JPH03292325A - Production of borane-modified polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene having a desired number of reactive functional groups in the molecule by reacting a polyphenylene ether having an ethylenic unsaturation in a substituent with a specified borane compound. CONSTITUTION:A monomer of formula I [wherein m is 1-4; at least one R group is a substituent having ethylenic or/and acetylenic unsaturations, R is halogen, 1-20C prim. or sec. alkyl, aryl, haloalkyl, aminoalkyl or (halo) hydrocarbonoxy (in which the halogen atom and the oxygen atom are bonded through at least two C atoms)] to obtain a polyphenylene ether having an ethylenic unsaturation in a substituent and an intrinsic viscosity (in a chloroform solution at 30 deg.C) of 0.1dl/g or above. The obtained ether is hydroborated with a borane compound having at least one B-H bond, represented by formula II (wherein Z1 and Z2 are each H, alkyl, alkenyl, aryl, hydrocarbonoxy or halogen) at -10 to 150 deg.C in an inert gas atmosphere in a dehydrated aprotic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides the following methods for improving the compatibility of polymer blends:
The present invention relates to a method for producing a polyphenylene ether precursor having an arbitrary number of reactive functional groups in the molecule that forms a physical or chemical bond with a different polymer.

Specifically, the present invention relates to a method for producing poran-modified polyphenylene ether in which functional groups such as hydroxy groups, amino groups, ester groups, cyano groups, and keto groups useful for improving compatibility can be introduced very easily.

(Prior art) When producing a polymer blend, polyphenylene ether (hereinafter abbreviated as PPE) is generally incompatible with other resins and has an affinity with other resins, except for special resins. Therefore, when the two components are simply mixed, they exhibit an energetically stable phase-separated structure, and the adhesion at the interface of this two-layer structure is poor, resulting in a decrease in mechanical strength and impact resistance. This poses a major problem, such as the tendency to cause layer peeling 11f (delamination) during molding.

In order to solve the above problem, it is effective to use a block body or a graft body having an affinity segment as a compatibilizer in the polymer to be blended with PPE. To synthesize these, there are cases in which a bifunctional small molecule such as maleic anhydride is used as a binder, and cases in which polymers having functional groups that react with each other are bonded together, but in both cases, the polymer The type and number of functional groups in the molecule are important.

Examples of these are often unsaturated carboxylic acids,
Although unsaturated imides or unsaturated epoxies are kneaded and reacted, there are limitations on the number and types of functional groups that can be introduced.

In addition, examples of induction into various functional groups using the terminal phenolic hydroxyl group of PPE as a reaction site have been shown.
For example, the terminal carboxylic anhydride modified product shown in Japanese Patent Application Publication No. 62-500456, and the
There are terminal alcoholic hydroxy-modified products shown in the publication, and terminal glycidyl-modified products shown in US Pat. However, we cannot say that we are satisfied with the selectivity of numbers.

One of the effective methods for introducing functional groups is reaction with borane compounds. It is known that borane compounds can be efficiently converted into various functional groups through characteristic reactions, and by applying this to polymer molecules, they can become useful precursors to functionalized polymers.

These borane compounds are easily produced by an electrophilic addition reaction of a boron-hydrogen bond to a carbon-carbon unsaturated bond, a so-called hydroboration reaction.
anes in organic 5 synthesis
, Marcel Dekker (197311, Amination (H,C, Brownet al J, of Am
, (:hem, soc, 1964, 86356
5.1966.1 2870), esterification (H, C
, Brown et al., J. of Am., Che.
m, Soc.

], 968.90 818), cyanation (H, C, Br
ownet al, J, of Am, Chem, Soc.
,, 1969, 916854.1970.92
5790) and ketoification (H, C, Brown et al.
,J,of,Am,Chem,5oc1969'
It has been shown that it can be selectively and efficiently converted into a number of functional groups, such as , 6852).

