KR102101394B1 - Polysiloxane-based copolymer which has high heat-resistant and hydrophobic characteristics, and coating composition comprising thereof - Google Patents

Abstract

The present invention provides a modified polysiloxane-based polymer having a perfluorinated group and an alkoxy silane reactor 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 can be used in various fields such as solar cell cover glass, metal tube coating of heat exchangers, paints, paints, and the like.

Description

A polysiloxane-based polymer for high heat resistance and hydrophobic coating and a composition for coating containing the same {Polysiloxane-based copolymer which has high heat-resistant and hydrophobic characteristics, and coating composition comprising thereof}

The present invention relates to a modified polysiloxane-based polymer having a perfluorine group and an alkoxy silane reaction group and a coating composition comprising the polymer. In more detail, 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, heat exchanger metal tube coating agent or paint, paint.

Recently, various industrial facilities such as desulfurization facilities, power generation facilities, dust collectors, incinerators, boilers, or casting equipment are manufactured, and parts such as a pouring box that performs metal molten metal transfer, hot water supply, support, internal materials of the pouring box, or metal tubes of a heat exchanger As a member, a heat-resistant coating is widely used.

In addition, in particular, in the case of industrial facilities in certain fields such as steel, steel, and petrochemical, it is easily exposed to high temperature heat in each process, so it is easy to cause aging and heat loss, and there is a risk of industrial accidents due to fire, heat-resistant coating agent It is essential to protect industrial equipment by using. In the case of general paints and paints used in indoor construction, it is preferable to use the heat-resistant coating agent because it is exposed to a high temperature environment such as a fire, and when it is burned, it releases toxic gases and causes personal injury. In the case of paints and paints containing heat-resistant coatings, it prevents the generation of toxic gases during a fire, thereby minimizing damage to buildings.

Such heat-resistant coatings used in various fields cause damage to the coating film, such as discoloration, cracking, softening, or peeling, to a predetermined level or less even when applied to an object maintaining 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, conventional heat-resistant coatings are not only difficult to respond to changes in the surface of an object with temperature, but also cause serious pollution problems caused by heavy metal contamination, such as generating harmful substances at high temperatures due to organic compounds or metal compounds added to improve heat resistance. Caused. In particular, the limitations of conventional heat-resistant coatings in the steel industry and other fields have been prominent. Specifically, due to limitations of heat-resistant coatings in molten iron L / D, molten steel, charged L / D, topetocar, coke oven door, OLC (Open Ladle Car) and other anti-bonding points, environmental pollution caused by scattering A large amount of back occurred.

Accordingly, there is an urgent need to develop a coating agent that can be used in various industrial fields while having high heat resistance 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 material can be distinguished by the water droplet contact angle. In general, when the water droplet contact angle is less than 10 °, super hydrophilic, 10 ° to 40 ° hydrophilic, 80 ° to 110 ° prime (or water repellent), and 140 ° to 180 ° super hydrophobic (or super water repellent) Is called. This property of the material surface may vary depending on which compound is coated with the coating material.

In the case of coatings that enhance hydrophobicity, their utility is very diverse. For example, it can be used not only for objects enclosed in the atmosphere, but also for objects in environments that frequently come into contact with water. Specifically, it can be applied to walls, container surfaces, partitions, platforms, posts, or structures that have long-term contact with fresh water or sea water. You can. In addition, by applying such a hydrophobic coating to a variety of materials, such as metal, glass and plastic, it can be applied in various business fields such as coatings for electronic products such as semiconductors, road signboards, as well as antifouling paints for ships. As described above, the demand for a highly utilized hydrophobic coating material and the need for a coating material having excellent hydrophobicity are gradually increasing, whereas in recent years, a hydrophobic coating material using hydrocarbons has been spotlighted, but these hydrocarbon hydrophobic materials are at least 250 ° C. As the dehydrogenation reaction gradually occurred at the temperature, there was a problem in that the properties of the material were significantly deteriorated.

Therefore, there is a need to develop a composition for coatings that has high heat resistance and maintains hydrophobicity even at high temperatures and which does not change its properties and an active ingredient thereof.

