JPH1180345A - Production of polyaddition copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing the subject copolymer in a solid elastomer state, excellent in heat resistance and cold resistance by reacting a specific perfluoropolyetherdicarboxylic acid and a specified compound. SOLUTION: (A) A perfluoropolyetherdicarboxylic acid of the formula HOOCCFXO(CF2 CFXO)p (C2 )r (OCFXCF2 )q OCFXCOOH [X is F or CF3 ; (p)+(q) is 2-100; (r) is 2-5] is reacted with (B) a bisimidazoline compound, a bisoxazoline compound or a bisoxazine compound at about 100-350 deg.C to provide the objective polyaddition copolymer in the method for producing the polyaddition copolymer. The component A is obtained by reacting (p+q)+2 mol of hexafluoropropene oxide (X=CF3 ) or tetrafluoroethylene oxide (X=F) with 1 mol of dicarboxylic acid fluoride compound of the formula FOC(CF2 )n COF [(n) is 0-2] to provide a perfluoroetherdicarboxylic acid fluoride of the formula FOCCFXO(CF2 CFXO)p (CF2 )r (OCFXCF2 )q OCFXCOF and hydrolyzing the obtained perfluoroetherdicarboxylic acid fluoride.

Description

[Detailed description of the invention]

[0001]

TECHNICAL FIELD The present invention relates to a method for producing polyaddition copolymers. More particularly, it relates to a method for producing a solid elastomeric polyaddition copolymer from a liquid oligomer perfluoropolyetherdicarboxylic acid.

[0002]

2. Description of the Related Art It has been studied to obtain curable polymers that can be used as coating agents, sealants, etc. from liquid perfluoropolyether compounds.

[0003] JP-A-8-198926 describes that the following fluorine-containing amides are used.
This copolymer has the disadvantage that when the perfluoropolyether chain in the main chain decomposes and HF begins to be generated, the Si-containing bond is rapidly broken, resulting in a significant decrease in physical properties.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a solid elastomeric polyaddition copolymer excellent in heat resistance and cold resistance directly from a liquid oligomer, perfluoropolyetherdicarboxylic acid. is to provide

[0005]

DISCLOSURE OF THE INVENTION The object of the present invention is to:
General formula HOOCCFXO( _CF2CFXO )p(CF2)r( _OCFXCF2 ) _qOCFXCOOH (where X is a fluorine atom or a _CF3 group, p+q is 2-1
is an integer of 00 and r is an integer of 2 to 5) is reacted with a bisimidazoline compound, a bisoxazoline compound or a bisoxazine compound to produce a polyaddition copolymer. achieved by

[0006]

DETAILED DESCRIPTION OF THE INVENTION The perfluoropolyether dicarboxylic acid represented by the above general formula used as a starting material is hexafluoropropene oxide (X=CF ₃ ) or tetrafluoroethylene oxide (X=F) (p +q)+2
Dicarboxylic acid fluoride compound FOC(CF ₂ )nCOF(n:0
1 mol of perfluoropolyetherdicarboxylic acid fluoride FOCCFXO(CF ₂ CFXO) p(CF ₂ )r(OCFXCF ₂ )qOCFXCOF obtained by reacting 1 mol of P&M Company, Moscow, Russia). and its synthesis cost is relatively low. where the value of p+q is 2
~100, preferably 30-100 is based on the reason that good mechanical properties are obtained.

As the bisimidazoline compound, bisoxazoline compound or bisoxazine compound capable of polyaddition reaction with the liquid perfluoropolyetherdicarboxylic acid in an equimolar amount, the following compounds are used. Bisimidazoline compounds:

These bisimidazoline compounds are synthesized by reacting a dinitrile compound, a _{dicarbothioamide} compound, a diimide ester compound or a dithiocarboxylic acid compound with a diamine compound. ) ₄ CN and ethylenediamine
H ₂ N(CH ₂ ) ₂ NH ₂ and H 2 N(CH 2 ) 2 NH 2 are easily obtained by deammonification reaction in the presence of a sulfur catalyst. Bisoxazoline compounds, bisoxazine compounds:

