WO2017119657A1

WO2017119657A1 - Novel polyorganosiloxane and copolycarbonate prepared using same

Info

Publication number: WO2017119657A1
Application number: PCT/KR2016/015339
Authority: WO
Inventors: 박정준; 황영영; 반형민; 이기재; 홍무호
Original assignee: 주식회사 엘지화학
Priority date: 2016-01-07
Filing date: 2016-12-27
Publication date: 2017-07-13

Abstract

The present invention relates to novel polyorganosiloxane capable of producing copolycarbonates with improved hardness and copolycarbonate prepared using the same. The novel polyorganosiloxane according to the present invention may be used as a monomer of copolycarbonate and can improve the hardness while maintaining inherent physical properties of the copolycarbonate due to a structure derived from an alkylene or isosorbide structure included in the structure thereof.

Description

【Specification】

[Name of invention]

Novel polyorganosiloxanes, and copolycarbonates prepared using the same

Technical Field

Cross Citation with Related Application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0002245 of January 7, 2016, and Korean Patent Application No. 10-2016-0179495 of December 26, 2016, and the Korean patent application All content disclosed in these references is included as part of this specification. The present invention relates to a novel polyorganosiloxane capable of producing copolycarbonates with improved hardness and chemical resistance and to copolycarbonates prepared using the same.

Background Art

Polyorganosiloxane is a kind of silicon (si li cone) means a polymer mainly composed of siloxane bonds substituted by organic groups (organi c groups), for example, aromatic diols such as bisphenol A and carbonate precursors such as phosgene Manufactured by condensation polymerization, colorless odorless, slow oxidation and stable at room temperature, hypoallergenic insulator, used in electrical, electronics, automotive, machinery, medical, cosmetics, lubricants, adhesives, gaskets, molded artificial aids, Patent Publication No. 10-2002-0016922 (published Mar. 06, 2002) discloses polyorganosiloxanes that are endblocked with trimethylsilyl useful as hydrogel contact lens materials. In addition, it has excellent laminar strength, numerical stability, heat resistance and transparency, and is applied to a wide range of fields such as exterior materials for automobiles, automobile parts, building materials, and optical parts. Such copolycarbonate resins have recently been copolymerized with aromatic diols of two or more different structures in order to be applied to a wider variety of fields, thereby introducing different structural units into the main chain of polycarbonate. Many studies have been attempted to obtain desired physical properties. In particular, research into introducing a polysiloxane structure into the main chain of polycarbonate has been conducted, but most of the technologies have high production costs, and if the chemical resistance, the laminar strength, especially the low temperature laminar strength increases, the transparency decreases, and the transparency is improved. If there is a problem that the chemical resistance or the laminar strength is lowered. Specifically, Eugenol-polydimethylsiloxane is used in US Patent Nos. 5,932 and 677 to improve low temperature laminar properties, and Al lylphenol-polydimethylsiloxane is used in Japanese Patent Nos. 3, 195 and 848. I'm proposing. However, as the field of copolycarbonate expands, the required hardness of copolycarbonate gradually increases. In addition, there is a need for the development of a copolycarbonate having a novel structure that can increase the hardness while maintaining the intrinsic physical properties and copolycarbonate. Accordingly, the present inventors have diligently studied the copolycarbonate with improved hardness and chemical resistance, and thus, include alkylene or isosorbide in the polyorganosiloxane structure used as a monomer of the copolycarbonate, as described below. The present invention was completed by confirming that the inherent physical properties of H can improve hardness and chemical resistance at the same time.

[Content of invention]

[Problem to solve]

The present invention is to provide a novel polyorganosiloxane and a method for producing the same, which can produce copolycarbonate with improved hardness and chemical resistance.

In addition, the present invention is to provide a copolycarbonate prepared using the polyorganosiloxane and a method for producing the same. In addition, the present invention is to manufacture a molded article and a method for producing the same produced with the codley carbonate.

[Measures of problem]

In order to solve the above problems, the present invention provides a polyorganosiloxane represented by the following formula (1).

