KR101527272B1 - Novel Polyorganosiloxane, Polycarbonate Composition Containing the Same And Polycarbonate Modified by the Same - Google Patents

Abstract

(R₁~R₃, R'₁~R'₃은 CH₃- 또는 C₆H₅-이고, R₄는

이며, R'₄는 CH₃-, C₆H₅- 또는

이고, R₅는 H 또는 CH₃-이며, R₆은 C₂~C₆의 알킬렌기 또는 C₆~C₁₂의 시클로알킬렌기이고, 0＜n+m≤99이며, n과 m은 정수이다)로 표시되는 화합물인 것을 특징으로 하는 신규한 폴리오르가노실록산, 이를 포함하는 폴리카보네이트 수지 조성물 및 개질 폴리카보네이트 수지에 관한 것이다.
본 발명에 따르면, 다양한 용도에 적용 가능하고, 특히 폴리카보네이트 수지의 충격보강제, 개질제 또는 공단량체로 사용 가능한 신규한 폴리오르가노실록산 유도체 등을 제공하는 효과가 있다. The present invention relates to a novel polyorganosiloxane, a polycarbonate resin composition containing the same, and a modified polycarbonate resin, and more particularly,
[Chemical Formula 1]

(R ₁ to R ₃ , R ' ₁ to R' ₃ are CH ₃ - or C ₆ H ₅ -, and R ₄ is

, R ' ₄ is CH ₃ -, C ₆ H ₅ - or

, R ₅ is H or CH ₃ -, R ₆ is a C ₂ -C ₆ alkylene group or a C ₆ -C ₁₂ cycloalkylene group, 0 <n + m≤99, and n and m are integers ), A polycarbonate resin composition containing the same, and a modified polycarbonate resin. [0002] The present invention relates to a novel polyorganosiloxane, a polycarbonate resin composition containing the same, and a modified polycarbonate resin.
According to the present invention, there is provided an effect of providing a novel polyorganosiloxane derivative which can be applied to various applications, and which can be used as an impact modifier, a modifier, or a comonomer of a polycarbonate resin.

Description

[0001] The present invention relates to a novel polyorganosiloxane, a polycarbonate resin composition containing the same, and a modified polycarbonate resin (Novel Polyorganosiloxane, Polycarbonate Composition Containing the Same and Polycarbonate Modified by the Same)

The present invention relates to a novel polyorganosiloxane and the like, and more particularly to a novel polyorganosiloxane which can be applied to various applications, and which can be used as an impact modifier, modifier or comonomer particularly for a polycarbonate resin.

Polyorganosiloxane is a kind of silicone, which means a polymer mainly composed of siloxane bonds substituted by organic groups. It is a colorless odorless, hypoallergenic and stable at room temperature, , Automobiles, machinery, medical, cosmetics, lubricants, adhesives, gaskets, molded artificial aids and the like.

Prior art KR Patent Publication No. 2002-0016922 (published Mar. 23, 2002) discloses trimethylsilyl terminated polyorganosiloxanes useful as hydrogel contact lens materials.

It is an object of the present invention to provide a novel polyorganosiloxane derivative that can be used for various applications, particularly as an impact modifier, modifier or comonomer for polycarbonate resin.

These and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object,

[Chemical Formula 1]

이며, R'₄는 CH₃-, C₆H₅- 또는

이고, R₅는 H 또는 CH₃-이며, R₆은 C₂~C₆의 알킬렌기 또는 C₆~C₁₂의 시클로알킬렌기이고, 0＜n+m≤99이며, n과 m은 정수이다)로 표시되는 신규한 폴리오르가노실록산을 제공한다. (R ₁ to R ₃ , R ' ₁ to R' ₃ are CH ₃ - or C ₆ H ₅ -, and R ₄ is

, R ' ₄ is CH ₃ -, C ₆ H ₅ - or

, R ₅ is H or CH ₃ -, R ₆ is a C ₂ -C ₆ alkylene group or a C ₆ -C ₁₂ cycloalkylene group, 0 <n + m≤99, and n and m are integers ). &Lt; / RTI &gt;

The present invention also provides a process for preparing an organopolysiloxane comprising: a) reacting an organosiloxane and an organocyclosiloxane in the presence of an acid catalyst to produce an unmodified polyorganosiloxane; And b) reacting the unmodified polyorganosiloxane and the hydroxyalkyl (meth) acrylate compound thus prepared in the presence of a metal catalyst to produce a polyorganosiloxane having a terminal modified group. .

The present invention also provides a modified polycarbonate resin characterized by being modified with the polyorganosiloxane.