Korean Registered Patent 1,492,251 Korean Registered Patent 1,297,368 Korean 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-based polymer containing a fluorine group and an alkoxy silane reactor having high heat resistance and maintaining hydrophobicity at high temperatures to solve the problems of the existing heat-resistant or hydrophobic coating agents, or a coating composition comprising the same as an active ingredient .

In order to achieve the above object, the present invention

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

[Formula 1]

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

이고, B는

이며, C는

이고,Where A is

And B is

Is, C is

ego,

이고,R ₁ is

ego,

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

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

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

f is 0 or 1,

b is an integer from 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, provided i + j is 3,

이며, R ₂ is

And

Wherein R ₅ and R ₆ are each independently 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 'is

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

k is 0 or 1,

In Formula 1, Y and Y 'are each independently 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 as a increases, either A, B, or C is selected.

In one aspect of the present invention, the weight average molecular weight of the modified polysiloxane-based polymer may range from 500 to 1,000,000.

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

ego,

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

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

R ₇ is C ₁ -C ₅ alkyl,

부분은 Si와 결합하는 부위이고,In the above formula '

Part is a site that bonds with Si,

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

In addition, the present invention is a polysiloxane-based polymer backbone represented by the following formula (1) graft using a polymer containing a polymer containing fluorine represented by the following formula (2) and an alkoxysilane group represented by the following formula (3) using a metal catalyst It provides a modified polysiloxane-based polymer having a (graft) moieties.

<Formula 1>

<Formula 2>

<Formula 3>

In the above formula,

Y and Y 'are each independently 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, 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- is at least one member selected from the group consisting of,

f and k are each independently 0 or 1,

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

n is an integer from 1 to 20.

In one aspect of the invention, the moiety may be represented by the following formula (4):

<Formula 4>

In the above formula,

Y and Y 'are each independently 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, 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 or may not exist, and when present, each independently

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

n is an integer from 1 to 20,

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

The order of c, d and e possible moieties is arbitrary.

Here, the meaning that the order of each of the moieties that can be c, d and e is arbitrary is as illustrated below.

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

case 1)

case 2)

case 3)

case 4)

case 5)

case 6)

In various cases, such as when c is 0, d is 1, e is 1, and c is 1, d is 0, and e is 1, the order may be arbitrarily arranged, and it may be appropriately applied by those skilled in the art. .

In one embodiment of the present invention, the fluorine-containing polymer may be a compound of Formula 5:

<Formula 5>

R ₃ in the above formula 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- is at least one member selected from the group consisting of,

f is 0 or 1,

n is an integer from 4 to 10.

In one embodiment of the present invention, the polymer comprising the alkoxysilane group may be a compound of Formula 6:

<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 'is

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

k is 0 or 1.

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

In addition, the present invention provides a coating composition comprising the modified polysiloxane-based polymer.

In one aspect of the present invention, the coating composition may further include at least one additive selected from curing agents, release agents, surfactants, antioxidants, metal particles, oxide particles, and nitride particles.

In addition, the present invention

1) mixing a polysiloxane-based polymer of Formula 1, a polymer containing fluorine of Formula 2 and a polymer comprising an alkoxysilane group of Formula 3;

2) adding a metal catalyst to the 1) mixture; And

3) stirring the mixture 2) to provide a modified polysiloxane-based polymer production method comprising the step of obtaining a modified polysiloxane-based polymer having a moiety of the following formula (4).

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

In the above formula,

Y and Y 'are each independently 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, 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- is at least one member 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 if present, each independently

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

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

n is an integer from 1 to 20,

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

The order of c, d and e possible moieties is arbitrary.

In one aspect of the present invention, the metal catalyst of step 2) may be one or more of a platinum catalyst or Karstedt catalyst.

The modified polysiloxane-based polymer containing the fluorine group of the present invention and the coating composition containing it as an active ingredient have excellent hydrophobicity and high heat resistance, and thus can be used in various industrial fields such as solar cell cover glass , heat exchanger metal tube, paint, and paint.

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

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

Is, C is

ego,

이고 여기서 R₃ 및 R₄는 각각 독립적으로 분지 또는 비분지된 C₁-C₁₀ 알킬렌이며,R ₁ is

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

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

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

f is 0 or 1,

b is an integer from 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, provided i + j is 3,

이며, R ₂ is

And

Wherein R ₅ and R ₆ are each independently 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 'is

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

k is 0 or 1,

Y and Y 'are each independently 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 as a increases, either A, B, or C is selected.

