JPH0368632A - Polyphenylene ether/polyester copolymer obtained from polyphenylene ether having terminal epoxytriazine group - Google Patents

Abstract

PURPOSE: To improve the processability and solvent resistance by reacting a polyphenylene ether having terminal epoxytriazine groups with a specified polyester.

CONSTITUTION: A polyphenylene ether of formula I (Q¹ is halogen, a primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or a halohydrocarbonoxy group having a structure wherein a halogen atom and O are separated by at least two carbon atoms; and Q² is H, halogen, a primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or a halohydrocarbonoxy group defined in Q¹) is reacted with epoxychlorotriamine to give a polyphenylene ether having terminal epoxytriazine groups. This polyphenylene ether is then reacted with a polyester containing structural units of formula II (R⁴ is a divalent aliphatic, alicyclic or aromatic hydrocarbon group, or polyoxyalkylene; and A¹ is a divalent aromatic group).

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to the production of polyphenylene ether-polyester copolymers.

BACKGROUND OF THE INVENTION Polyphenylene ether is a layer of widely used thermoplastic engineering resins characterized by excellent hydrolytic stability, dimensional stability, toughness, heat resistance and dielectric properties. However, polyphenylene ethers are unsatisfactory in certain other properties such as processability and solvent resistance. Therefore, research continues to develop means of modifying polyphenylene ethers to improve these other properties.

One of the drawbacks that inhibits the use of polyphenylene ethers for molding articles such as automotive parts is their low resistance to non-polar solvents such as gasoline. To increase solvent resistance, it may be desirable to form compositions in which polyphenylene ethers are combined with resins that have a high degree of crystallinity and therefore exhibit high resistance to solvents.

Examples of such resins are thermoplastic polyesters including poly(alkylene dicarboxylates), especially poly(alkylene terephthalates). There are other reasons for producing compositions containing polyphenylene ethers and other polyesters, such as polyarylates and elastomeric polyesters.

However, polyphenylene oxide-polyester blends often experience phase separation and delamination. Such formulations typically contain large, poorly dispersed polyphenylene ether particles, and no phase interaction occurs between the two resins.

Molded articles made from such formulations are typically characterized by very low impact strength, delamination, etc.

A number of methods have been developed to compatibilize polyphenylene ether-polyester blends. For example, WO 87/850 describes polyphenylene ether-polyester blends which have been made compatibilized by the addition of aromatic polycarbonates. Such formulations are extremely versatile in a number of critical applications such as the manufacture of automobile body parts. However, the presence of polycarbonate can lead to a reduction in certain other properties, such as heat distortion temperature.

Furthermore, with certain commercially available polyphenylene ethers, problems may arise due to the presence of aminoalkyl substituted end groups, as detailed below. To achieve optimal impact strength, it is often necessary to remove this aminoalkyl substituted end group and other amine components that are often present as impurities in polyphenylene ethers. Measures such as the use of amine scavengers and/or vacuum venting of polyphenylene ethers are effective in reducing amino nitrogen content, but in some cases add undesirable additional steps to the processing operation.

Various methods are also known for producing copolymers of polyphenylene ether and polyester.

Such copolymers are often useful as compatibilizers for the resin formulations. It is often advisable to use polyphenylene ethers containing functional groups to facilitate the formation of copolymers. For example, epoxy groups can react with nucleophilic groups in polyesters and polyamides, such as amino, hydroxy and carboxy groups, resulting in the formation of copolymers.

Various methods for producing epoxy-functionalized polyphenylene ethers are described in numerous patent specifications and publications. For example, U.S. Patent No. 4,460.
No. 743 describes the reaction of polyphenylene ether with epichlorohydrin to produce epoxy-functionalized polymers. However, this method is disadvantageous in that the polyphenylene ether must be dissolved in a large excess of epichlorohydrin, and epichlorohydrin is a relatively expensive reagent, is highly irritating to the skin, and can be harmful to the kidneys.