[Formula 1]

In Chemical Formula l,

Ri to R4 are each independently hydrogen; Unsubstituted or oxiranyl group, a d- ₁₀ alkoxy substituted by oxiranyl group, or a C ₆ - ₁₅ alkyl substituted with a d- ₂₀ aryl; halogen; Cwo alkoxy; Allyl; ₍₁₀ halo-alkyl, C ₆ - ₂₀ aryl, and,

¾ is each independently hydrogen, d- ₆ alkyl, halogen, hydroxy, d-6

¾ koksi, or C ₆ - ₂₀ aryl,

Each X is independently selected from -C0-, -C0- or - a (C ₆ arylene ₁₀₎ -CO-,

Y is independently alkylene,

Z are each independently a bond, or -C00-,

L is d- ₁₀ alkylene, or ^*

ego,

n is each independently an integer of 1 to 99. The polyorganosiloxane represented by the formula (1) is used as a monomer of the copolycarbonate, as will be described later, by the structure (L) derived from alkylene or isosorbide contained in the structure of the copolycarbonate It is characterized by improving hardness and chemical resistance while maintaining duct ili ty. Preferably, to R4 are each independently hydrogen, methyl, ethyl, Propyl 3—phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ecoxy, propoxy, allyl, 2, 2,2-tri Fluoroethyl, 3, 3, 3—trifluoropropyl, phenyl, or naphthyl. Also preferably, are each independently d- ₁₀ alkyl, more preferably d- ₆ alkyl, more preferably d- ₃ alkyl, and most preferably methyl. Also preferably, R ₅ is hydrogen or C ₁ alkoxy, more preferably hydrogen or methoxy. Also preferably, X is -co- or -CO- (phenylene) -CO-. Also preferably, Y is alkylene, more preferably propylene, butylene, isobutylene, pentylene, isopentylene or neopentylene. Also, Z is ^• If the C00-, carbonyl group of Z is preferred to combine a benzene ring ^0.

In addition, preferably, L is a C ₅ - ₉ straight chain alkylene, or ^*

to be. More preferably, L is C ₈ straight chain alkylene. Also preferably, the polyorganosiloxane represented by Chemical Formula 1 is represented by the following Chemical Formula 1-1 or 1-2:

[Formula 1-1]

In Formula 1-1, n is as defined above.

In Formula 1-2, n is as defined above. Also, preferably the weight average molecular weight of the polyorganosiloxane is

700-8000, More preferably, it is 1500-3500. Also preferably, n is 1 to 99, more preferably 20 to 50. In addition, the present invention provides a method for producing a polyorganosiloxane represented by the formula (1) as shown in Scheme 1 below.

[Banungsik 1]

In the reaction formula 1, Ri to R ₅ , X, Y, Z, L and n are represented by the formula As defined in 1, Rio is hydroxy or halogen, preferably hydroxy or chloro. The reaction is a step of preparing a compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula A with the compound represented by Chemical Formula B. The molar ratio of the compound represented by Formula A and the compound represented by Formula B is preferably 2: 1 to 3: 1. In addition, the present invention provides a weight average molecular weight of 1,000 to 100, 000 g / mol copolycarbonate comprising a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3).

[Formula 2]

In Formula 2, Ri to, X, Y, Z, L and n are as defined in Formula 1,

In Chemical Formula 3,

To ¾ are each independently hydrogen, dK) alkyl, d- ₁₀ alkoxy, or halogen,

¾ is unsubstituted or substituted with d- ₁₀ alkylene, unsubstituted or Cwo alkyl, substituted phenyl C ₃ - ₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO. Preferably, R ₆ to ¾ are each independently hydrogen, methyl, chloro, or bromo. Also preferably, ¾ is straight or branched chain alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2, 2-diyl butane-2, 2 -Diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, ¾ nucleic acid is a cycloalkyl-1, 1-diyl, 0, S, SO, S0 ₂ or CO _l. The copolycarbonate is prepared by polymerizing a polyorganosiloxane, an aromatic diol compound, and a carbonate precursor represented by Formula 1, and as described above, alkylene or isosorb in the polyorganosiloxane represented by Formula 1 The bead-derived structure allows the duct ili ty to be maintained while improving hardness and chemical resistance. The aromatic diol compound corresponds to the compound represented by Formula 4 below.

