KR20030014476A - Dihydroxy monomers containing P and F, and process for preparing them - Google Patents

Abstract

PURPOSE: A dihydroxy monomer containing both phosphorous oxide and fluorine(F) and a preparation process thereof are provided, thereby synthesizing a high quality polymer with a phosphine oxide group having improved heat resistance, heat stability, mechanical properties and adhesive activity. CONSTITUTION: The dihydroxy monomer containing both phosphorous oxide and fluorine(F) is represented by formula(1), wherein R is hydrogen or C1-C6 alkyl; X is fluorine or C1-C6 fluoroalkyl; and n is an integer of 1 to 4. The process for preparing the dihydroxy monomer comprises the steps of: chlorination of bis(4-alkoxyphenyl)phosphinic acid represented by formula(2) to prepare bis(4-alkoxyphenyl)phosphinic chloride represented by formula(3); and reacting the compound of formula(3) with a fluorine-substituted Grignard reagent, wherein R' is C1-C6 alkyl; and R is hydrogen or C1-C6 alkyl.

Description

Dihydroxy monomers containing phosphorus oxide and florin simultaneously and preparation method thereof {Dihydroxy monomers containing P and F, and process for preparing them}

The present invention relates to a dihydroxy monomer and a polymer thereof containing phosphorus oxide and fluorine at the same time, and more particularly, a fluorinated Grignard after chlorination of a dihydroxy monomer containing phosphorus oxide. The present invention relates to a novel monomer prepared by reacting with a reagent and simultaneously containing phosphorus oxide and florin represented by Chemical Formula 1, and a novel polymer having low refractive index, birefringence, ease of preparation, and thermal stability. .

Formula 1

In the general formula 1: R represents a hydrogen atom or an alkyl group of C ₁ ~C _6, X denotes a flow Oro alkyl C ₁ ~C _6, n is an integer from 1 to 4 as number of substituents of the alkyl group Oro flow.

Since the polymer containing florin (F) has excellent thermal stability, low dielectric constant, moisture absorption rate, fire resistance, chemical resistance, etc., it is used as a thermoplastic polymer, membrane, elastomer, etc. It is also widely used to manufacture devices for optical waveguides. However, it has been pointed out that the polymer containing an excessive amount of florin (F) has a great difficulty in manufacturing an actual electronic device due to poor adhesion with a silicon wafer. As the polymer containing florin (F), poly (arylene ether) s (hereinafter, abbreviated as 'PAEs') are typical. PAEs are engineering plastics that are used in aerospace as well as electronic materials. 4,4 '-(hexafluoroisopropylidene) diphenol (6FBPA) is mainly used as a dihydroxy monomer for producing such PAEs, and other monomers containing florin are very rare.

The present invention has been researched for many years to solve the problem that the polymer containing Florin (F) has a poor adhesiveness and a lot of difficulties in the actual manufacturing of information communication devices. As a result, the hydroxy group of the dihydroxy monomer containing phosphorus oxide was chlorinated to be modified, and then reacted with Florin substituted Grignard reagent to prepare a new monomer in which both florin and phosphorus oxide were simultaneously present in one monomer. In addition, the polymer prepared by using the novel monomer has completed the present invention by finding that the adhesive force is remarkably improved while maintaining the general physical properties of the polymer containing florin.

Accordingly, an object of the present invention is to provide a novel dihydroxy monomer containing phosphorus oxide and florin at the same time and a method for producing the same.

1 is an FT-IR spectra for BMPA and BMPC.

2 is a ¹ H-NMR spectra for BTPO and BHTPOPSI.

3 is ¹⁹ F-NMR spectra for BTPO and BHTPOPSI.

4 is ³¹ P-NMR spectra for BTPO and BHTPOPSI.

5 is a ¹³ C-NMR spectra for BTPO and BHTPOPSI.

6 is an FT-IR spectra for BTPO and BHTPO.

7 is the ¹ H-NMR spectra for BBPO and BHTPO.

8 is a ¹⁹ F-NMR spectra for BBPO and BHBPO.

9 is ³¹ P-NMR spectra for BBPO and BHBPO.

10 is ¹³ C-NMR spectra for BBPO and BHBPO.