WO 87/7279 describes a process for reacting polyphenylene ethers with terephthaloyl chloride and glycidol to produce polyphenylene ethers with epoxy functional groups useful, for example, in the production of copolymers with polyesters. However, the production of copolymers with polyesters by this method requires a solution reaction in a relatively expensive, high-boiling solvent such as trichlorobenzene, and the reaction is extremely slow.

2 and 2 describes the reaction of polyphenylene ether with various epoxy-functionalized ethylenic monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether in the presence of free radical initiators. has been done. The resulting epoxy-functionalized polyphenylene ethers are useful as intermediates for the preparation of copolymers by melt reaction with polyesters. However, functionalization of polyphenylene ethers by this method requires the use of large amounts of monomers, and certain monomers, including glycidyl methacrylate, are toxic. Furthermore, this reaction generally involves the homopolymerization of monomers with epoxy functionality, thus following complex processes such as dissolution of the crude polymeric product and subsequent formation and decomposition of the polyphenylene ether-methylene chloride complex. It is necessary to remove the homopolymer by manipulation. These materials are therefore not easily compatible with the production of copolymers on an industrial scale.

The present invention provides polyphenylene ether-polyester copolymers made from highly reactive epoxy-functionalized polyphenylene ethers that can be prepared using relatively inexpensive reagents under simple solution or interfacial reaction conditions. It is something. Such copolymers have excellent physical properties, especially when blended with conventional impact modifiers for polyphenylene ethers. It has been found that these copolymers can also be used as compatibilizers for formulations containing unfunctionalized polyphenylene ethers.

SUMMARY OF THE INVENTION Accordingly, the present invention provides a polyphenylene ether having an epoxytriazine terminal group and the formula: The present invention also provides a composition containing a polyphenylene ether-polyester copolymer produced by reaction with at least one polyester comprising a structural unit of (AI is a divalent aromatic group).

DETAILED DISCLOSURE OF THE INVENTION Polyphenylene ethers with epoxy triazine end groups suitable for use in preparing the compositions of the present invention and methods for their preparation are described in applicant's own U.S. Patent Application No. 210.54.
It is described in the specification of No. 7. These have the formula: ha(I[+) where each Ql is independently /% rogen, primary or secondary lower alkyl (i.e. alkyl containing up to 7 carbon atoms), phenyl, )roalkyl, aminoalkyl, hydrocarbonoxy, or a hydrocarbonoxy group having a structure in which a norogen atom and an oxygen atom are separated by at least two carbon atoms; each Ql is independently hydrogen , halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or Q
X is an alkyl, cycloalkyl or aromatic group or a group of formula: and R1 is a divalent aliphatic, alicyclic, heterocyclic or unsubstituted or a substituted aromatic hydrocarbon group)
It comprises a polymer molecule having a terminal group of

Polyphenylene ethers with epoxy triazine end groups can be prepared from polyphenylene ethers known in the art, as described below. The latter, polyphenylene ether, includes, but is not limited to, those described below, and broadly encompasses various modifications and modifications thereof, all of which are applicable to the present invention.

Polyphenylene ethers are comprised of a number of structural units having the formula: % Formula % where independently in each of the units each Ql and Ql are as defined above. Examples of suitable primary lower alkyl groups as Ql and Ql are methyl, ethyl, n-propyl, n-
Butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl,
2-23- or 4-methylpentyl and the corresponding heptyl group. Examples of secondary lower alkyl groups are isopropyl, secondary bruti and 3-pentyl groups.

It is preferred that all alkyl groups are linear rather than branched. Often each Ql is an alkyl or phenyl group, especially a Cl-4 alkyl group and each Ql is hydrogen. Suitable polyphenylene ethers are described in numerous patent documents.