In Formula 4, and ¾ to as defined in Formula 3. Specific examples of the aromatic diol compound include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide bis (4- Hydroxyphenyl) sulfide bis (4-hydroxyphenyl) ketone, 1, 1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2, 2 Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclonucleic acid (bisphenol Z), 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane, 2, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2, 2-bis (4-hydroxy-3-bromophenyl) propane, 2,2- Bis (4-hydroxy-3-chlorophenyl) propane, 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 2 ′ 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane Or 1,1-bis (4-hydroxyphenyl) -1-phenylethane. Preferably, the aromatic diol compound is 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A). The carbonate precursor serves to connect the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 4, and specific examples thereof include phosgene, triphosgene, diphosgene, ^ lomophosgene, dimethyl carbonate, diethyl carbonate, di Butyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate or bishaloformate. . Preferably, the carbonate precursor is phosgene. In addition, the present invention provides a method for producing the copolycarbonate comprising the step of polymerizing a polyorganosiloxane, an aromatic diol compound and a carbonate precursor represented by the formula (1). Preferably, the aromatic diol compound and the carbonate precursor may be used in an amount of 0.01 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight, respectively, relative to 100 parts by weight of the polyorganosiloxane represented by Formula 1. . The polymerization is preferably carried out by interfacial polymerization and interfacial polymerization and pressure during the ^'possible polymerization at low temperature, and it is easy to control molecular weight. The polymerization temperature is 0 ^° C to 40 ^° C, the reaction time is preferably 10 minutes to 5 hours. In addition, pH of reaction should be kept at 9 or more or 11 or more. desirable. As a solvent which can be used for the said superposition | polymerization, if it is a solvent used for superposition | polymerization of copolycarbonate in the art, it will not specifically limit, For example, halogenated hydrocarbons, such as methylene chloride and chlorobenzene, can be used. In addition, the polymerization is preferably carried out in the presence of an acid binder, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or an amine compound such as pyridine may be used as the acid binder. In addition, to control the molecular weight of the copolycarbonate during the polymerization, it is preferable to polymerize in the presence of a molecular weight regulator. Alkylphenol may be used as the molecular weight regulator, and specific examples thereof include p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecylphenol, eicosylphenol, doco Silphenol or triacontylphenol. The molecular weight regulator may be added before the start of the polymerization, during the start of the polymerization or after the start of the polymerization. The molecular weight modifier may be, for example, 0.01 part by weight, 0, 1 part by weight, or 1 part by weight, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of aromatic diol compound. The desired molecular weight can be obtained within this range. In addition, in order to promote the polymerization reaction, reaction agents such as triethylamine, tetra-n-butylammonium bromide, tertiary amine compounds such as tetra-n-butylphosphonium bromide, quaternary ammonium compounds and quaternary phosphonium compounds Can be used additionally. In addition, the present invention provides a molded article made of the copolycarbonate. As described above, the duct ili ty of the copolycarbonate is maintained by the structure derived from alkylene or isosorbide in the polyorganosiloxane represented by Chemical Formula 1, As the chemical resistance is increased, the field is wider than the molded articles made of copolycarbonate. The molded article is selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, ultraviolet absorbers, pigments and dyes, if necessary, in addition to copolycarbonates according to the present invention.

It may further comprise one or more. As an example of the method for producing the molded article, the copolycarbonate and other additives according to the present invention are well mixed by using a mixer, and then extruded into an extruder to produce pellets, and the pellets are dried and then injected into an injection molding machine. It can include steps.

【Effects of the Invention】

The novel pylorganosiloxane according to the present invention can be used as a monomer of the copolycarbonate, and by the alkylene or isosorbide-derived structure included in the structure thereof, the hardness and The chemical resistance can be improved.

[Brief Description of Drawings]

1 shows NMR data of a polyorganosiloxane according to an embodiment of the present invention.

[Specific contents to carry out invention]

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 2.40 g (17.8 μl) of tetramethyldisiloxane were mixed, and then the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane to 1 weight of acidic clay (DC-A3). It was put in a 3L flask with a portion and reacted at 60 ^° C for 4 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. The repeating unit ( _n ) of the terminal unmodified polyorganosiloxane thus obtained was found to be 34 NMR. To the terminal unmodified polyorganosiloxane, 4.81 g (35.9 讓 ol) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's plat inum catalyst were added to the terminal unmodified polyorganosiloxane at 90 ^° C. for 3 hours. The reaction was over. After the reaction was completed, Mibanung siloxane was removed by evaporation at 120 ^° C and 1 torr. The terminal modified polyorganosiloxane thus obtained was named AP-PDMS (n = 34). AP-PDMS confirmed that the repeating unit (n) was 34 by NMR using light yellow oil, Var i an 500 MHz, and no further purification was necessary. Preparation Example 2 Preparation of Compound Represented by Chemical Formula 1-1

