JPH04372624A - Production of modified polyarylene sulfide - Google Patents

Abstract

PURPOSE:To obtain a compound excellent in compatibility with other polymers and adhesion to an inorganic material such as metal by reacting a specified polyarylene sulfide with a specified carboxylic acid anhydride. CONSTITUTION:A polyarylene sulfide having amino groups at the side chain and/or the terminal (e.g. a compound obtained by reacting p-dichlorobenzene with p-dichloroaniline and Na2S) is reacted with carboxylic acid anhydrides of formula I (wherein R1 is a trivalent organic group) and/or formula II (wherein R2 is a 2 C or higher tetravalent organic group, and at most two of the carbonyl groups are bonded to any one of the carbon atoms of the tetravalent organic group) (e.g. trimellitic anhydride).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing modified polyarylene sulfide, and more particularly to a method for producing imidized polyarylene sulfide in which a carboxyl group and/or a carboxylic acid anhydride structure is introduced into the molecule.

0002

[Prior art] Polyarylene sulfide (hereinafter referred to as P
It is also called PS. ) Resins have excellent properties such as heat resistance, but their drawbacks include (1) low impact resistance, and (2) insufficient adhesion to inorganic materials such as metals. Traditionally, PPS resin has been used for the purpose of improving the impact resistance of PPS resin and imparting other properties.
Many polymer blends of resins and other plastics have been proposed. For example, polyphenylene oxide (P
PO) (Japanese Unexamined Patent Publication No. 50-156651), blend with polycarbonate (Japanese Unexamined Patent Publication No. 51-59)
No. 952), blend with polyamide (Japanese Patent Laid-open No. 53
69255), but they have the disadvantage that they are not necessarily sufficiently compatible and cannot exhibit sufficient performance. As an improvement method, a method of adding epoxy resin as a compatibilizer has been proposed (Japanese Patent Laid-Open No. 59-6
4657, 155461, 155462, etc.), in this case there are problems such as smoke generation during molding.

0003

[Problems to be Solved by the Invention] The present invention solves the drawbacks of the prior art, and particularly aims to improve the adhesion of PPS to inorganic materials such as metals and the compatibility with other polymers. The aim is to provide technology that can Other objects and novel features of the invention will become apparent from the following description.

0004

[Means for Solving the Problems] The present invention provides side chains and/or
Alternatively, a carboxyl group and/or a carboxylic acid anhydride structure is formed in the molecule by reacting a polyarylene sulfide having an amino group at the terminal with a carboxylic acid anhydride represented by the following chemical formulas 1 and/or 2. This invention relates to a method for producing the introduced imidized polyarylene sulfide.

[Chemical formula 1] (However, in Chemical Formula 1, R1 is a trivalent organic group)

[chemical 2
] (However, in Chemical Formula 2, R2 is a tetravalent organic group containing at least two carbon atoms, and two or less of the carbonyl groups in Chemical Formula 2 are carbon atoms of any one of the tetravalent organic groups. bonded to atoms.)

[0005] The present invention involves reacting PPS having an amino group with a carboxylic acid anhydride represented by Formula 1 and/or Formula 2 to form a carboxyl group and/or a carboxylic acid anhydride in the PPS molecular chain.
Alternatively, a carboxylic acid anhydride structure is introduced to achieve the desired objectives of the present invention, such as increasing compatibility with other polymers and improving adhesion to inorganic materials such as metals. .

An example of the reaction is shown below.

[0007] PP having the above amino group in the present invention
The method for synthesizing S can be carried out, for example, by reacting the following components (a) and (b). (a) Alkali metal sulfide (typically sodium sulfide)
(b) Mixture of dihalides and halides having an amino group as a substituent In the above production method, examples of dihalides used as raw materials include dihalogenated benzenes shown in Chemical Formula 3 below. .

[Chemical Formula 3] (In the formula of Chemical Formula 3, R represents an alkyl or alkoxy group having 1 to 3 carbon atoms, n represents an integer of 0 to 3, and X represents a halogen atom) Specific examples thereof include the following: Compounds represented by formulas 4 to 14 can be mentioned. However, chemical compounds 4 to 1
In 4, examples of X1 include CI or Br.