Polyphenylene ethers include both homopolymers and copolymers. Suitable homopolymers are, for example, those containing 2,6-dimethyl-1,4-phenylene ether units in the t-position. Suitable copolymers have positions 711 (for example) of 2, 3, 6. Includes random copolymers containing trimethyl-1,4-phenylene ether units in combination. A large number of suitable random copolymers, as well as homopolymers, are disclosed in the patent literature.

Also included among the polyphenylene ethers that can be used in the present invention are polyphenylene ethers that contain molecular moieties that improve properties such as molecular weight, melt viscosity, and/or impact strength. Such polymers are described in the patent literature and are prepared by known methods such as polymers such as vinyl monomers such as acrylonitrile and vinyl aromatics (e.g. styrene) or polystyrenes and elastomers on polyphenylene ethers. It can be manufactured by grafting with. The product typically includes both grafted and ungrafted molecular portions. Other suitable polymers are coupled polyphenylene ethers, i.e., a coupling agent is reacted with the hydroxy groups of the two polyphenylene ether chains in a known manner, but under conditions such that a substantial proportion of free hydroxy groups remains. a higher molecular weight polymer comprising the reaction product of the hydroxyl group of a polyphenylene ether and a coupling agent, formed by
It is. Examples of coupling agents are low molecular weight polycarbonates, quinones, heterocycles and formals.

Polyphenylene ethers generally have number average molecular weights ranging from about 3,000 to 40,000 and about 20°000 to go, ooo as determined by gel permeation chromatography.
It has a weight average molecular weight in the range of . Its intrinsic viscosity is often about 0.35 to 0, measured at 25°C in chloroform.
．． It is in the range of 6 dl/g.

Polyphenylene ethers are typically produced by oxidative coupling of at least one corresponding monohydroxy aromatic compound. Particularly useful and readily available monohydroxy aromatic compounds are 2,6-xylenol (where each Ql is methyl and each Ql is hydrogen) and 2. 3. 6 = trimethylphenol (each Ql and one Ql is methyl and the other Ql is hydrogen), in which case the intervening polymer is poly(2,6-dimethyl-1,4-phenylene ether) and poly(2,
3,6-trimethyl-1,4-phenylene ether).

Various catalyst systems are known that can be used for the production of polyphenylene ethers by oxidative coupling. There are no particular restrictions on the selection of catalyst, and any known catalyst may be used. Often such catalysts contain at least one heavy metal compound, such as a copper, manganese or cobalt compound, in combination with various other conventional substances.

A first group of preferred catalyst systems consists of catalyst systems containing copper compounds. Such catalysts are disclosed, for example, in U.S. Pat. No. 3,306,
No. 874, same No. 3. 306. No. 875, No. 3, 9
No. 14,266 and N4,028.341. These are usually a combination of cuprous or cupric ions, halide (ie chloride, bromide or iodite) ions and at least one amine.

Catalyst systems containing manganese compounds constitute a second preferred group of catalysts. These are generally alkaline systems combining divalent manganese with various anions of halides, alkoxides or phenoxides.

Manganese is often used in dialkylamines, alkanolamines, alkylene diamines, O-hydroxyaromatic aldehydes, O-hydroxyazo compounds, ω-hydroxyoximes (monomeric and polymeric)% O-hydroxyaryloximes and β - Present as a complex with one or more complexing and/or chelating agents such as diketones.

Known cobalt-containing catalyst systems are also useful. Manganese- and cobalt-containing catalyst systems suitable for the production of polyphenylene ethers are disclosed in various patents and publications and are known to those skilled in the art.

Polyphenylene ethers which are particularly useful for the purposes of the present invention have the formula: %Formula %) in which Ql and Ql have the meanings given above; each R2 has a total number of carbon atoms in the two R2 groups of 6 or less; and each R3 is independently hydrogen or a C1-6 primary alkyl group). It is something that each R2 is hydrogen and each R
It is preferred that 3 is an alkyl group, especially a methyl or n-butyl group.