The present invention also provides a polycarbonate resin composition comprising the polyorganosiloxane and the polycarbonate resin.

As described above, according to the present invention, a novel polyorganosiloxane derivative, which can be applied to various applications and can be used as an impact modifier, modifier, or comonomer of a polycarbonate resin (or PC) .

1 is an IR spectrum of HEMA-PDMS prepared in Example 1. Fig.
2 is a ¹ H NMR spectrum of HEMA-PDMS prepared in Example 1. Fig.

Hereinafter, the present invention will be described in detail.

The novel polyorganosiloxanes of the present invention are represented by the following general formula

[Chemical Formula 1]

이며, R'₄는 CH₃-, C₆H₅- 또는

이고, R₅는 H 또는 CH₃-이며, R₆은 C₂~C₆의 알킬렌기 또는 C₆~C₁₂의 시클로알킬렌기이고, 0＜n+m≤99이며, n과 m은 정수이다)로 표시되는 화합물인 것을 특징으로 한다.
(R ₁ to R ₃ , R ' ₁ to R' ₃ are CH ₃ - or C ₆ H ₅ -, and R ₄ is

, R ' ₄ is CH ₃ -, C ₆ H ₅ - or

, R ₅ is H or CH ₃ -, R ₆ is a C ₂ -C ₆ alkylene group or a C ₆ -C ₁₂ cycloalkylene group, 0 <n + m≤99, and n and m are integers ). &Lt; / RTI &gt;

The R ₆ is preferably a C ₂ to C ₆ alkylene group or a C ₆ to C ₁₂ cycloalkylene group, more preferably a C ₆ to C ₁₂ cycloalkylene group, and is applicable to polycarbonate within this range There is an effect that the heat resistance is not greatly affected while the impact strength is greatly improved.

It is preferable that m + n is 0 to 99, more preferably 20 to 70, 25 to 60, or 35 to 55. Within this range, when applied to a PC, the mechanical properties are greatly improved, The effect is great.

The m and n may be an integer of 0 or more, for example.

The polyorganosiloxane is preferably used in at least one selected from the group consisting of comonomers, modifiers, and impact modifiers.

The polyorganosiloxane is preferably applied to a polycarbonate resin. In this case, the impact strength of the polycarbonate is improved and the flowability is improved.

The process for producing the polyorganosiloxane of the present invention comprises, for example, a) preparing an unmodified polyorganosiloxane by reacting an organosiloxane and an organocyclosiloxane under an acid catalyst; And b) reacting the prepared unmodified polyorganosiloxane and hydroxyalkyl (meth) acrylate compound under a metal catalyst to produce a polyorganosiloxane having a modified terminal.

The organosiloxane may be at least one selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, hexamethyldisiloxane, and hexaphenyldisiloxane.

The organosiloxane may be used in an amount of 0.1 to 10 parts by weight or in an amount of 2 to 8 parts by weight based on 100 parts by weight of the organocyclosiloxane.

The organocyclosiloxane may be, for example, an organocyclotetrasiloxane, and another example may be octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.

 The acid catalyst is not particularly limited when it is an acid catalyst that can be used in the synthesis of the polyorganosiloxane, and examples thereof include sulfuric acid, hydrochloric acid, acidic clay, and the like.

The acid catalyst may be, for example, 0.1 to 10 parts by weight, 0.5 to 5 parts by weight, or 1 to 3 parts by weight based on 100 parts by weight of organocyclosiloxane.

The metal catalyst is not limited as long as it is a metal catalyst that can be used for the reaction of the polysiloxane and the (meth) acrylate compound, and may be, for example, a Pt catalyst.

The metal catalyst may be, for example, 0.001 to 1 part by weight, 0.005 to 0.1, or 0.01 to 0.05 part by weight based on 100 parts by weight of the organocyclosiloxane.

The hydroxyalkyl (meth) acrylate compound may be, for example, an alkyl group of C ₂ to C ₆ or a C ₆ to C ₁₂ cycloalkyl group.

In another example, the hydroxyalkyl (meth) acrylate compound may be (meth) acrylate methacrylate or acrylate.

The hydroxyalkyl (meth) acrylate compound may be, for example, 0.1 to 20 parts by weight, 1 to 15 parts by weight, or 5 to 12 parts by weight based on 100 parts by weight of the organocyclosiloxane.

The reaction for preparing the unmodified polyorganosiloxane of a) may be carried out at 50 to 70 ° C for 1 to 6 hours, for example.

The reaction for preparing the polyorganosiloxane of b) may be carried out at 80 to 100 ° C for 1 to 5 hours, for example.

As another example, the process for producing the polyorganosiloxane of the present invention may be a process according to the following Reaction Scheme 1.

