KR20130116666A - Polysiloxane and method for preparing the same - Google Patents

Abstract

PURPOSE: Ploysiloxane is provided to be able to maintain a high transparency, a low haze and an excellent impact strength even in a high temperature molding condition when forming a copolymer with polycarbonate, polyurethane or polyester. CONSTITUTION: Polysiloxane is represented by Chemical formula 1, wherein R^1, R^2, R^3 and R^4 are, respectively, substituted or non-substituted C1-C10 alkyl, or substituted or non-substituted C6-C18 aryl, R" is C4-C20 aliphatic or cycloaliphatic hydrocarbon, the carbon positioned in the second position from the hydroxyl is substituted with alkyl or cycloalkyl, and n is an integer of 30-90. A manufacturing method of the polysiloxane comprises a step of reacting an end hydrogen siloxane and an aliphatic hydroxyl derivative represented by Chemical formula 2.

Description

POLYSILOXANE AND METHOD FOR PREPARING THE SAME}

The present invention relates to polysiloxanes and methods for their preparation. More specifically, the present invention relates to a polysiloxane having excellent thermal stability and a method for producing the same by introducing a substituent to a carbon adjacent to a hydroxy group and a neighboring carbon.

Many studies have been conducted to increase the chemical resistance and impact strength of polycarbonates using polysiloxanes. However, a major problem of these studies is that the polycarbonate and polysiloxane are incompatible with each other, and the physical transparency of the polycarbonate, which is one of the advantages of the polycarbonate, is significantly reduced.

Various copolymerization methods have been introduced to solve the problems resulting from such physical mixing. Among them, research and application of polycarbonate-polysiloxane copolymers copolymerized with polycarbonates with phenol functional groups attached to both ends of polysiloxanes are active.

Recently, application of functional groups other than phenol to polysiloxanes has been attempted, and polysiloxanes having an aliphatic reactor as a terminal have been applied.

Polycarbonate-polysiloxane copolymers with hydroxy-terminated aliphatic polysiloxanes exhibit excellent impact properties, transparency, high ductility and melt flow. However, it has been observed that the decomposition occurs at high temperature.

As described above, carbon dioxide is generated by decomposition under high temperature molding conditions, which causes problems such as a flow mark is generated in the molded article, becomes opaque, and the impact strength decreases as the molecular weight decreases.

Accordingly, there is a need for the development of a new polysiloxane capable of maintaining excellent impact strength while maintaining high transparency and low haze even in high temperature molding conditions when forming a copolymer with polycarbonate, polyurethane, or polyester.

It is an object of the present invention to provide a polysiloxane having excellent thermal stability and a method for producing the same.

Another object of the present invention is to provide a polysiloxane capable of maintaining excellent impact strength while maintaining high transparency and low haze even under high temperature molding conditions when forming a copolymer with polycarbonate, polyurethane, or polyester, and a method of manufacturing the same.

Still another object of the present invention is to provide a polysiloxane and a method for producing the same, which can be advantageously applied to thin molded articles requiring high temperature molding.

One aspect of the invention relates to polysiloxanes. The polysiloxane is represented by the following formula (1):

[Formula 1]

(In the above, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,

R ″ is C4-C20 aliphatic or cycloaliphatic hydrocarbon, and the carbon located second from the double hydroxy group is all substituted by alkyl or cycloalkyl group,

n is an integer from 30 to 90).

The polysiloxane may have an acid value change rate (ΔAV) of 1% or less according to Formula 1 below:

[Formula 1]

(In the above, ΔAV is the acid value change rate, AVa is the acid value after leaving 10 g of polysiloxane at 280 ° C. for 1 hour, and AVb is the initial acid value of polysiloxane).

Another aspect of the invention relates to a method for producing a polysiloxane represented by the formula (1). The method includes reacting a terminal hydrogen siloxane with an aliphatic hydroxy group derivative represented by Formula 2:

(2)

(Wherein R " is a C4-C20 aliphatic or cycloaliphatic hydrocarbon containing a double bond at the terminal, and the carbon located second from the double hydroxy group is all substituted by an alkyl group or a cycloalkyl group).

The terminal hydrogen siloxane may be represented by the following formula (3):

(3)

(In Formula 3, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group, n is an integer of 30 to 90 to be).

Another aspect of the invention relates to a polysiloxane copolymer derived from the polysiloxane. The polysiloxane may be copolymerized with a polycarbonate or polyester, polyurethane.