Polymers containing aminoalkyl substituted end groups of formula (V) are
In particular when using copper- or manganese-containing catalysts, this can be obtained by incorporating the corresponding primary or secondary monoamine as one of the components of the oxidative coupling reaction mixture. Such amines, especially dialkylamines, preferably di-n-butylamine and dimethylamine, are often used to form polyphenylene ethers, often by substituting one of the α-hydrogen atoms on one or more Q1 groups. chemically bonded to. The main reactive site is the Qi adjacent to the hydroxyl group on the terminal unit of the polymer chain.
It is the basis. During subsequent processing and/or compounding steps, the aminoalkyl-substituted end groups undergo various reactions, presumably during which they form quinone methide-type intermediates of the formula, often resulting in improved impact strength and other It provides a number of benefits including increased compatibility with formulation ingredients. Regarding these points, please refer to U.S. Patent No. 4.054.553, U.S. Pat.
No. Z94, No. 4,477.649, No. 4,477
．． No. 651 and No. 4.517.341.

Polymers with 4-hydroxybiphenyl end groups of formula (VI) are typically used especially for steel-halide-secondary or tertiary polymers.
When a grade amine catalyst system is used, a diphenoquinone of the formula: % is obtained from the reaction mixture as a by-product.

In this regard, the above-cited U.S. Pat. No. 4,477.
No. 649 and U.S. Pat. Nos. 4,234.706 and 4,482.69, incorporated herein by reference.
Please refer to the description in Specification No. 7. In mixtures of this type, the diphenoquinone is ultimately bound in substantial proportions into the polymer, primarily as end groups.

In many polyphenylene ethers obtained under the conditions described above, a substantial proportion of the polymer molecules, typically comprising about 90% by weight of the polymer, have one or often both formulas (V) and (Vl). Contains terminal groups. However, it should be understood that other end groups may be present and that the present invention does not depend in a broad sense on the molecular structure of the polyphenylene ether end groups, so long as a substantial proportion of free hydroxy groups are present. .

The use of polyphenylene ethers containing significant amounts of unneutralized amino-type nitrogen atoms generally results in compositions with undesirably low impact strength.

Possible reasons for this point will be discussed later. In addition to the aminoalkyl terminal group mentioned above, amino compounds have
It includes trace amounts of amines (particularly secondary amines) in the catalysts used in the production of polyphenylene ethers.

Accordingly, the present invention includes the use of polyphenylene ethers from which a substantial proportion of the amino compounds have been removed or inactivated. The treated polymer contains less than 800 pp of unneutralized amino nitrogen, if any at all.
In an amount not exceeding 1 liter, more preferably about 100 to 800 liters
It is contained in an amount in the range of ppIII.

One preferred method for passivation is by extruding the polyphenylene ether at a temperature in the range of about 230 DEG to 390 DEG C. under vacuum.

This is done during the pre-extrusion step (sometimes this method is preferred)
Alternatively, this can be accomplished by connecting the extruder vent to a vacuum pump capable of producing a pressure of about 200 torr or less during the extrusion process of the composition of the invention.

This inactivation method eliminates any traces of free amines (especially the This is thought to promote the removal of secondary amines by evaporation.

From the foregoing, it will be clear to those skilled in the art that polyphenylene ethers that can be used in the present invention include all presently known polyphenylene ethers, regardless of variation in structural units or incidental chemical properties.

The end groups on the polyphenylene ether with epoxy triazine end groups have formula (n). In formula (II), Ql and Ql are as defined above. X is an alkyl or cycloalkyl group, typically a lower alkyl group, especially a primary or secondary lower alkyl group; an aromatic group, typically monocyclic and containing 6 to 10 carbon atoms It can be an aromatic group, especially an aromatic hydrocarbon group; or a group of formula (III). In formulas (n) and (m), R1 can be aliphatic, cycloaliphatic, aromatic (including aromatic groups with art-recognized substituents), or heterocyclic groups. R1 is usually a lower alkylene group, especially a methylene group.

