000, provided that c + d + e is 2 to 2000,

The order of each moiety that can be c, d, and e is arbitrary.

More specifically, in the step 1), it is appropriate to mix the raw materials in the nitrogen condition for 5 to 20 minutes, preferably 10 minutes, and the type of the metal catalyst in the step 2) is not particularly limited, And Karstedt catalysts are preferably used. The step 3) is preferably carried out at 20 to 150 ° C for 2 to 6 hours, preferably 30 to 100 ° C, more preferably 40 ° C.

Therefore, the modified polysiloxane-based polymer prepared by the above method has excellent hydrophobicity and heat resistance and can be usefully used in various industrial fields.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. It is to be understood, however, that this description is intended to assist the understanding of the present invention and is not intended to limit the scope of the present invention thereto.

< Example  1> PMHS  Hydrophobic modified high heat resistance Polysiloxane-based Polymer  Produce

30 g of polymethylhydrosiloxane (PMHS (= PDMS-H), M _n 1700-3200, Sigma-Aldrich) was added to a reaction tank equipped with a stirrer and a nitrogen inlet. 1H, 1H, 2H, 2H-tridecafluoro-n- 5 g of methacrylate (FMA, TCI) and 5 g of 3- (trimethoxysilyl) propyl methacrylate (TMSPMA, Sigma-Aldrich) were added and nitrogen was added thereto. The mixture was stirred at room temperature for 10 minutes and a small amount of Karstedts catalyst was slowly dropped ) And mixed with the reactants. This mixture was stirred at 40 占 폚 for 4 hours to prepare a hydrophobic high-heat-resistant fluorine-modified polysiloxane polymer of the present invention. The modified polysiloxane-based polymer prepared by the above method has a transparent color.

< Example  2 to 9> varying proportions of PMHS  Hydrophobic modified high heat resistance Polysiloxane-based Polymer  Produce

The same raw materials as in Example 1 were used, but the mixing ratios of raw materials were different. The raw material mixing capacity of each example is shown in Table 1 below.

Sample PDMS-H
(g) FMA
(g) TMSPMA
(g) Example 1 (H0005) 30 0 5 Example 2 (H0010) 30 0 10 Example 3 (H0510) 30 5 10 Example 4 (H0015) 30 0 10 Example 5 (H0515) 30 5 15 Example 6 (H1515) 30 15 15 Example 7 (H0030) 30 0 30 Example 8 (H1530) 30 15 30 Example 9 (H3030) 30 30 30

< Example  10> PDMS  Hydrophobic modified high heat resistance Polysiloxane-based Polymer  Produce

30 g of poly (dimethylsiloxane-co-methylhydrosiloxane), trimethylsilyl terminated (PDMS-MH, Mn ~ 950, methylhydrosiloxane 50 mol%, Sigma-Aldrich) and 3- (trimethoxysilyl) propyl methacrylate (TMSPMA) were placed in a reaction vessel equipped with a stirrer and a nitrogen inlet. (Sigma-Aldrich) and 0 g of 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (FMA; TCI) were added to the flask. Nitrogen was added thereto and stirred at room temperature for 10 minutes. A small amount of Karstedts catalyst Dropping and mixing with the reactants. This mixture was stirred at 40 占 폚 for 4 hours to prepare a hydrophobic high-heat-resistant fluorine-modified polysiloxane polymer of the present invention. The modified polysiloxane-based polymer prepared by the above method has a transparent color.

< Example  11-14 > Various proportions of PDMS  Hydrophobic modified high heat resistance Polysiloxane-based Polymer  Produce

The same raw materials as in Example 10 were used, but only the mixing ratios of the raw materials were different. The raw material mixing capacity of each example is shown in Table 2 below.

Sample PDMS-MH
(g) FMA
(g) TMSPMA
(g) Example 10 (C0005) 30 0 5 Example 11 (C0015) 30 0 15 Example 12 (C0505) 30 5 5 Example 13 (C1005) 30 10 5 Example 14 (C3030) 30 30 30

< Experimental Example  1> fluorine denaturation Polysiloxane-based The polymer  Coated glass surface Contact angle  Measurement result

In order to evaluate the hydrophobicity of the modified polysiloxane-based polymer of the present invention, the fluorine-modified polysiloxane-based polymer prepared in Examples 1 to 14 was coated on a glass substrate to form a coating film, water drops were dropped, Were measured.

Table 3 shows the water contact angle of the coating film containing the fluorine-modified polysiloxane-based polymer prepared in Examples 1 to 14.