11 is FT-IR spectra for BBPO and BHBPO.

12 is a ¹⁹ F-NMR spectra of polyarylene ether phosphine oxide.

Fig. 13 is the ¹ H-NMR spectra of polyarylene ether phosphine oxide.

14 is a graph showing the glass transition temperature of polyarylene ether phosphine oxide.

15 is a graph showing the thermal stability of polyarylene ether phosphine oxide.

The present invention is characterized by a dihydroxy monomer containing phosphorus oxide and florin simultaneously represented by the following formula (1).

Formula 1

In the general formula 1: R represents a hydrogen atom or an alkyl group of C ₁ ~C _6, X denotes a flow Oro alkyl C ₁ ~C _6, n is an integer from 1 to 4 as number of substituents of the alkyl group Oro flow.

Referring to the present invention in more detail as follows.

Since the novel monomer according to the present invention contains phosphorus oxide and florin at the same time, the polymer prepared by using the monomer of the present invention retains the thermal stability of the common florin-containing polymer as it is, as well as glass transition by phosphorus oxide As temperature increases, oxidation resistance and adhesion increase, it is useful as information communication device.

As a monomer of the present invention, a monomer containing R as a hydrogen atom and a fluorine (F) may not be prepared in one step due to the reaction characteristics between two reactors, ie, a hydroxyl group and a fluorine atom. Therefore, in the present invention, a material having an alkoxy group instead of a hydroxy group was used as a starting material, and a method of converting an alkoxy group into a hydroxy group at the end of the reaction after adhering a substance containing florin thereto was adopted. The preparation method of the novel monomer according to the present invention is briefly shown in the following Scheme 1.

In Scheme 1, R 'represents an alkyl group having _{1 to 6} carbon atoms, and R represents a hydrogen atom or an alkyl group having _{1 to 6} carbon atoms.

According to Scheme 1, first, bis (4-alkoxyphenyl) phosphonic chloride represented by Chemical Formula 3 is prepared by chlorination reaction of bis (4-alkoxyphenyl) phosphonic acid represented by Chemical Formula 2. The chlorination reaction is by a conventional method using a chlorinating agent such as thionyl chloride (SOCl ₂ ), N-chlorosuccinimide, chlorine gas (Cl ₂ ), and the reaction temperature is 25 to 55 ° C.

The chlorinated compound represented by Formula 3 is reacted with a Grignard reagent substituted with florin to prepare the target compound represented by Formula 1, wherein R is an alkyl group. The Grignard reaction conditions correspond to the usual conditions. For example, the reaction temperature is 0 to 70 ° C, and tetrahydrofuran, ether or the like is used as the reaction solvent. In addition, in order to synthesize the target compound represented by Chemical Formula 1, wherein R is a hydrogen atom, it is appropriately treated with acid. Specifically, the acid treatment is performed at room temperature using 5% sulfuric acid solution.

Each step reaction applied by the production method of the present invention described above is only a known method, but it is characterized by the selection of starting materials, the order of introducing substituents, and the like.

On the other hand, PAEs prepared using the novel monomers according to the present invention were at the same level or higher than the existing florin-containing polymers in terms of thermal stability, low dielectric constant, and the like, and showed excellent results in adhesion.

Such a present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1 Preparation of Bis- (4-methoxyphenyl) Phosonic Chloride (BMPC)

Bis- (4-methoxyphenyl) phosphonic acid (BMPA; 25 g) was mixed with 200 mL of thionyl chloride and reacted for one hour at 55 ° C. After completion of the reaction, the temperature was raised to 80 ° C. to remove thionyl chloride, and then vacuum (2 mm Hg) was added to remove the remaining thionyl chloride. The obtained product was used as it was without further purification.

As a result of NMR analysis of the obtained BMPC product, all peaks of ¹ H, ¹⁹ F, ³¹ P, and ¹³ C-NMR were shifted toward the low-long field, thereby confirming the substitution of the hydroxy group with chlorine. As shown in FIG. 1, the hydroxy group of BMPA disappeared in the FT-IR spectra, thereby confirming the conversion of the hydroxyl group to another group.