For example, the above compound (A) is synthesized through the following series of steps. _{2HO ( CH2} ) _{2NH2 + C2H5OCOCOOC2H5} →HO( _CH2 ) _{2NHCOCONH (} CH
₂ ) ₂ OH→Cl(CH ₂ ) ₂ NHCOCONH(CH ₂ ) ₂ Cl→[A] The reaction in step 1 was carried out in ethanol solvent at room temperature, and the reaction in step 2 was carried out using SOCl ₂ . The final step cyclization reaction is carried out under reflux conditions of KOH-MeOH.

The polyaddition reaction of the perfluoropolyetherdicarboxylic acid with the bisimidazoline compound, bisoxazoline compound or bisoxazine compound is carried out at a temperature of about 100-350°C, preferably about 120-250°C, in the absence of a reaction solvent. It is done by heating.

For example, in the case of the bisimidazoline compound (A), the above perfluoropolyetherdicarboxylic acid HOOCRf
COOH is thought to react as follows.

[0012]

INDUSTRIAL APPLICABILITY The polyaddition copolymer obtained by the method of the present invention is directly obtained as a solid elastomeric copolymer from a liquid oligomer of perfluoropolyetherdicarboxylic acid, and has the following characteristics. ing. (1) It has excellent heat resistance and cold resistance, and since it does not contain Si, it has excellent resistance to HF. (2) It is insoluble in methanol, ethanol, acetone, chloroform, dimethylformamide, dimethylsulfoxide, etc. and has excellent solvent resistance. (3) TGA (Thermo-Gravimeter Analysis) from room temperature to 650℃
The temperature is raised at a rate of 5°C/min under a nitrogen gas stream until the sample reaches 5 _% weight reduction from the initial sample weight. (4) It is effectively used as a sealing material, sealant, etc. for chemical reaction vessels, petroleum plants, etc.

[0013]

EXAMPLES The present invention will now be described with reference to examples.

Reference Example 1 (Synthesis of Bisimidazoline A) 19.8 g (0.33 mol) of ethylenediamine and 17.8 g of adiponitrile were placed in a 100-ml glass reactor equipped with a stirrer.
(0.165 mol) and 0.5 g (15.6 mmol) of sulfur are charged and stirred under a stream of nitrogen gas until the sulfur dissolves. After that, 50 ml of n-pentyl alcohol was added, and the temperature was raised to 100° C., and formation of ammonia was observed. After reacting at this temperature for 3 hours, the mixture was allowed to stand at room temperature for 1 hour under a stream of nitrogen gas. The product was filtered, washed with n-pentyl alcohol, and recrystallized with benzonitrile to obtain 19.8 g of the desired product having a melting point of 219°C (yield 62%). ¹ H-NMR (TMS standard, heavy methanol): 1.81ppm(4H) 2.37ppm(4H) 3.54ppm(8H) 5.05p
pm(2H) elemental analysis value ( _C10H18N4 ): calculated value C _{; 61.82} %, H; 9.34%, N; 28.84% measured value C; 61.73%, H; 9.50%, N; 28.71%

Reference Example 2 (Synthesis of Bisimidazoline D) 19.8 g (0.33 mol) of ethylenediamine and 21 g of terephthalonitrile were placed in a 100-ml glass reactor equipped with a stirrer.
3 g (0.165 mol) and 0.5 g (15.6 mmol) of sulfur are charged and stirred with slight heating under a stream of nitrogen gas until the sulfur dissolves. After that, 50 ml of n-pentyl alcohol was added, and the temperature was raised to 100° C., and formation of ammonia was observed. After reacting at this temperature for 3 hours, the mixture was allowed to stand at room temperature for 1 hour under a stream of nitrogen gas. The product was filtered and washed successively with n-benzonitrile and acetone to a melting point of 307°C.
12.3 g of the desired product was obtained (yield 35%). ¹ H-NMR (TMS standard, heavy methanol/CDCl ₃ =1/1): 4.16 ppm (8H) 7.99 ppm (4H) Elemental analysis value (C ₁₂ H ₁₄ N ₄ ): Calculated value C; 67.27%, H; 6.59%, N;26.15% Measured value C;67.49%, H;6.62%, N;25.77%