Sample Water contact angle (°) Example 1 (H0005) 90.9 Example 2 (H0010) 89.33 Example 3 (H0510) 91.05 Example 4 (H0015) 91.4 Example 5 (H0515) 92.2 Example 6 (H1515) 94.7 Example 7 (H0030) 92.6 Example 8 (H1530) 94.7 Example 9 (H3030) 95.2 Example 10 (C0005) 94.26 Example 11 (C0015) 94.3 Example 12 (C0505) 96.32 Example 13 (C1005) 98.23 Example 14 (C3030) 102.13

The contact angles of water droplets ranging from 80 ° to 110 ° were said to be hydrophobic. In all of Examples 1 to 13 of the present invention, the water contact angle was from 89.33 ° to 102.13 °.

Therefore, the fluorine-modified polysiloxane polymer of the present invention has excellent hydrophobicity, and in particular, Example 6 (FMA 15 g, TMSPMA 15 g), which contains both FMA and TMSPA and has a relatively high content, (FMA 15 g, TMSPMA 30 g), Example 9 (FMA 30 g, TMSPMA 30 g), Example 12 (FMA 15 g, TMSPMA 5 g), Example 13 (FMA 10 g, TMSPMA 5 g) and Example 14 (30 g of FMA and 30 g of TMSPMA) were 94.7 ° 94.7 ° 95.2 °, 96.32 ° 98.23 ° and 102.13 °, respectively.

As a result, it was confirmed that the fluorine-modified polysiloxane-based polymer prepared by including both FMA and TMSPMA had the highest hydrophobic property, and the optimum mixing ratio of the raw materials for producing the polysiloxane polymer having excellent hydrophobicity was confirmed.

As shown in Fig. H-F15S15 (PMHS 30 g, FMA 5 g, TMSPMA 15 g) The water contact angle on the glass surface coated with the polysiloxane polymer was 92.2 °, and H-F15S15 (PMHS 30 g, FMA 15 g, TMSPMA 15 g) coated glass surface showed a water contact angle of 95.1 °. Therefore, it can be seen that as the content of FMA, that is, the acrylate containing fluorine is increased, it has a superior hydrophobicity.

< Experimental Example  2> fluorine denaturation Polysiloxane-based Of polymer  Weight reduction measurement result at 300 ℃

In order to confirm whether the fluorine-modified polysiloxane-based polymer of the present invention had high heat-resistant properties, the weight loss was measured at 300 ° C. As a result, as shown in Fig. 2, no significant weight reduction due to thermal decomposition was observed even at a high-temperature heat treatment of 300 DEG C or more, and it was confirmed that the fluorine-modified polysiloxane polymer of the present invention had high heat resistance. Table 4 below shows measurement results of the weight loss (%) of the fluorine modified polysiloxane polymer of Examples 1 to 14 at 300 占 폚.

Sample Weight reduction at 300 ° C (%) Example 1 (H0005) 3.45 Example 2 (H0010) 5.03 Example 3 (H0510) 6.29 Example 4 (H0015) 5.83 Example 5 (H0515) 2.48 Example 6 (H1515) 4.31 Example 7 (H0030) 8.45 Example 8 (H1530) 13.71 Example 9 (H3030) 14.29 Example 10 (C0005) 4.99 Example 11 (C0015) 8.44 Example 12 (C0505) 7.02 Example 13 (C1005) 8.26 Example 14 (C3030) 8.1

Claims (12)

Modified polysiloxane-based polymer having the following general formula 1:
[Formula 1]

In the general formula (1), X is selected from A, B or C,
Here, A is

And B is

And C is

ego,
Wherein R &lt; _{1 &}

ego,
Wherein R ₃ and R ₄ are each independently a branched or unbranched C ₁ -C ₁₀ alkylene,
Z is

, -CONH, and -O-, and at least one group selected from the group consisting of
f is 0 or 1,
b is an integer of 1 to 10,
g is 0, 1 or 2,
h is 0, 1 or 2, provided that g + h is 2,
i is 0, 1 or 2,
j is 0, 1, 2 or 3, with the proviso that i + j is 3,
Wherein R &lt; _{2 &}

Lt;
Wherein R ₅ and R ₆ are each independently a branched or unbranched C ₁ -C ₁₀ alkylene,
R ₇ is C ₁ -C ₁₀ alkyl,
Z '

, -CONH-, and -O-, and at least one group selected from the group consisting of
k is 0 or 1,
Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,
In the general formula 1,
a is an integer of 1 or more, and one of A, B, or C is selected as a increases.
The method according to claim 1,
Wherein the modified polysiloxane-based polymer has a weight average molecular weight of 500 to 1,000,000.
The method according to claim 1,
R ₃ and R ₅ are each independently

ego,
R ₄ is branched or unbranched C ₁ -C ₅ alkylene,
R ₆ is a branched or unbranched C ₂ -C ₅ alkylene,
R ₇ is a C ₁ -C ₅ alkyl,
In the above formula,