Example 2 Preparation of Bis (4-methoxyphenyl) trifluoromethylphenyl phosphine oxide (BTPO)

THF (50 mL) and magnesium (3 g) were added to a 250 mL two-necked flask equipped with a condenser, a dropping funnel and a magnetic stub. Added slowly. After reacting at room temperature for 12 hours, bis- (4-methoxyphenyl) phosphonic chloride (BMPC) was diluted with 30 mL of THF and added. Thereafter, the reaction mixture was heated to 65 ° C. for 12 hours, and the reaction was diluted with 2 L of ion-exchanged water. After extraction three times with methylene chloride and treated with magnesium sulfate to remove moisture, the organic solvent was removed by an evaporator. Thereafter, the resultant was dried for 48 hours in a vacuum dryer and used in the next reaction step. The reaction was at room temperature and the yield was more than 95%.

The obtained BTPO was analyzed by ¹ H, ¹⁹ F, ³¹ P, ¹³ C-NMR, and FT-IR. ^{In 1} H-NMR, hydrogen peaks corresponding to trifluoromethylphenyl groups appeared newly at 7.71 and 7.80 ppm, indicating that BTPO was successfully synthesized. In addition, as shown in ¹⁹ F (reference material CFCl ₃ ; 0 ppm), ³¹ P (reference material H ₃ PO ₄ ; 0 ppm) -NMR results, only one peak appeared, indicating that the material was very pure. The analysis results of FT-IR showed CF bond peaks at 1368, 1281, 1174, and 827 cm ^-1 , and the peaks of aromatic CHs were found around 3000 cm ^-1 .

Example 3 Preparation of Bis (4-hydroxyphenyl) -4-trifluoromethylphenyl phosphine oxide (BHTPO)

In a 250 mL two-necked flask, bis (4-methoxyphenyl) -4-trifluoromethylphenyl phosphine oxide (BTPO), acetic acid and HBr were added and reacted at 125 ° C. for 48 hours. The reaction was then precipitated in water and filtered to give the final product. The product obtained was vacuum dried at 50 deg. The reaction was carried out at room temperature and the yield was more than 90%.

The obtained BHTPO was analyzed by ¹ H, ¹⁹ F, ³¹ P, ¹³ C-NMR and FT-IR. ^{In 1} H-NMR, the peak corresponding to 3.83 ppm of methoxy group disappeared and the peak corresponding to hydroxy group appeared at 10.24 ppm, indicating that BHTPO was successfully formed. In addition, as a result of analysis of F, P-NMR showed only one peak to confirm that it was obtained very pure. Analysis of the FT-IR confirmed the peak by the hydroxyl group at 3168 cm ^-1 .

Example 4 Preparation of Bis (4-methoxyphenyl) -3,5-bistrifluoromethylphenyl phosphine oxide (BBPO)

3,5-bistrifluoromethylphenylmagnesium bromide was used instead of 4-trifluoromethylphenylmagnesium bromide as a starting material. Yield was more than 95%.

The obtained BBPO was analyzed by ¹ H, ¹⁹ F, ³¹ P, and ¹³ C-NMR. ^{From 1} H-NMR, peaks corresponding to hydrogen of the 3,5-bistrifluoromethylphenyl group appeared at 8.01 and 8.11 ppm, indicating that the reaction was performed. ^{In the case of 19} F and ³¹ P-NMR, only one peak appeared, indicating that there was only one substance. In the case of ¹³ C-NMR, the peak of 3,5-bistrifluoromethylphenyl group was also the same as that of ¹ H-NMR. Appears anew to confirm that the title compound is formed. The analysis results of FT-IR showed CF bond peaks at 1363, 1274, 1122, and 896 cm ^-1 , and the peaks of aromatic CHs were found around 3000 cm ^-1 .

Example 5 Preparation of Bis (4-hydroxyphenyl) -3,5-bistrifluoromethylphenyl phosphine oxide (BHBPO)

In the same manner as in Example 4, except that bis (4-methoxyphenyl) -3,5-bistrifluoro instead of bis (4-methoxyphenyl) -4-trifluoromethylphenyl phosphine oxide as a starting material Romethylphenyl phosphine oxide was used. The yield was very high, above 95%.