More specifically, the definition that any one of A, B, or C is selected while a increases, means that as the number of X monomers increases, A, B, or C structures may be randomly generated without specific rules. , It means that a large number of polymers having a structure satisfying the above definition can be produced. The structure of a possible compound that satisfies the above definition is shown below. However, the scope 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 aspect of the invention, the weight average molecular weight of the modified polysiloxane-based polymer may be 500 to 1,000,000.

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

ego,

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

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

R ₇ is C ₁ -C ₅ alkyl,

부분은 Si와 결합하는 부위이고,In the above formula '

Part is a site that bonds with Si,

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

In addition, the present invention is a polysiloxane-based polymer backbone represented by the following formula (1) graft using a polymer containing a polymer containing fluorine represented by the formula (2) and an alkoxysilane group represented by the formula (3) using a metal catalyst It provides a modified polysiloxane-based polymer having a (graft) moieties.

<Formula 1>

<Formula 2>

<Formula 3>

In the above formula,

Y and Y 'are each independently 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, 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- is at least one member selected from the group consisting of,

f and k are each independently 0 or 1,

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

n is an integer from 1 to 20.

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

<Formula 4>

In the above formula,

Y and Y 'are each independently 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, 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 or may not be present, and if present, each independently

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

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

n is an integer from 1 to 20,

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

The order of c, d and e possible moieties is arbitrary.

More specifically, the polymer containing fluorine may include the compound of Formula 5 below. In the following formula R ₃ , Z, f and n are as defined above.

<Formula 5>

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

Meanwhile, the polymer containing the alkoxysilane group includes a compound represented by the following Chemical Formula 6 (3- (trimethoxysilyl) propyl methacrylate). In the following formula, Z 'and k are as defined above.

<Formula 6>

On the other hand, the metal catalyst is not particularly limited in its kind, Pt, Pb, Ir, Rh, Fe, Ni, Co, Ag, Hg, Karstedt (Karstedt), etc. can be used, preferably a platinum catalyst and One or more of Karstedt's catalysts can be used.

The following examples and experimental examples show examples in which polysiloxane-based polymers, fluorine-containing polymers, and alkoxysilane group-containing polymers are mixed and prepared in various ratios, and the number of droplets measured after treating each example polymer on the surface in the experimental examples. The contact angle and the weight loss% at 300 ° C were measured to confirm the excellent hydrophobicity and heat resistance of the fluorine-containing polysiloxane-based polymer of the present invention.

Therefore, the modified polysiloxane-based polymer containing a moiety in which the polysiloxane-based polymer of the present invention, a fluorine-containing polymer, and a polymer containing an alkoxysilane group are reacted under a metal catalyst and a coating agent containing the same have excellent hydrophobicity and heat resistance and are utilized in various industrial fields Can be.

In addition, the present invention provides a coating composition comprising the modified polysiloxane-based polymer.

The solvent used to prepare the coating composition is not particularly limited as long as it is a solvent capable of dissolving the modified polysiloxane-based polymer, but propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), iso Propyl alcohol (IPA), ethyl alcohol, butyl solsolve, methyl soloxol, ethylene glycol (EG), propylene glycol (PG), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), or A mixture of two or more of these can be used as a solvent.

In addition, the coating composition may include one or more additives such as curing agents, mold release agents, surfactants, antioxidants, metal particles, oxide particles and nitride particles.

Meanwhile, fields in which the coating composition can be applied are very diverse, and may be used for increasing heat resistance and increasing hydrophobicity in metal tubes of heat exchangers, parts of various industrial equipment exposed to high temperatures, paints, paints, and the like.

In addition, the present invention

1) mixing a polysiloxane-based polymer of Formula 1, a polymer containing fluorine of Formula 2, and a polymer comprising an alkoxysilane group of Formula 3;

2) adding a metal catalyst to the 1) mixture; And

3) stirring the mixture 2) to provide a modified polysiloxane-based polymer production method comprising the step of obtaining a modified polysiloxane-based polymer having a moiety of the following formula (4).