The moiety is a moiety bonding to Si,
R ₈ is a hydrogen atom, or a branched or unbranched C ₁ -C ₅ alkyl,
Modified polysiloxane-based polymer.
A fluorine-containing polymer represented by the following formula (2) and an alkoxysilane group represented by the following formula (3) are grafted on a polysiloxane-based polymer backbone represented by the following formula (1) Modified polysiloxane-based polymer having a carboxyl group:
&Lt; Formula 1 >

(2)

(3)

In the above formulas,
Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,
R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,
R ₃ and R ₇ are each independently a hydrogen atom or a branched or unbranched C ₁ -C ₅ alkyl group,
R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,
R ₅ may be the same or different from each other, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,
R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,
Z and Z 'are each independently

, -CONH-, and -O-, and at least one group selected from the group consisting of
f and k are each independently 0 or 1,
m is an integer of 1 to 2000, and as m increases, R ₁ and R ₂ are each independently selected from a hydrogen atom or a methyl group,
n is an integer of 1 to 20;
5. The method of claim 4,
The modified polysiloxane-based polymer according to claim 1, wherein the moiety is represented by the following formula (4)
&Lt; Formula 4 >

In the above formulas,
Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,
R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,
R ₃ and R ₇ are each independently a hydrogen atom or a branched or unbranched C ₁ -C ₅ alkyl group,
R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,
R _{5, which} may be the same or different, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,
R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,
Z and Z ' may be present or absent and, if present, each independently

, -CONH-, and -O-, and at least one group selected from the group consisting of
n is an integer of 1 to 20,
c, d and e are each an integer of 0 to 2000, provided that c + d + e is 2 to 2000,
The order of each moiety that can be c, d, and e is arbitrary.
5. The method of claim 4,
Wherein the fluorine-containing polymer is a compound represented by the following general formula (5):
&Lt; Formula 5 >

Wherein R ₃ is a hydrogen atom or a branched or unbranched C ₁ -C ₅ alkyl group,
Z is

, -CONH-, and -O-,
f is 0 or 1,
and n is an integer of 4 to 15.
5. The method of claim 4,
Wherein the polymer containing an alkoxysilane group is a compound represented by the following formula (6): < EMI ID =
(6)

In the above formula
Z '

, -CONH-, and -O-, and at least one group selected from the group consisting of
k is 0 or 1;
5. The method of claim 4,
Wherein the metal catalyst is a platinum catalyst or a Karstedt catalyst.
A coating composition comprising a modified polysiloxane-based polymer according to any one of claims 1 to 8.
10. The method of claim 9,
Wherein the coating composition further comprises at least one additive selected from a curing agent, a releasing agent, a surfactant, an antioxidant, metal particles, oxide particles and nitride particles.
1) mixing a polysiloxane-based polymer of the following formula 1 with a polymer containing fluorine of the following formula 2 and an alkoxysilane-containing polymer of the following formula 3;
2) introducing the metal catalyst into the 1) mixture; And
3) stirring the mixture 2) to obtain a modified polysiloxane-based polymer having a moiety of the following formula 4:
&Lt; Formula 1 >

(2)

(3)

&Lt; Formula 4 >

In the above formulas,
Y and Y 'are each independently a branched or unbranched C ₁ -C ₁₀ alkyl or branched or unbranched C ₁ -C ₁₀ alkylene,
R ₁ and R ₂ are each independently a hydrogen atom or a methyl group,
R ₃ and R ₇ are each independently a hydrogen atom or a branched or unbranched C ₁ -C ₅ alkyl group,
R ₄ is a branched or unbranched C ₁ -C ₁₀ alkylene group,
R ₅ may be the same or different from each other, are each independently a branched or unbranched C ₁ -C ₅ alkyl group,
R ₆ is a branched or unbranched C ₁ -C ₁₀ alkylene group,
Z and Z 'are each independently

, -CONH-, and -O-, and at least one group selected from the group consisting of
f and k are each independently 0 or 1,
In Formula 4,
Z and Z &apos; may be present or absent and, if present, each independently

, -CONH-, and -O-,
m is an integer of 1 to 2000, and as m increases, R ₁ and R ₂ are each independently selected from a hydrogen atom or a methyl group,
n is an integer of 1 to 20,
c, d and e are each an integer of 0 to 2000, provided that c + d + e is 2 to 2000,
The order of each moiety that can be c, d, and e is arbitrary.
12. The method of claim 11,
Wherein the metal catalyst of step 2) is at least one of a platinum catalyst or a Karstedt catalyst.

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