In an embodiment the polysiloxane copolymer has the following formula 4 units:

[Formula 4]

-P1-P2-

Wherein P1 is derived from Formula 1,

[Formula 1]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group, and R ″ is an aliphatic C4-C20 or Alicyclic hydrocarbon, wherein the carbon located second from the hydroxy group is all substituted by an alkyl group or a cycloalkyl group, and n is an integer of 30 to 90)

P2 is a group derived from any one of polycarbonate, polyester and polyurethane.

The present invention is excellent in thermal stability, it is possible to maintain excellent impact strength while maintaining high transparency and low haze even under high temperature molding conditions when forming a copolymer with polycarbonate, polyurethane or polyester, and is advantageous for thin molded articles requiring high temperature molding It has the invention effect to provide a polysiloxane and a method for producing the same can be applied easily.

1 is an NMR photograph of a polysiloxane prepared in Example 1 of the present invention.
2 is an NMR photograph of the polysiloxane prepared in Example 2 of the present invention.

In the present invention, "substituted" means a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or Salts thereof, sulfonic acid groups or salts thereof, phosphate groups or salts thereof, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and 6-30 carbon atoms An aryl group, an aryloxy group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, a cycloalkynyl group having 3 to 30 carbon atoms, or a combination thereof.

The polysiloxane of the present invention has a hydroxyl group at the terminal of the silonic acid unit, and the second position carbon (hereinafter, β-position carbon) from the terminal hydroxy is all substituted by an alkyl group or a cycloalkyl group such that hydrogen is not substituted. It is done.

R may be an alkyl group, a cycloalkyl group, or an aryl group, and may be linked to carbon (hereinafter, ω-position carbon) linked with the siloxane to form a ring.

In embodiments, the β-position carbon and the ω-position carbon may be connected to a linear or branched alkyl group.

In another embodiment, the β-position carbon and the ω-position carbon may be connected by cyclic alkyl to have a cyclic structure.

In any case, all of the β-position carbons are substituted and are not connected to hydrogen. Therefore, it is possible to suppress the eilimination reaction, which is an alkene-producing reaction that can occur in the hydroxyl group connected to the first position carbon (hereinafter referred to as α position carbon) from hydroxy.

In an embodiment the polysiloxane of the invention is represented by the formula

[Formula 1]

(In the above, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,

R ″ is C4-C20 aliphatic or cycloaliphatic hydrocarbon, and the carbon located second from the double hydroxy group is all substituted by alkyl or cycloalkyl group,

n is an integer from 30 to 90).

In one embodiment, the polysiloxane of the present invention may be represented by the following Chemical Formula 1-1:

[Formula 1-1]

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C5-C18 cycloalkyl group, or a substituted or unsubstituted C6-C18 aryl group,

R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C4-C18 cycloalkyl group, or a substituted or unsubstituted C5-C18 aryl group,

A is C1-C20 divalent to tetravalent aliphatic or cycloaliphatic hydrocarbon,

Y is substituted or unsubstituted C0-C10 alkylene (where C0 is an A-C single bond), C5-C18 cycloalkylene,

X and Z are each independently a di- tetravalent hydrocarbon of C1-C20,

Q is C1-C5 substituted or unsubstituted alkylene, oxygen, sulfur, sulfur dioxide (SO2), NR (wherein R is hydrogen, substituted or unsubstituted C1-C10 alkyl group),

a, b, c, d, e and f are each independently 0 or 1,

(If any one of a + b + c + d + e = 3, a, b, and c is 0, either d or e is 0.)

n is an integer from 30 to 90.

The meaning of 0 in a, b, c, d, e and f means that the group does not exist, and the meaning of 1 in a, b, c, d, e and f means that the group exists. it means.

When b is 0, the β-position carbon and A may form an alicyclic ring.

For example, b may be 0, d may be 0, and f may be 1.

In another embodiment, b may be 0, d may be 0, and f may be 0.

Also when b is 1, when a is 1, c is 0, d is 1, and e is 0, the β-position carbon and A may form an alicyclic ring.

In another embodiment when a and c are 0 and b is 1, β-position carbon and A may be connected by linear or branched alkylene. D and e are 1 in this case.

N is an integer of 30 to 90, preferably 35 to 70, more preferably 40 to 65. It is excellent in transparency in the said range.

For example, the polysiloxane of the present invention may have the following structure:

The polysiloxanes of the present invention can be prepared by reacting terminal hydrogen siloxanes with aliphatic hydroxy group derivatives.