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

In the above formula,

Y and Y 'are each independently 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, 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- is at least one member selected from the group consisting of,

f and k are each independently 0 or 1,

In Chemical Formula 4,

, -CONH, 및 -O-로 구성된 그룹으로부터 선택되는 적어도 1종이며,Z and Z 'may or may not be present, and if present, each independently

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

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

n is an integer from 1 to 20,

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

The order of c, d and e possible moieties is arbitrary.

More specifically, in step 1), the raw materials are mixed for 5 to 20 minutes under nitrogen conditions, preferably 10 minutes, and the metal catalyst of step 2) is not particularly limited in its kind, but a platinum catalyst. And it is preferred to use at least one of Karstedt (Karstedt) catalyst. The step 3) is preferably stirred for 2 to 6 hours under the conditions of 20 to 150 ° C, preferably 30 to 100 ° C, and more preferably 40 ° C.

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

Hereinafter, the present invention will be described in more detail through examples and experimental examples. However, this is to aid the understanding of the present invention and is not intended to limit the scope of the present invention to it.

< Example  1> PMHS  Used hydrophobic high heat resistance denaturation Polysiloxane Polymer  Produce

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

< Example  2 to 9> various ratios PMHS  Used hydrophobic high heat resistance denaturation Polysiloxane Polymer  Produce

The same raw material as in Example 1 was used, but only the mixing ratio of the raw materials was different, and the same manufacturing method as in Example 1 was used. The raw material mixing capacity of each example is presented 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  Used hydrophobic high heat resistance denaturation Polysiloxane Polymer  Produce

30 g, 3- (trimethoxysilyl) propyl methacrylate (TMSPMA) poly (dimethylsiloxane-co-methylhydrosiloxane), trimethylsilyl terminated (PDMS-MH, Mn ~ 950, methylhydrosiloxane 50 mol%, Sigma-Aldrich) in a reactor equipped with a stirrer and nitrogen inlet ; Sigma-Aldrich) 5g and 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate (FMA; TCI) were added and nitrogen was added and stirred at room temperature for 10 minutes, and a small amount of Karstedts catalyst was slowly introduced into the container. Dropping and mixing with the reaction. The mixture was stirred at 40 ° C. for 4 hours to prepare the hydrophobic high heat-resistant fluorine-modified polysiloxane-based polymer of the present invention. The modified polysiloxane-based polymer prepared by the above method has a transparent color.

< Example  11 to 14> various ratios PDMS  Used hydrophobic high heat resistance denaturation Polysiloxane Polymer  Produce

The same raw material as in Example 10 was used, but only the mixing ratio of the raw materials was different, and the same manufacturing method as in Example 10 was used. The raw material mixing capacity of each example is presented 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 Polymer  Of 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 polymers prepared in <Examples 1 to 14> were coated on a glass substrate to form a coating film, and then dropped water droplets to drop the contact angle between the coating film and the water droplets. Was measured.

Table 3 below shows the droplet contact angle of the coating film containing the fluorine-modified polysiloxane-based polymers 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 droplet contact angle is said to be hydrophobic from 80 ° to 110 °, and in Examples 1 to 13 of the present invention, the water contact angle was 89.33 ° to a maximum of 102.13 °.

Therefore, the fluorine-modified polysiloxane-based polymer of the present invention has excellent hydrophobicity, and especially when compared with other examples, FMA and TMSPA are all included, and Example 6 (FMA 15 g, TMSPMA 15 g) having a relatively high content. , Example 8 (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 (FMA 30 g, TMSPMA 30 g) showed the highest water contact angles of 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 most excellent hydrophobic properties, and the optimum mixing ratio of raw materials for preparing the polysiloxane-based polymer excellent in hydrophobicity was confirmed.

As shown in FIG. 1. H-F05S15 (PMHS 30 g, FMA 5 g, TMSPMA 15 g) The water contact angle on the glass surface coated with a polysiloxane polymer was 92.2 °, and H-F15S15 (PMHS 30 g, FMA 15 g, The water contact angle on the glass surface coated with TMSPMA 15 g) was 95.1 °. Therefore, it can be seen that as the content of acrylate containing FMA increases, it has excellent hydrophobicity.