The aforementioned polyphenylene ether composition with epoxytriazine end groups comprises at least one polyphenylene ether and an epoxychlorotriazine of the formula: (wherein R1 and can be produced by contacting in the presence of

A typical epoxychlorotriazine of formula (IX) is 2-
Chlor-4,6-siglycidoxy-1.3゜5-triazine, 2-chloro-4-(n-butoxy)-6-glycidoxy-1,3-5-triazine and 2-chloro-4-
Includes (2,4,6-trimethylphenoxy)-6-glycidoxy-1,3,5-triazine. These compounds can also be named as derived from cyanuric acid, diglycidyl chlorocyanurate, n-
Butylglycidylchlorcyanurate and 2,4゜6-
It is called trimethylphenylglycidyl chlorocyanurate. For convenience, these will be referred to as "DGCC,""BGCC," and "MGCC" below, respectively.
It is sometimes abbreviated as. These compounds include, for example, 2,
4.6-Trichlortriazine (cyanuric acid chloride)
and glycidol or a mixture of glycidol and n-butanol or meditol. Both cyanuric chloride and n-butyl dichlorocyanurate are commercially available.

Intermediates such as DGCC%BGCC and MGCC and methods for their preparation are described in Applicant's own US Patent Application No. SN filed January 19, 1988.

No. 144.901. Examples of the preparation of these compounds are illustrated by the following examples.

Example 1 220 ml of cyanuric acid chloride in 1500 ml of chloroform cooled to 0-10°C. Glycidol 266 was added to a mechanically stirred 8 g (1.2 mol) solution.
．． 4 g (3.6 mol) were added in batches. While stirring this mixture, the reaction temperature was kept at 10°C or less, preferably 0°C.
While maintaining the temperature at about ~5°C, aqueous sodium hydroxide solution (50% solution; 192 g) was added to the mixture for about 3 hours. After the reaction mixture was slowly warmed to room temperature, the chloroform layer was washed with distilled water until neutral and dried over magnesium sulfate. The reaction product was determined by proton nuclear magnetic resonance spectroscopy to be 2-chloro-4°6-siglycidoxy1. 3. 5-) It was confirmed to be riazine (DGCC). Analysis by liquid chromatography showed a chlordiglycidoxytriazine content of about 95% by weight. The reaction mixture was also found to contain small amounts of triglycidoxytriazine and dichloroglycidoxytriazine.

Example 2 n in 757 ml of chloroform cooled to 0-10°C
250 g (3,375 mol) of glycidol were added to a mechanically stirred solution of 250 g (1,125 mol) of butyl dichlorocyanurate in one portion. An aqueous sodium hydroxide solution (
50% solution; 90 g) was added dropwise over about 2 hours. After the reaction mixture was brought to room temperature over about 30 minutes, the chloroform layer was washed with distilled water until neutral and dried over magnesium sulfate. Proton nuclear magnetic resonance analysis is 2-chloro-4-(n-butoxy)-6-glycidoxy-1,3
The yield of ,5-triazine (BGCC) was 95%.

Example 3 2.2% in 170 ml of methylene chloride cooled to 0-10°C.
4. A mechanically stirred solution of 50 g (0,175 mol) of 6-trimethylphenyldichlorocyanurate (prepared by reaction of equimolar amounts of meditol and cyanuric acid chloride) is treated with 26.38 g of glycidol.
g (0,356 mol) were added at a time. To this mixture was added an aqueous sodium hydroxide solution (50% solution; 14, Z6g) over about 25 minutes while stirring and maintaining the reaction temperature between θ°C and 10°C, preferably between about 0 and 5°C. Added dropwise. After stirring for an additional 30 minutes, the reaction mixture was allowed to warm to room temperature. The methylene chloride layer was washed with distilled water until neutral and dried over magnesium sulfate. This reaction product was determined to be 2-chloro-4 by proton nuclear magnetic resonance analysis.
-(2,4,6-trimethylphenoxy)-6-glycidoxy-1,3,5-1-riazine (MGCC).