[C4]

[C5]

[C6]

[C7]

[Chemical formula 8]

[Chemical formula 9]

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

[Chemical formula 14]

[0008] In the above, an example of a halide having an amino group as a substituent and used as a raw material is halogenated aminobenzene shown by the following chemical formula 15.

[Formula 15] (In the formula 15, R and n have the same meanings as defined above, R3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y represents a halogen atom, and m (indicates 1 or 2) Specific examples include the following compounds 16 to 2.
Examples include halogenated aminobenzene compounds represented by the formula 3. However, in Chemical Formulas 16 to 23, examples of Y1 include CI or Br.

[Chemical formula 16]

[Chemical formula 17]

[Chemical formula 18]

[Chemical formula 19]

[C20]

[C21]

[C22]

[C23]

In the above, in order to achieve the desired objectives of the present invention, such as increasing compatibility with other polymers and improving adhesion to inorganic materials such as metals, it is necessary to use amino groups as substituents. The halide is present in the mixture from 0.2 to
It is preferable that the content is 25 mol%. Further, it is preferable that the mixture contains 85 mol % or more of the para dihalide.

In the present invention, in the above reaction, a trihalide such as trichlorobenzene may be added in an amount of 5 mol % or less based on the dihalide, if necessary. The polymerization reaction is preferably carried out in a polar solvent, preferably an amide solvent such as N-methylpyrrolidone (NMP) or dimethylacetamide, or a sulfone solvent such as sulfolane. At this time, in order to adjust the degree of polymerization, it is desirable to add an alkali metal salt of carboxylic acid or sulfonic acid, an alkali hydroxide, or the like. Preferred polymerization reaction temperatures and times are approximately 120-300°C and 2-300°C.
It is 10 hours. The reaction is preferably carried out under an inert gas atmosphere. After the reaction is completed, the solid product is filtered, thoroughly washed with deionized water, and dried to obtain a PPS resin having amino groups. Next, the PPS resin and a carboxylic acid anhydride as described below are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide. The preferred reaction temperature and time are room temperature to 300 ℃
℃ for 30 minutes to 10 hours. After completion of the reaction, the reaction product is filtered, washed with acetone, etc., and then heated and dried to obtain a polyarylene sulfide in which a carboxyl group and/or a carboxylic acid anhydride structure is introduced into the desired PPS molecular chain.

The carboxylic acid anhydride represented by the formula 1 used in the present invention is represented by the above formula, and R1 in the formula is a trivalent organic group, preferably a trivalent organic group having 2 to 2 carbon atoms.
20 aliphatic, aromatic or cycloaliphatic organic groups. Specific examples of the carboxylic acid anhydride include trimellitic acid, 2
, 6,7-naphthalenetricarboxylic acid, 3,3',4-
Diphenyltricarboxylic acid, 3,3',4-benzophenonetricarboxylic acid, 1,3,4-cyclopentanetricarboxylic acid, 2,2',3-diphenyltricarboxylic acid, diphenylsulfone-3,3',4-tricarboxylic acid , ethylenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 3,4-dicarboxyphenyl-3'-carboxyphenyl ether, 1,3,4-cyclohexanetricarboxylic acid, etc. Examples include carboxylic acid anhydrides in which the group is ring-closed, and among these, trimellitic anhydride is preferred.

The carboxylic acid anhydride represented by the formula 2 used in the present invention is exemplified by the tetracarboxylic dianhydride having the formula 2, in which R2 has at least 2 carbon atoms. and at least two carbonyl groups of the dianhydride must be bonded to any one carbon atom of the tetravalent organic group. Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,4
, 3',4'-diphenylsulfonetetracarboxylic dianhydride, 3,4,3',4'-benzophenonetetracarboxylic dianhydride, 3,4,3',4'-diphenyldimethylmethanetetracarboxylic acid dianhydride, 2,3,6,
7-naphthalenetetracarboxylic dianhydride, 3,4,3
',4'-diphenyltetracarboxylic dianhydride, 3,
Examples include 4,3',4'-diphenyl ether tetracarboxylic dianhydride and 3,4,3',4'-diphenylmethane tetracarboxylic dianhydride.