Regarding the reaction of borane compounds as mentioned above, H, C, B
A famous study was carried out in detail by Dr. Rown (H,C
, Brown, Organic 5 synthesis
via BoranesJohn-Wiley (19
75), etc.), and the range of applications has expanded rapidly in recent years. However, the hydroporation reaction and subsequent reaction of borane with PPE having unsaturated bonds (e.g. 2-
Until now, no examples have been shown in which it has been applied to resins obtained by oxidative copolymerization of allyl-6-methylphenol and 2,6-dimethylphenol (e.g., U.S. Pat. No. 3,422,062). do not have.

(Problems to be Solved by the Invention) The present invention aims to improve the compatibility of polymer blends by:
PPE having any number of various reactive functional groups in the molecule
An object of the present invention is to provide a method for producing borane-modified PPE, which is a precursor for obtaining.

(Means for Solving the Problems) The present invention provides PP having a carbon-carbon unsaturated bond in a substituent.
E, - formula (wherein Z and Z2 are independently a hydrogen atom, an alkyl group,
This is a method for producing borane-modified PPE, characterized by reacting a borane compound having at least one boron-hydrogen bond represented by an alkenyl group, an aryl group, a hydrocarbon oxy group, or a halogen atom.

The PPE having a carbon-carbon unsaturated bond as a substituent used in the present invention has the general formula (where m is an integer of 1 to 4, and at least one R
is a substituent having a carbon-carbon double bond or/and a carbon-carbon triple bond, and R is independently a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, an aryl group, or a haloalkyl group. group, aminoalkyl group, hydrocarbonoxy group, or halohydrocarbonoxy group in which a halogen atom and an oxygen atom are bonded via at least two carbon atoms). This is PPE obtained by Specific examples of this monomer include:
2-allylphenol, 2,6-diallylphenol,
2-allyl-6-methylphenol, 2-allyl-5-
Examples include chlorophenol, 2-allyl-3-methoxyphenol, 2-allyl-3-isobutyl-6-methylphenol, and 2-allyl-6-nitylphenol, and preferably 2,6-diallylphenol, 2-allylphenol, and 2-allyl-6-nitylphenol. Allyl-6-methylphenol or 2-allyl-6-nitylphenol.

In addition, as a substituent of phenol or a phenol derivative, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, or a halogen atom and oxygen A monomer having a halohydrocarbonoxy group in which the atoms are bonded via at least two carbon atoms is defined by the formula (
It may be oxidatively copolymerized with the monomer II), and specific examples of typical monomers of the latter derivatives include:
0-lm- or p-cresol, 26-12.5-
2.4- or 3.5-dimethylphenol, 2.6
-diphenylphenol, 2.6-diallylphenol, 2,3.5- or 2.3.6-dolimethylphenol or 2-methyl-6-t-butylphenol, and the like. Preferred among these are 2,6-dimethylphenol, a large amount of 2,6-dimethylphenol and a small amount of 2,3,6-)-dimethylphenol, 〇- or p-cresol. These include those in which one type or two or more types of monomers are used in combination.

Furthermore, the above monomers are used as main components, bisphenol A, tetrabromobisphenol A, resorcinol, hydroquinone, 2,2-bis(3',5'-dimethyl-
4'-hydroxyphenyl)propane, bis(3,5-
dimethyl-4-hydroxy-phenyl)methane, 3.3
It is also possible to use a polymer containing a polyvalent hydroxy aromatic compound such as ',5,5'-tetramethyl-4,4'dihydroxybiphenyl or 4,4'-dihydroxybiphenyl as a copolymer component.

Further, the production of the polymer can be carried out in the same manner as ordinary oxidative polymerization of PPE, for example, US Pat. No. 3,422,062
No. 3306874, No. 3306875, No. 3257257, and No. 3257358.

The catalyst used for oxidative polymerization is not particularly limited, and any catalyst that can provide a desired degree of polymerization may be used.