The aliphatic hydroxy group derivative may be represented by the following Formula 2:

(2)

(Wherein R " is a C4-C20 aliphatic or cycloaliphatic hydrocarbon containing a double bond at the terminal, and the carbon located second from the double hydroxy group is all substituted by an alkyl group or a cycloalkyl group).

In an embodiment, the aliphatic hydroxy group derivative may be represented by the following Chemical Formula 2-1.

[Formula 2-1]

In Formula 2-1, R ⁵ and R ⁶ are each independently hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C5-C18 cycloalkyl group, or a substituted or unsubstituted C6-C18 aryl group ego,

R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C4-C18 cycloalkyl group, or a substituted or unsubstituted C5-C18 aryl group,

A is C1-C20 divalent to tetravalent aliphatic or cycloaliphatic hydrocarbon,

Y is substituted or unsubstituted C0-C10 alkylene (where C0 is an A-C single bond), C5-C18 cycloalkylene,

X and Z are each independently a di- tetravalent hydrocarbon of C1-C20,

Q is C1-C5 substituted or unsubstituted alkylene, oxygen, sulfur, sulfur dioxide (SO2), NR (wherein R is hydrogen, substituted or unsubstituted C1-C10 alkyl group),

a, b, c, d, e and f are each independently 0 or 1,

Provided that any one of a + b + c + d + e = 3, a, b, c is 0, and either d or e is 0.

A includes a double bond at the end for hydrosilylation.

The terminal hydrogen siloxane may be represented by the following formula (3):

(3)

(In Formula 3, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group, n is an integer of 30 to 90 to be).

The reaction of the terminal hydrogen siloxane with the aliphatic hydroxy group derivative may be reacted in the presence of a catalyst. As the catalyst, a conventional catalyst applied to hydrosilylation may be used. In an embodiment, the catalyst comprises platinum and palladium. Preferred catalysts include H2PtCl6, Pt2 {[(CH2 = CH) Me2Si] 2O} 8, Rh [(cod) 2] BF4, Rh (PPh3) 4Cl, Pt / C, or Pd / C alone or in combination. It is not limited to these. The catalyst may be used with a metal content of less than 500 ppm, preferably less than 100 ppm on a polysiloxane basis.

In an embodiment, after dissolving the terminal hydrogen siloxane in a solvent, a catalyst may be added and the aliphatic hydroxy group derivative may be added dropwise to react. The reaction temperature may be 50 to 150 ° C, preferably 70 to 130 ° C.

In specific examples, the equivalent ratio between the terminal hydrogen siloxane and the aliphatic hydroxy group derivative is preferably 1: 2 to 1: 2.2.

In addition, the acid value change rate (ΔAV) according to the following formula 1 may be 1% or less, preferably 0.1% or less, more preferably 0%:

[Formula 1]

(Wherein, ΔAV is the acid value change rate, AVa is the acid value after leaving 10 g of polysiloxane at 280 ° C. for 1 hour, and AVb is the initial acid value of polysiloxane)

The polysiloxanes of Formula 1 thus prepared may be used to form copolymers with polycarbonates, polyurethanes, polyesters.

Polycarbonate, polyurethane, or polyester copolymerized with the polysiloxane of Formula 1 may maintain excellent impact strength while maintaining high transparency and low haze even under high temperature molding conditions. Therefore, it can be especially preferably applied to thin molded articles requiring high temperature molding, for example, light guide plates.

Another aspect of the invention relates to a polysiloxane copolymer derived from the polysiloxane. The polysiloxane may be copolymerized with a polycarbonate or polyester, polyurethane.

In an embodiment the polysiloxane copolymer has the following formula 4 units:

[Formula 4]

-P1-P2-

Wherein P1 is derived from Formula 1,

[Formula 1]

(In the above, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,

R ″ is C4-C20 aliphatic or cycloaliphatic hydrocarbon, and the carbon located second from the double hydroxy group is all substituted by alkyl or cycloalkyl group,

n is an integer from 30 to 90)

P2 is a group derived from any one of polycarbonate, polyester and polyurethane.