[Reaction Scheme 1]

HEMA-PDMS in the above scheme 1 is an abbreviation of?,? - hydroxy ethyl methacrylate functionalized polydimethylsiloxane (?,? - hydroxy ethyl methacrylate end-capped polydimethylsiloxane).

The modified PC of the present invention is characterized by being PC modified with the polyorganosiloxane of the present invention.

For example, the modified PC of the present invention is characterized by being produced by polymerizing the corresponding monomers under the polyorganosiloxane of the present invention.

The modified PC may include a polyorganosiloxane as a comonomer in the chain.

The modified PC may have a weight average molecular weight of 10,000 to 100,000, 20,000 to 50,000 or 30,000 to 4, for example.

The modified PC may comprise, for example, i) a polyorganosiloxane, ii) a bisphenol, and iii) a phosgene or carbonic acid diester.

As another example, the modified PC may be one prepared by polymerizing the polyorganosiloxane, bisphenol, and phosgene of the present invention.

As another example, the modified PC may be one prepared by polymerizing the polyorganosiloxane, bisphenol, and carbonic acid diester of the present invention.

The polyorganosiloxane may include, for example, 0.1 to 20% by weight, 1 to 10% by weight, or 2 to 8% by weight based on 100% by weight of total modified PC.

The modified polyorganosiloxane may be 10 wt% or less, 5 wt% or less, or 1 wt% or less based on 100 wt%

The PC composition of the present invention is characterized by comprising the polyorganosiloxane of the present invention and PC.

The PC composition may comprise, for example, from 0.1 to 20% by weight of the polyorganosiloxane of the invention and from 80 to 99.9% by weight of PC, and in another example from 1 to 10% by weight of the polyorganosiloxane of the present invention and PC And 90 to 99% by weight of the total weight of the composition. Within this range, impact reinforcement and flowability are significantly improved.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example ]

Example  One

< New Of the polyorganosiloxanes  Manufacturing>

50 g (168 mmol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 mmol) of tetramethyldisiloxane were mixed and the mixture was treated with an acid clay (DC-A3, manufactured by Donghae Kogyo Kagaku Co., Ltd.) 1 part by weight of 100 parts by weight of siloxane was placed in a 3 L flask and reacted at 60 DEG C for 4 hours. After the completion of the reaction, it was diluted with ethylacetate and then rapidly filtered using a celite. The unmodified polyorganosiloxane thus obtained had a repeating unit of 45 (repeating units were measured by ¹ H-NMR). To the obtained unmodified polyorganosiloxane (crude product) were added 4.02 g (30.9 mmol) of HEMA and 0.52 g 0.01 g (50 ppm) of a catalyst (Karstedt's platinum catalyst) was added thereto and reacted at 90 ° C for 3 hours. After the completion of the reaction, unreacted polysiloxane was evaporated under the conditions of 120 DEG C and 1 torr. The HEMA capped polydimethylsiloxane (HEMA-PDMS) fluid thus obtained was a slightly yellow oil with a repeat unit of 45 and no further purification was required. In addition, the preparation of HEMA-PDMS was confirmed by IR and &lt; ^{1 &gt;} H NMR. FIG. 1 is an IR spectrum of the prepared HEMA-PDMS showing the carbon-carbon double bond peak of acrylate at 1,600 to 1,700 nm ^-1 and the Si-H peak at 2,100 to 2,200 nm ^-1 (Peak). 2 is a ¹ H NMR spectrum of the prepared HEMA-PDMS, which confirms the respective hydrogen peaks of HEMA-PDMS.

< PC  Composition and modification PC Gt;

978.4 g of bisphenol A (BPA), 1,620 g of NaOH 32% aqueous solution, and 7,500 g of distilled water were placed in a 20 L glass reactor. After confirming that BPA was completely dissolved in a nitrogen atmosphere, 3,650 g of methylene chloride, p-tert-butylphenol) and 5.5 g of HEMA-PDMS (5 wt% of PC) prepared in Example 1 were added and mixed. 3,650 g of methylene chloride dissolved in 49 g of triphosgene was added dropwise thereto over 1 hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the mixture was aged for 15 minutes, and 10 g of triethylamine was dissolved in methylene chloride. After 15 minutes, the pH was adjusted to 3 with a 1N hydrochloric acid aqueous solution, and the mixture was washed three times with distilled water. The methylene chloride phase was separated and precipitated in methanol to obtain a modified PC resin in powder form. The modified PC resin (PC-PDMS copolymer) obtained was measured for molecular weight by GPC using a PC Standard and found to have a weight average molecular weight of 34,000.