50 g of Isosorbide (hereinafter referred to as ISB) was added to a 1000 mL equilibrium flask reactor capable of reflux, 400 mL of methylene chloride was added, and the mixture was stirred under a nitrogen atmosphere. Thereafter, 80 g of triethylamine was added thereto. Then, 65 g of triphenylphosgene was added and reacted at room temperature for 10 minutes to 3 hours. Using Fi lter The triethylamine salt was removed, and then 100 g of AP-PDMS prepared in Preparation Example 1 was added thereto. Workup with sodium bicarbonate, washing with distilled water, and adjusting the pH to neutral and overnight under reduced pressure to prepare a compound represented by the formula (1-1).

200 mL of chloroform was added to a 500 mL round flask reactor, and 10 g of AP-PDMS prepared in Preparation Example 1 was added thereto. Subsequently, 0.4 g of sebacoyl chloride was added dropwise and reacted under reflux for 2 hours. After completion of reaction, washing was neutralized to prepare a compound represented by Chemical Formula 1-2. NMR data of the prepared compound is shown in FIG. 1. Example 1

1784 g of water, 385 g of NaOH, and 232 g of BPA bisphenol A) were added to the polymerization reactor, and mixed and dissolved in an N ₂ atmosphere. 4.3 g of PTBP (para-tert butylphenol) and 6.57 g of the compound represented by Chemical Formula 1-2 prepared in Preparation Example 3 were dissolved and dissolved in MC (methylene chloride). Then, 128 g of TPG (tr iphosgene) was dissolved in MC and added for 1 hour while maintaining the pH at 11 or more. After 10 minutes, 46 g of TEA (triethyl amine) was added to form a reaction. . After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a methanol and nucleic acid mixture solution, which was then dried at 120 ^° C. to obtain a final copolycarbonate. Example 2

Copolycarbonate was prepared by the same method as Example 1, except that Compound 14 (14 g) represented by Chemical Formula 1-2 prepared in Preparation Example 3 was used. Example 3

Copolycarbonate was prepared by the same method as Example 1, but using 3.94 g of a compound represented by Formula 1-2 prepared in Preparation Example 3. Example 4

Copolycarbonate was prepared by the same method as Example 1, but using 1.31 g of the compound represented by Formula 1-2 prepared in Preparation Example 3. Example 5

Copolycarbonate was prepared by the same method as Example 1, except that 6.57 g of the compound represented by Chemical Formula 1-1 prepared in Preparation Example 2 was used. Comparative example

1784 g of water, 385 g of NaOH, and 232 g of bisphenol A (BPA) were added to the polymerization reactor, and mixed and dissolved under an N ₂ atmosphere. Here, 4.3 g of PTBP (para- tert butylphenol) was dissolved in MCXmethylene chloride and added. Then, 128 g of TPG (tr iphosgene) was dissolved in MC and added for 1 hour while maintaining the pH at 11 or higher. After 10 minutes, 46 g of TEA (tr iethyl amine) was added for coupling reaction. I was. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resulting polymer was washed three times with distilled water. 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a methanol and nucleic acid mixture solution, which was then dried at 120 ^° C. for final Copolycarbonate was obtained. Experimental Example

For each copolycarbonate prepared in Examples and Comparative Examples, the weight average molecular weight was measured by GPC using PC standard (Standard) using Agi lent 1200 ser ies. Further, 0.05 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite, octadecyl-3- (3, 5), relative to 1 part by weight of each copolycarbonate prepared in Examples and Comparative Examples. 0.010 parts by weight of -di-tert-butyl-4-hydroxyphenyl) propionate and 0.030 parts by weight of pentaerythritol tetrastearate, and pelletized using a φ30 kV twin-screw extruder with a bed, A specimen was prepared by injection molding ^at a cylinder temperature of 300 ^° C. and a mold temperature of 90 ^° C. using a JSW Co., Ltd. N—20C injection molding machine. Using this, physical properties were measured as follows.

1) Pencil Hardness: The extruded pellets were made of 10X 10 specimens using a heat ing press, and then the specimens were drawn with a pencil hardness tester (500 g) and visually checked.

2) Glass transition temperature (Tg): Using a differential scanning calorimeter, the temperature increase rate is 10 ^° C / min to raise the temperature from 20 ^° C to 200 ^° C, quenched to 20 ^° C, then raised to 200 ^° C Was measured.