Many catalyst systems are known in the art, such as cuprous salt-amine, cupric salt-amine-alkali metal hydroxide, manganese salt-primary amine, and the like. Furthermore, it is also possible to use polymer components in which some of them have been modified by a catalyst component, a polymerization solvent component, or by heat or oxygen during the manufacturing process and molding process. The range of the degree of polymerization is not particularly limited, but if the degree of polymerization is too low, the compatibilizing ability will be reduced, so the intrinsic viscosity of the chloroform solution at 30°C (η1
．． ) is about 0.1 cff/g is the practical lower limit, preferably 0.2 dI/g or more, more preferably 0.3 #/g
g or more.

The poran compound used in the present invention has at least one boron-hydrogen bond, and the substituents are independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydrocarbon oxy group, or a halogen atom. Specific examples include diborane and complex compounds of trivalent borane and Lewis bases, such as poran-tetrahydrofuran complex, poran-triethylamine complex, poran-pyridine complex, poran-ammonia complex, and borane. -t
-butylamine complex, borane-N,N-diethylaniline complex, borane-N,N-diisopropylethylamine complex, borane-dimethylamine complex, borane-4-dimethylaminopyridine complex, borane-4-ditylmorpholine complex, borane-2 , 6-lutidine complex, borane-4
-Methylmorpholine complex, borane-methylsulfide complex, borane-morpholine complex, borane-1,4-thioxane complex, borane-4-phenylmorpholine complex, borane-piperidine complex, borane-poly(2-vinylpyridine) complexes, borane-pyridine complexes, borane-tributylphosphine complexes, borane-triphenylphosphine complexes, and the like.

Further, examples of the divalent borane compound include 3-(methylthio)propylborane and thexylborane.

Furthermore, as monovalent borane compounds, catecholborane,
9-borabicyclo[3,3,1]nonane (abbreviation: 9-
BBN), dithiamylborane, dichloroborane, dicyclohexylborane, etc.

Preferred borane compounds include borane-tetrahydrofuran complexes, borane-pyridine complexes, borane-methylsulfide complexes, and 9-BBN from the viewpoint of being used in large numbers and being easily available, and from the viewpoint of chemical stability.

The borane-modified PPE produced in the present invention has a carbon-carbon substituent.
It is obtained by the hydroboration reaction shown below between PPE having a carbon unsaturated bond and a borane compound having at least one boron-hydrogen bond, and a boron atom is directly bonded to the PPE.

The hydroboration reaction of the present invention is carried out under an inert gas atmosphere, preferably under a nitrogen gas or argon gas atmosphere, and the solvent is not particularly limited as long as it is a sufficiently dehydrated aprotic solvent, such as tetrahydrofuran, dioxane or diglyme. Aprotic polar solvents are preferred.

The number of carbon-carbon unsaturated bonds in PPE is not particularly limited, but when considered as a compatibilizer, the proportion of units containing unsaturated bonds is preferably 1 to 20 in one molecule. , 1 to 10 are more preferable, and there is no restriction on the amount of the borane compound used, but it is preferable that the number of boron-hydrogen bonds is equal to or higher than the number of carbon-carbon unsaturated bonds, and is twice as large as the number of carbon-carbon unsaturated bonds. The above is more preferable, and on the other hand, when converting the organoborane derivative to another functional group,
There are some reactions in which trisubstituted derivatives are preferable, and in such cases, when using a borane compound containing 2 to 3 boron-hydrogen bonds, the number of boron-hydrogen bonds should be equal to or greater than the number of unsaturated bonds. is suitable.

The reaction temperature is between -10°C and 150°C, and higher temperatures are advantageous for the reaction to proceed. Boron-hydrogen bond 2
When using a borane compound containing 3 to 3, gelation of PPE occurs due to hydroboration reaction,
This is not preferable because the reaction rate of carbon-carbon unsaturated bonds decreases. In this case, the reaction temperature is preferably in the range of 40 to 110°C.

Although the reaction time depends on reaction conditions such as temperature, the reaction is almost completed within 30 minutes, and sufficient results can be obtained in 1 hour.

(Examples) In order to illustrate the present invention more specifically, Examples thereof are shown below, but the present invention is not limited thereto.