Example  2

The procedure of Example 1 was repeated, except that 3.59 g (30.9 mmol) of hydroxyethyl acrylate was used instead of HEMA in Example 1.

Example  3

The same procedure as in Example 1 was carried out except that 6.13 g of cyclohexanedimethanol monoacrylate (CAS No. 23117-36-4) was used instead of HEMA in Example 1, in which R ₆ was a C ₈ cycloalkylene group. .

Comparative Example  One

A PC resin in powder form was prepared in the same manner as in Example 1, except that the obtained HEMA capped polydimethylsiloxane (HEMA-PDMS) was not used.

 [Test Example]

The properties of the PC resin prepared in Examples 1 to 3 and Comparative Example 1 were measured by the following methods, and the results are shown in Table 1 below.

* Weight average molecular weight: Measured with a PC standard using an Agilent 1200 series.

* Flowability: Measured according to ASTM D1238 (condition at 300 캜, 1.2 kg).

Impact strength: Measured according to ASTM D256 (1/8 inch, Notched Izod).

* Repeating unit: Measured by ¹ H-NMR using Varian 500 MHz.

division Example 1 Example 2 Example 3 Comparative Example 1 Weight average molecular weight 34,000 34,500 33,000 32,000 Flowability 18 17 14 10 Impact strength (J / m, 23 캜) 880 890 930 900 Impact strength (J / m, -30 ℃) 450 500 520 170

As shown in Table 1, the PC resins (Examples 1 to 3) containing the polyorganosiloxane of the present invention had a higher viscosity than the PC resin (Comparative Example 1) containing no polyorganosiloxane of the present invention The impact strength and transparency were maintained, while the flowability and the low temperature impact strength were remarkably excellent.

Claims (13)

(1)
[Chemical Formula 1]

(R ₁ to R ₃ , R ' ₁ to R' ₃ are CH ₃ - or C ₆ H ₅ -, and R ₄ is

, R ' ₄ is CH ₃ -, C ₆ H ₅ - or

, R ₅ is H or CH ₃ -, R ₆ is a C ₂ -C ₆ alkylene group or a C ₆ -C ₁₂ cycloalkylene group, 0 <n + m≤99, and n and m are integers ) &Lt; / RTI &gt;
Polyorganosiloxane. The method according to claim 1,
Wherein R ₆ is a C ₅ to C ₆ alkylene group or a C ₆ to C ₁₂ cycloalkylene.
Polyorganosiloxane. The method according to claim 1,
Wherein the polyorganosiloxane is used in at least one selected from the group consisting of a comonomer, a modifier, and an impact modifier
Polyorganosiloxane. a) at least one organosiloxane selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, hexamethyldisiloxane and hexa-phenyldisiloxane, and at least one organometallic compound selected from the group consisting of octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane, Reacting the at least one selected organosiliconosiloxane with an acid catalyst to produce an unmodified polyorganosiloxane; And
b) a hydroxyalkyl (meth) acrylate compound wherein the alkyl group is a C ₂ to C ₆ alkyl group or a C ₆ to C ₁₂ cycloalkyl group, and the (meth) acrylate is methacrylate or acrylate, And reacting the polyorganosiloxane with a metal catalyst to produce a polyorganosiloxane having a modified terminal.
A process for producing a polyorganosiloxane. delete Characterized in that it is modified with the polyorganosiloxane of any one of claims 1 to 3
Modified polycarbonate resin. The method according to claim 6,
The modified polycarbonate resin is characterized in that the polyorganosiloxane is contained in the chain
Modified polycarbonate resin. The method according to claim 6,
The modified polycarbonate resin is characterized in that it comprises i) polyorganosiloxane, ii) bisphenol and iii) phosgene or carbonic acid diester
Modified polycarbonate resin. The method according to claim 6,
Wherein the polyorganosiloxane is 0.1 to 20% by weight based on 100% by weight of the modified polycarbonate resin
Modified polycarbonate resin. The method according to claim 6,
Wherein the modified polycarbonate resin has a weight average molecular weight of 10,000 to 100,000
Modified polycarbonate resin. The method according to claim 6,
The modified polycarbonate resin is characterized in that the amount of free polyorganosiloxane relative to 100% by weight of the total polyorganosiloxane is 10% by weight
Modified polycarbonate resin. Characterized in that it comprises the polyorganosiloxane and the polycarbonate resin according to any one of claims 1 to 3
Polycarbonate resin composition. 13. The method of claim 12,
Wherein the polyorganosiloxane is 0.1 to 20% by weight, and the polycarbonate resin is 80 to 99.9% by weight
Polycarbonate resin composition.

Images