The invention can be better understood by the following examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example 1

300 g [0.1 mol, number average molecular weight Mn = 3026] of oligodimethylsiloxane and 270 mL of toluene were added to the reaction vessel, and 0.5 g of Pt / C (Pt 5% wt, 0.025 g Pt) was added thereto, followed by stirring and heating to 110 ° C. . 27.4 g (0.24 mol) of 2,2-dimethyl-4-penten-1-ol was slowly added dropwise. The reaction solution was stirred for 1 hour and then cooled to room temperature. After the reaction was filtered, the solvent and unreacted material were removed under high temperature vacuum to give 320 g of oily product. NMR analysis results are shown in FIG. 1.

Example 2

As in Example 1, except that 33.2 g of (2-Methyl Bicyclo [2.2.1] hept-5-en-2-yl) Methanol was used instead of 2,2-dimethyl-4-penten-1-ol Was performed.

Example 3

Except for using the compound represented by the following formula 2-3 instead of 2,2-dimethyl-4-penten-1-ol 25 g was carried out in the same manner as in Example 1.

Comparative Example 1

The polysiloxane represented by the following formula (4-1) was used.

[Formula 4-1]

How to measure property

(1) The number average molecular weight and 1 H-NMR were measured using Bruker's Ultrashield 300 MHz.

(2) Acid value (KOH mg / g): 1 ~ 20g of sample was dissolved in dimethylsulfoxide (50ml), 0.03ml ~ 0.2ml of BTB solution was added, and titrated with 0.1N NaOH solution.

Acid value = ((0.1N-NaOH solution consumption ml) * (0.1N-NaOH solution Factor) * 5.61) / sample amount (g)

(3) Acid value change rate ((DELTA) AV): About the measured acid value, it calculated by following formula 1.

[Formula 1]

(Wherein, ΔAV is the acid value change rate, AVa is the acid value after leaving 10 g of polysiloxane at 280 ° C. for 1 hour, and AVb is the initial acid value of polysiloxane)

Physical properties of the polysiloxanes of Examples 1 to 3 and Comparative Example 1 were measured according to the above methods, and the results are shown in Table 1 below.

Polysiloxane molecular weight
(Mn) Early mountain Acid value change rate
(△ AV) Example 1 3181 35 0 Example 2 3229 34 0 Example 3 3232 35 0 Comparative Example 1 3153 35 20

As shown in Table 1, it can be seen that in Example 1-3 in which all β-position carbon is substituted, there is no excellent thermal stability and acid value change rate. On the other hand, in the case of Comparative Example 1 in which hydrogen is connected to β-position carbon, the thermal stability is lower than that of Examples 1-3 and the acid value change rate is significantly increased.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (5)

A polysiloxane represented by the following formula (1):
[Formula 1]

(In the above, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,
R ″ is C4-C20 aliphatic or cycloaliphatic hydrocarbon, and the carbon located second from the double hydroxy group is all substituted by alkyl or cycloalkyl group,
n is an integer from 30 to 90).
The polysiloxane according to claim 1, wherein the polysiloxane has an acid value change rate (ΔAV) of 1% or less according to the following Formula 1:
[Formula 1]

(In the above, ΔAV is the acid value change rate, AVa is the acid value after leaving 10 g of polysiloxane at 280 ° C. for 1 hour, and AVb is the initial acid value of polysiloxane).
Method for preparing a polysiloxane represented by the following formula (1) comprising the step of reacting the terminal hydrogen siloxane and an aliphatic hydroxy group derivative represented by the formula (2):
(2)

(In Formula 2, R ″ is a C4-C20 aliphatic or cycloaliphatic hydrocarbon containing a double bond at the terminal, and the carbon located second from the double hydroxy group is all substituted by an alkyl group or a cycloalkyl group).
[Formula 1]

(In Formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group, and R ″ is a C4-C20 group. Aliphatic or cycloaliphatic hydrocarbon, wherein the carbon located second from the double hydroxy group is all substituted by an alkyl group or a cycloalkyl group, and n is an integer of 30 to 90).
The method of claim 3, wherein the terminal hydrogen siloxane is represented by Formula 3:
(3)

(In Formula 3, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group, n is an integer of 30 to 90 to be).
Polysiloxane copolymer having the formula 4 units
[Chemical Formula 4]
-P1-P2-
Wherein P1 is derived from Formula 1,
[Formula 1]

(In Formula 1, R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group, and R ″ is a C4-C20 group. Aliphatic or cycloaliphatic hydrocarbon, wherein the carbon located second from the double hydroxy group is all substituted by an alkyl group or a cycloalkyl group, n is an integer of 30 to 90)
P2 is a group derived from any one of polycarbonate, polyester and polyurethane.

Images