In the examples, parts and % indicate parts by weight and % by weight, respectively.

The PPE used was a copolymerized PPE produced by oxidative coupling of 2.6 xylenol and 2-allyl-6-methylphenol in the presence of a manganese chloride/jetanolamine/dibutylamine catalyst, as shown in Table 1. Ta.

The 'H-NMR chart of No. 2PPH in Table 1 is shown in FIG.

The allyl group content and reaction rate were determined by 'H-NMR.3.
Calculation was made from the integrated intensity of signals originating from allyl groups around 20 ppm and 4.95 ppm.

Table 1 Copolymer of 2-allyl-6-methylphenol and 2,6-xylenol a) Ratio of the number of moles of allyl group to PPE units. '
Calculated by H-NMR integrated intensity (allyl group hydrogen/aromatic hydrogen).

b) Intrinsic viscosity, measured at 30°C in chloroform solvent.

Porampa A-formation Example 1 of PPE Tetrahydrofuran (hereinafter abbreviated as THF) in which 10 parts of No. 2 PPE in Table 1 was sufficiently dried under a nitrogen atmosphere.
200 parts of a THF solution of poran-THF complex at a temperature of 50°C (3.6 parts of poran concentration, 1 mol/liter)
When added, a precipitate formed immediately. After refluxing for 3.5 hours, the resin was precipitated with a large amount of methanol to obtain borane-modified PPE. A 'H-NMR chart of this resin is shown in FIG.

Yield 99%, reaction rate of allyl group 100%.

Example 2 Under the same conditions as Example 1, No. I P P E in Table 1
After adding 1.9 parts of the poran solution used in Example 1 to 10 parts, the mixture was refluxed for 40 minutes to obtain poran-modified PPE.

Yield 97%, reaction rate of allyl group 100%.

Example 3 38 parts of a THF solution of 0.5 mol/liter 9-BBN was added to 0 parts of No. 2 P PE I in Table 1 Example 2
A borane-modified PPE was obtained by reacting under the same conditions. In this case no gelation occurred. A 'H-NMR chart of the obtained borane-modified PPE is shown in FIG.

Yield 98%, reaction rate of furyl group 100%.

Example 4 No. 2 P P in Table 1 dissolved in 89 parts of THF
1.9 parts of the borane solution of Example 1 was added to the ElO portion and reacted at room temperature for 30 minutes to obtain borane-modified PPE.

Yield 95%, reaction rate of allyl group 51%.

Poran PPE alcohol application example The Poran modified PPE resin of Example 1 was swollen in 180 parts of THF, and 5 parts of sodium hydroxide was dissolved in 7.6 parts of pure water.
．． After slowly dropping 48 parts of 30% hydrogen peroxide at 30°C, the mixture was stirred at 40°C for 2 hours, and the resulting resin was precipitated with methyl alcohol to obtain alcohol-modified PPE.

Yield 92%. IR (OH stretching vibration 3580cm-'),
'H-NMR(-Cdan'-(OH)3, 55ppm
), alcohol conversion rate 61% (from 'H-NMR)
.

(Effects of the Invention) The production method of the present invention makes it possible to provide a novel PPE having a poran group that can easily bind various functional groups that can serve as compatibilizers for polymer blends of PPE resins. can.

[Brief explanation of the drawing]

Figure 1 shows 'H-NMR of No. 2 PPH in Table 1.
FIG. 2 is a 'H-NMR chart of the borane-modified PPE obtained in Example 1, and FIG. 3 is a 'H-NMR chart of the borane-modified PPE obtained in Example 3.

Claims (1)

[Claims] Polyphenylene ether having a carbon-carbon unsaturated bond as a substituent has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (I) (In the formula, Z_1 and Z_2 independently represent a hydrogen atom, an alkyl A method for producing a borane-modified polyphenylene ether, which comprises reacting a borane compound having at least one boron-hydrogen bond represented by the following formula (representing a group, an alkenyl group, an aryl group, a hydrocarbon oxy group, or a halogen atom).