< Experimental example  2> Fluorine denaturation Polysiloxane Polymer  Weight loss measurement result at 300 ℃

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

Sample Weight loss at 300 ℃ (%) 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)

delete delete delete Moyers in which a polymer containing fluorine represented by Formula 2 and a polymer containing alkoxysilane represented by Formula 3 is grafted on a polysiloxane polymer backbone represented by Formula 1 using a metal catalyst. Modified polysiloxane-based polymer having tee:
<Formula 1>

<Formula 2>

<Formula 3>

In the above formula,
Y and Y 'are each independently branched or unbranched C ₁ -C ₁₀ alkyl,
m is an integer from 1 to 2000,
When m is 1, R ₁ ′ and R ₂ ′ are both hydrogen atoms,
When m is an integer of 2 or more and 2000 or less, R ₁ ′ and R ₂ ′ increased by the number of m are each independently a hydrogen atom or a methyl group, but R ₁ ′ and R ₂ ′ increased by the number of m. At least two of a hydrogen ^atom,.
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, 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- is at least one member selected from the group consisting of,
f and k are each independently 0 or 1,
n is an integer from 1 to 20.
According to claim 4,
The moiety is characterized in that represented by the formula (4), modified polysiloxane-based polymer:
<Formula 4>

In the above formula,
Y and Y 'are each independently branched or unbranched C ₁ -C ₁₀ alkyl,
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, 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 or may not be present, and if present, each independently

, -CONH-, and -O- is at least one member selected from the group consisting of,
n is an integer from 1 to 20,
c and e are each an integer from 1 to 2000, d is an integer from 0 to 2000,
The order of c, d and e possible moieties is arbitrary.
According to claim 4,
The polymer containing fluorine is a modified polysiloxane-based polymer characterized in that it is a compound of Formula 5:
<Formula 5>

R ₃ 'in the above formula is a hydrogen atom, or a branched or unbranched C ₁ -C ₅ alkyl group,
Z is

, -CONH-, and -O- is at least one member selected from the group consisting of,
f is 0 or 1,
n is an integer from 4 to 15.
According to claim 4,
Modified polysiloxane-based polymer, characterized in that the polymer comprising an alkoxysilane group is a compound of Formula 6:
<Formula 6>

In the above formula
Z 'is

, -CONH-, and -O- is at least one member selected from the group consisting of,
k is 0 or 1.
According to claim 4,
The metal catalyst is a platinum catalyst or Karstedt (Karstedt) catalyst, characterized in that the modified polysiloxane polymer.
A coating composition comprising the modified polysiloxane-based polymer according to any one of claims 4 to 8.
The method of claim 9,
Coating composition characterized in that it further comprises at least one additive selected from curing agents, mold release agents, surfactants, antioxidants, metal particles, oxide particles and nitride particles.
1) mixing a polysiloxane-based polymer of Formula 1, a polymer containing fluorine of Formula 2, and a polymer comprising an alkoxysilane group of Formula 3;
2) adding a metal catalyst to the 1) mixture; And
3) stirring the mixture 2) to obtain a modified polysiloxane-based polymer having a moiety of the following formula (4), modified polysiloxane-based polymer production method:
<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

In Chemical Formulas 1 to 3,
Y and Y 'are each independently branched or unbranched C ₁ -C ₁₀ alkyl,
m is an integer from 1 to 2000,
When m is 1, R ₁ ′ and R ₂ ′ are both hydrogen atoms,
When m is an integer of 2 or more and 2000 or less, R ₁ ′ and R ₂ ′ increased by the number of m are each independently a hydrogen atom or a methyl group, and at least 2 of R ₁ ′ and R ₂ ′ increased by the number of m. Dog is a hydrogen atom,
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, 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- is at least one member selected from the group consisting of,
f and k are each independently 0 or 1,
n is an integer from 1 to 20,
In Chemical Formula 4,
Y and Y 'are each independently branched or unbranched C ₁ -C ₁₀ alkyl,
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, 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 or may not be present, and if present, each independently

, -CONH-, and -O- is at least one member selected from the group consisting of,
n is an integer from 1 to 20,
c and e are each an integer from 1 to 2000, d is an integer from 0 to 2000,
The order of c, d and e possible moieties is arbitrary.
The method of claim 11,
The metal catalyst of step 2) is characterized in that at least one of a platinum catalyst or Karstedt (Karstedt) catalyst, modified polysiloxane-based polymer production method.

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