Example 1 250 g (44 mmol) perfluoropolyetherdicarboxylic acid HOOCCF(CF ₃ )O[CF ₂ CF(CF ₃ )O]p(CF ₂ ) ₂ [OCF(CF ₃ )CF ₂ ]qOCF
(CF ₃ )COOH p+q: 32 and 8.5 g (44 mmol) of the bisimidazoline A obtained in Reference Example 1 were charged into a reaction vessel and heated to 160° C. over 30 minutes while stirring. After reacting for 1 hour, it was cooled.

The resulting polyaddition copolymer has the following properties. Tg (DSC, 1°C/min): -25°C Mooney viscosity ML ₁₊₁₀ (121°C, L rotor): 15pts T _5% reduction in temperature: 412°C

Example 2 In Example 1, instead of bisimidazole A, reference example
9.4 g (44 mmol) of the bisimidazole D obtained in 2 were used. The resulting polyaddition copolymer has the following properties. Tg (DSC, 1°C/min): -23°C Mooney viscosity ML ₁₊₁₀ (121°C, L rotor): 11pts T _5% reduction in temperature: 432°C

Example 3 In Example 1, 5.3 g (44 mmol) of bisoxazoline A was used instead of bisimidazole A. The resulting polyaddition copolymer has the following properties. Tg (DSC, 1°C/min): -24°C Mooney viscosity ML ₁₊₁₀ (121°C, L rotor): 13pts T _5% reduction in temperature: 378°C

Example 4 In Example 1, bisoxazoline D was used in place of bisimidazole A at 6.0 g (44 mmol). The resulting polyaddition copolymer has the following properties. Tg (DSC, 1°C/min): -22°C Mooney viscosity ML ₁₊₁₀ (121°C, L rotor): 9pts T _5% reduction in temperature: 408°C

Example 5 In Example 1, 250 g (25 mmol) of perfluoropolyether dicarboxylic acid with p+q=58 was used and reacted with 4.85 g (25 mmol) of bisimidazoline A. The resulting polyaddition copolymer has the following properties. Tg (DSC, 1°C/min): -29°C Mooney viscosity ML ₁₊₁₀ (121°C, L rotor): 23pts T _5% reduction in temperature: 416°C

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[Written Amendment]

[Submission date] September 10, 1998

[Procedural amendment 1]

[Name of document to be amended] Description

[Correction target item name] 0012

[Correction method] Change

[Correction details]

[0012]

INDUSTRIAL APPLICABILITY The polyaddition copolymer obtained by the method of the present invention is directly obtained as a solid elastomeric copolymer from a liquid oligomer of perfluoropolyetherdicarboxylic acid, and has the following characteristics. ing. (1) It has excellent heat resistance and cold resistance, and since it does not contain Si, it has excellent resistance to HF. (2) It is insoluble in methanol, ethanol, acetone, chloroform, dimethylformamide, dimethylsulfoxide, etc. and has excellent solvent resistance. (3) TGA (Thermo-Gravimeter Analysis) from room temperature to 650℃
The temperature is raised at a rate of 5°C/min under a nitrogen gas stream, and the temperature at which the weight of the sample is reduced by ₅ % from the initial weight is 370°C or higher . (4) It is effectively used as a sealing material, sealant, etc. for chemical reaction vessels, petroleum plants, etc.

Claims (2)

[Claims] 1. The general formula HOOCCFXO( _CF2CFXO )p(CF2)r( _OCFXCF2 ) _qOCFXCOOH (wherein X is a fluorine atom or a _CF3 group and p+q is 2-1)
is an integer of 00 and r is an integer of 2 to 5) is reacted with a bisimidazoline compound, a bisoxazoline compound or a bisoxazine compound. manufacturing method. 2. A polyaddition copolymer produced by the method of claim 1.