The modified polyarylene sulfide of the present invention has, in addition to the polyarylene sulfide bond shown by the following chemical formula 24, an ether bond shown by the following chemical formula 25, a sulfone bond shown by the following chemical formula 26, and the following A biphenyl bond shown by the following chemical formula 27, a substituted phenyl sulfide bond shown by the following chemical formula 28 (wherein, R represents an alkyl, nitro, phenyl, alkoxy, or carboxyl group.)
, may contain a copolymer component as exemplified by a trifunctional bond shown by the following chemical formula 29. However, the copolymerization component is preferably less than 30 mol%.

[C24]

[C25]

[C26]

[C27]

[C28]

[C29]

[0014]

EXAMPLES Next, the present invention will be further explained based on examples. Example 1. In an autoclave with a capacity of 1 liter and equipped with a stirrer, 250 cc of NMP and Na2S (water content 40 w) were added.
t%) and 127 g (0.98 mol) and 0.31 gr of N
AOH was charged, and the temperature was gradually raised to 205° C. over about 2 hours while stirring in a nitrogen atmosphere for dehydration. After that, the reaction system was cooled to 150°C, and 140g of
r paradichlorobenzene (0.95 mol), 8 gr P-dichloroaniline (0.05 mol) and 0.5 gr 1,2,4-trichlorobenzene (0.003 mol) in 80 gr NMP. The dissolved solution was added, and the temperature was further raised to 250°C over 1 hour, and reaction was carried out for 2 hours. After the reaction, the autoclave was cooled to room temperature, the contents were filtered, and the reaction product filter cake was washed three times with deionized water at 50°C to remove the by-product salt. and other unreacted substances were removed and dried at 100°C to obtain a PPS resin having amino groups. 15g of the above PPS resin and 2.0g of trimellitic anhydride were added to 60cc of NMP, and the mixture was heated to 180℃ for 1 hour.
The reaction was allowed to proceed while stirring for a period of time. After cooling to room temperature, the reaction slurry was filtered to obtain a cake, which was thoroughly washed with acetone and then dried at 150° C. overnight to obtain a reaction product. As a result of taking an infrared absorption spectrum of the product using the film method, it was found that the infrared absorption attributable to the amino group around 3400 cm-1, which was observed in PPS having an amino group before the reaction, decreased, and the infrared absorption attributed to the amino group decreased and Absorption based on carboxyl groups was observed around 1730 and 1700 cm-1.

Example 2. A reaction product was obtained in the same manner as in Example 1, except that the reaction temperature between the PPS resin and trimellitic anhydride was 240°C. Similarly, the 3400 observed in PPS with amino groups before reaction
Infrared absorption attributable to amino groups near cm-1 decreases,
Absorption based on imide group and carboxyl group is 1730,
It was seen around 1700cm-1.

Example 3 A reaction product was obtained in the same manner as in Example 2, except that 2.0 gr of pyromellitic anhydride was used in place of 2.0 gr of trimellitic anhydride used in Example 1. As a result of taking an infrared absorption spectrum of the reaction product using the film method, it was found that 3
Infrared absorption attributable to amino groups at around 400 cm-1 decreased, and absorptions due to imide groups and carboxylic anhydride groups were observed at around 1700, 1732, and 1780 cm-1.

Example 4. In Example 2, 1, 2, 4
A copolymerized PPS and a reaction product were obtained in the same manner as in Example 2, except that -trichlorobenzene was not added and 3,5-dichloroaniline was used instead of paradichloroaniline. As a result of taking an infrared absorption spectrum of the reaction product using a film method, the same results as in Example 2 were obtained.

Example 5 A copolymerized PPS and a reaction product were obtained in the same manner as in Example 4, except that 2.0 gr of pyromellitic anhydride was used in place of 2.0 gr of trimellitic anhydride in Example 4. Ta. As a result of taking an infrared absorption spectrum of the reaction product using a film method, the same results as in Example 3 were obtained.