The obtained BHBPO was analyzed by ¹ H, ¹⁹ F, ³¹ P, and ¹³ C-NMR. ^{In the 1} H-NMR spectrum, the peak of 3.91 ppm corresponding to the methoxy group disappeared and a new peak corresponding to the 10.33 ppm hydroxyl group appeared to confirm the formation of a new compound. ^In the case of ¹³ C-NMR as well as in the case of ¹ H-NMR it was confirmed that the peak of 78 ppm of carbon corresponding to methoxy disappeared. Analysis of the FT-IR confirmed the peak by the hydroxyl group at 3168 cm ^-1 .

Example 6: Preparation of Polymer

Polymers were prepared using monomers containing florin and phosphorus oxide prepared in Examples 1 to 5. Decafluorobenzophenone (5FK), decafluorobiphenyl (5FP) and pentafluorophenylsulfide (5FS) were used as the dihalide monomer, dimethylacetamide as a solvent, K ₂ CO ₃ , Benzene was used as a cosolvent, respectively. The reaction temperature was 155 ° C. and the reaction time was 12 hours. Table 1 shows the yield and molecular weight of the polymer.

Polymerization Results of Polyarylene Ether Phosphine Oxides Polymer Mn Mw Mw / Mn yield BHTPO + 5FP 14,924 30,292 2.02 94 BHTPO + 5FK 7,880 47,062 4.42 98 BHTPO + 5FS 12,000 37,680 3.14 94 BHBPO + 5FP 18,400 38,272 2.08 95 BHBPO + 5FK 7,750 28,287 3.65 91 BHBPO + 5FS 12,400 42,780 3.45 92

According to Table 1, the yield of the polymer was all 90% or more and the highest molecular weight when 5FP was used as the dihalide monomer.

12 and 13 show ¹⁹ F-NMR and ¹ H-NMR for each of the synthesized polymers. As shown in FIG. 12, the florin at the para position disappeared after the polymerization, and it was confirmed that the polymerization occurred at the para position of the dihalide monomer. In ¹ H-NMR of FIG. It became wider than that of this monomer and could confirm that the polymerization was successful. Thermal properties of the prepared polymer are shown in FIGS. 14 and 15. Among the polymers, PTF3P and PBTFT showed the highest thermal and glass transition temperatures.

As described above, the novel monomer of the present invention simultaneously contains phosphorus oxide and florin, thereby synthesizing PAEs having phosphine oxide groups excellent in heat resistance, thermal stability, mechanical properties, and adhesion, and synthesized PAEs. Is used to manufacture high-performance optical waveguide devices, thereby contributing to the development of the electronics industry.

Claims (4)

A dihydroxy monomer simultaneously containing phosphorus oxide and florin, characterized in that represented by the formula (1). Formula 1 In the general formula 1: R represents a hydrogen atom or an alkyl group of C ₁ ~C _6, X denotes a flow Oro alkyl C ₁ ~C _6, n is an integer from 1 to 4 as number of substituents of the alkyl group Oro flow. The compound represented by the formula (1) is bis (4-methoxyphenyl) -4-trifluoromethylphenyl phosphine oxide, bis (4-hydroxyphenyl) -4-trifluoromethylphenyl phosphine Oxide, bis (4-methoxyphenyl) -3,5-bistrifluoromethylphenyl phosphine oxide and bis (4-hydroxyphenyl) -3,5-bistrifluoromethylphenyl phosphine oxide A dihydroxy monomer containing phosphorus oxide and florin simultaneously. Chlorination reaction of bis (4-alkoxyphenyl) phosphonic acid represented by Formula 2 to produce bis (4-alkoxyphenyl) phosphonic chloride represented by Formula 3; And And reacting the compound represented by Chemical Formula 3 with a Grignard reagent substituted with florin to prepare a dihydroxy monomer simultaneously containing phosphorus oxide and florin represented by Chemical Formula 1. In Scheme 1, R 'represents an alkyl group having _{1 to 6} carbon atoms, and R represents a hydrogen atom or an alkyl group having _{1 to 6} carbon atoms. The method according to claim 3, wherein the R compound produced by the Grignard reaction is converted into a compound represented by Chemical Formula 1 wherein R is a hydrogen atom by treating the compound represented by Chemical Formula 1 with C ₁ to C ₆ with an acid solution. Characterized in the manufacturing method.