3) Chemical resistance: Izod layered specimens were fixed to small j ig (strain 48.5R), and a cloth (width X length = 1 cm X 0.5 cm) was placed on the specimen and 0.5 mL of nitra sunspay, a chemical solvent, was dropped. Then, the chemical resistance was evaluated by measuring the time until the crack progressed and broken in the Izod specimen. The results are shown in Table 1 below.

Claims

Claims Claim 1 Polyorganosiloxane represented by the following general formula (1):

[Chemical Machining 1]

In Chemical Formula 1,

Or each independently hydrogen; Unsubstituted or oxiranyl group, an alkoxy substituted by oxiranyl group, or a C ₆ - ₂₀ aryl substituted with a d- ₁₅ alkyl; halogen; Alkoxy; Allyl; d- ₁₀ haloalkyl; ₂₀ is an aryl, - or C ₆

¾ are each independently hydrogen, C ₆ alkyl, halogen, hydroxy, d- ₆ alkoxy, or C ₆ - ₂₀ aryl, and,

Each Y is independently d- ₁₀ alkylene,

Z are each independently a bond, ᅳ C00-

*

L is Cwo alkylene, or

ego:

n is each independently an integer of 1 to 99.

[Claim 2]

The method of claim 1,

Are each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxalanylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, Propoxy, allyl, 2, 2, 2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl,

Polyorganosiloxane. [Claim 3]

The method of claim 1,

¾ is hydrogen, or d- ₄ alkoxy,

Polyorganosiloxane.

[Claim 4]

The method of claim 1,

X is -C0-, or -CO- (phenylene) -CO—

Polyorganosiloxane.

[Claim 5]

The method of claim 1,

Y is alkylene,

Polyorganosiloxane.

[Claim 6]

The method of claim 1,

L is a C ₅ -9 straight chain alkylene, or *

sign,

Polyorganosiloxane.

[Claim 7]

The method of claim 1,

The polyorganosiloxane represented by Formula 1 is represented by the following Formula 1-1 or 1-2,

Polyorganosiloxanes:

[Formula 1-1]

_N in Formula 1-1 is as defined in claim 1,

In Chemical Formula 1-2, n is as defined in claim 1.

[Claim 8]

The method of claim 1,

Weight average molecular weight of said polyorganosiloxane 0

Characterized in that

Polyorganosiloxane.

[Claim 9]

A copolycarbonate having a weight average molecular weight of 1,000 to 100,000 g / irol comprising a repeating unit represented by the following Chemical Formula 2 and a repeating unit represented by the following Chemical Formula 3:

[Formula 2]

In Chemical Formula 2,

Ri to R4 are each independently hydrogen; Unsubstituted or oxiranyl A Ci- ₁₀ alkoxy substituted by oxiranyl group, or a C ₆ - ₂₀ aryl group substituted with a d- ₁₅ halogen; Alkoxy; Allyl; d-o haloalkyl; ₂₀ is an aryl, - or C ₆

R ₅ are each independently hydrogen, d- ₆ alkyl, halogen, hydroxyl入^'alkoxy, or C ₆ - ₂₀ aryl, and,

Each X is independently selected from -C0-, -C0- or a CO-, - (C ₆ - ₁₀ arylene)

Each Y is independently d- ₁₀ alkylene,

Z are each independently a bond, or -C00-,

*

L is alkylene, or ^*

ego,

n are each independently an integer of 1 to 99,

[anger

In Chemical Formula 3,

Re to R9 are each independently hydrogen, alkyl, alkoxy, or halogen,

₁₅ cycloalkylene, 0, S, SO, S0 _2, or CO - ¾ is unsubstituted or substituted phenyl or a d-) alkylene, substituted or unsubstituted Cwo alkyl, or C ₃ substituted.

[Claim 10]

According to claim 9,

¾ is unsubstituted or substituted with phenyl, straight or branched chain alkylene, cyclonucleic acid-1, 1-diyl, 0, S, SO, S0 ₂ , or CO,

Copolycarbonate.

[Claim 11] The method of claim 9,

¾ to ¾ are each independently hydrogen, methyl, chloro, or bromo,

Copolycarbonate.

[Claim 12]

A molded article made of the copolycarbonate of any one of claims 9 to 11.