Example 6 In Example 1, the composition of the solution added to the reaction system after dehydration of Na2S was changed to 145.5 gr of balajichlorobenzene (0.99 mol), 1.8 gr of paradichloroaniline ( 0.01 mol) was dissolved in 80 gr of NMP and reacted for 1.5 hours at 250°C, at which temperature 1.3 gr of parachloroaniline (0.01 mol) was dissolved in 10 cc of NMP. The solution was added to the reaction system and the reaction was continued for an additional hour. The post-polymerization treatment was carried out in the same manner as in Example 1. Next, 15 gr of PPS having an amino group at the side chain and molecular end and 0.5 gr of trimellitic anhydride produced here were placed in 60 cc of NMP.
The reaction was carried out at 240°C for 3 hours. The treatment after the reaction was carried out in the same manner as in Example 1. The infrared absorption spectrum of the reaction product contains 17
Absorption at 30,1700 cm-1 was observed.

Comparative Example 1 and Comparative Example 2. In Example 1, after dehydration of Na2S, the composition of the solution added to the reaction system was changed to 145.5 gr of paradichlorobenzene (0.99 gr).
PPS having no amino group in its molecular chain was synthesized in the same manner as in Example 1, except that only mol) was dissolved in 80 gr of NMP. 15 gr of PPS and 0.5 gr of trimellitic anhydride were placed in 60 cc of NMP and reacted at 240°C for 1 hour (Comparative Example 1) and at 180°C for 1 hour (Comparative Example 2), but in both cases, the film No absorption based on acid structure or imide structure was observed in the infrared absorption spectrum of . Also, as mentioned later,
Adhesion to aluminum foil was also not observed after hot pressing.

Next, using the reaction product obtained as described above, the molecular weight and modified PPS were determined according to the following test method.
The modification reaction rate inside and the adhesive strength with the aluminum plate were measured. The results are shown in Table 1. Measurement of Molecular Weight The intrinsic viscosity [η] of the copolymer before modification was measured, and the weight average molecular weight (Mw) was calculated from the following relational expression. This measurement was carried out by the Journal Applied Polymer Society (
J, Appl. Polym. Sci. ), 32 39
59 (1986). [η] = 8.91x10-5xMw0.747 [η
] was determined by measuring the viscosity of an α-chloronaphthalene solution of the copolymer at 210° C. using an Ubbelord viscometer. Calculation of modification reaction rate in modified PPS Calculate the amount of imidization caused by the modification reaction using the following method,
The denaturation reaction rate in denatured PPS was determined. That is, P.P.S.
Samples in the form of KBr tablets were prepared from a powder mixture of homopolymer and N-phenylphthalimide in several proportions, and the benzene ring skeletal vibration vibration was determined by infrared spectroscopy (IR).
00cm-1 and 1730c of C=O stretching vibration of imide group
Analyzing the IR of m-1, 1900 cm-1 and 1730c
A calibration curve was created by determining the absorbance ratio of m-1, and the imidization rate of modified PPS, that is, the modification reaction rate was calculated from the calibration curve. Measurement of adhesive strength One half of two aluminum plates (thickness 0.1 mm) was
The reaction product powder was sandwiched and preheated for 3 minutes using a press heated at 320° C., and then pressurized at 50 Kgf/cm 2 for 1 minute. Thereafter, it was immediately transferred to a cooling press and cooled to room temperature under the same pressure, and then a test piece with a width of 10 mm and a length of 150 mm was created. After fixing the test piece to a steel plate with double-sided tape, it was pulled in a direction of 180 degrees at a speed of 50 mm/min at room temperature, and the peel strength was calculated.

[0022]

[Table 1]

[0023]

As described above, according to the present invention, by introducing a carboxyl group or an acid anhydride structure as a polar group into the PPS molecular chain, the drawbacks of the prior art are overcome.
It was possible to increase compatibility with other polymers and to improve adhesion to inorganic materials such as metals.

Claims (1)

[Claims] [Claim 1] A modified polyarylene sulfide characterized by reacting a polyarylene sulfide having an amino group at the side chain and/or terminal with a carboxylic acid anhydride represented by the following formula 1 and/or formula 2. Production method. [Chemical 1] (However, in Chemical 1, R1 is a trivalent organic group) [Chemical 2
] (However, in Chemical Formula 2, R2 is a tetravalent organic group containing at least two carbon atoms, and two or less of the carbonyl groups in Chemical Formula 2 are carbon atoms of any one of the tetravalent organic groups. bonded to atoms.)