Various options are possible for the reaction between polyphenylene ether and epoxychlorotriazine. In one method, the reaction is carried out in a solution of a non-polar organic liquid, typically from about 80 to 150°C, preferably from about 100 to 125°C.
It is carried out at a temperature in the range of . The basic reagent used in this method should be soluble in the organic liquid and is generally a tertiary amine. Otherwise, the type of basic reagent is not critical, as long as it is sufficiently non-volatile to be retained in the reaction mixture at the temperature used. The use of pyridine is often preferred.

The amount of epoxychlortriazine used in this process generally ranges from about 1 to 20% by weight, based on the polyphenylene ether. The amount of the basic reagent to be used is an amount effective to promote the reaction, and usually about 1.0 to 1.1 equivalent per mole of epoxychlorotriazine is suitable.

Polyphenylene ethers with epoxy triazine end groups formed in solution by the methods described above generally contain a moderately high proportion of chemically bound chlorine, primarily covalently bound chlorine (e.g., at least about 0.4
% by weight). The presence of covalently bonded chlorine is believed to be the result of competitive reaction of the epoxy group with the organic base as a hydrogen chloride acceptor to form the chlorohydrin moiety. Subsequently, the chlorohydrin moiety may be condensed with another epoxy group to form species such as polyphenylene ether-epoxy triazine block copolymers and homopolymeric epoxy triazine oligomers. Because of the existence of such molecular species, polyphenylene ether compositions with epoxy triazine end groups are also conveniently defined by their method of preparation.

Compositions containing polyphenylene ether copolymers made from products containing such species can be molded to produce products that are ductile but have somewhat lower impact strength than desired under certain conditions. Form.

This is especially true for copolymers with polyesters.

A second preferred process produces polyphenylene ethers with epoxy triazine end groups containing little or no covalently bonded chlorine. In this method, the reaction takes place at an interface in a medium comprising water and an organic liquid as described above. The chlorinated reagent is a water-soluble base, typically an alkali metal hydroxide, preferably sodium hydroxide. Additionally, phase transfer catalysts are also used. Any catalyst that is stable and effective under the reaction conditions used may be used, and selection of a suitable catalyst will be within the skill of those skilled in the art. Particularly preferred catalysts are tetraalkylammonium chlorides in which at least two, typically two or three, alkyl groups per molecule contain about 5 to 15 carbon atoms.

Reaction temperatures in the range of about 20-70°C may be used in this method. The amount of epoxy triazine used may often be less than in the processes described above, typically ranging from about 1 to 5% by weight, preferably from about 2 to 5% by weight, based on the polyphenylene ether. This is because the reaction between epoxychlorotriazine and polyphenylene ether proceeds significantly more completely. Often the ratio of the number of equivalents of base to the number of moles of epoxychlortriazine is about 1.0-1.5:1 and the weight ratio of phase transfer catalyst to base is about O11-0.3:1. .

Still other methods use an organic liquid and a solid base, typically a solid alkali metal hydroxide or an anion exchange resin in free base form. Chloride salts can be removed by methods known to those skilled in the art, including washing with water when using hydroxides and filtration when using anion exchange resins.

Regardless of the manufacturing method used, polyphenylene ethers with epoxytriazine end groups can be prepared by conventional methods,
Typically, it can be isolated by precipitation using a non-solvent. Representative examples of non-solvents that can be used include methanol, 2-propanol, acetone, acetonitrile and mixtures thereof.

When the non-solvent is an alcohol, especially methanol, the alcohol can undergo a base-promoted reaction with the epoxy triazine moiety on the end-grouped polyphenylene ether, usually resulting in the loss of epoxy groups. Either or both of two methods of operation can be used to prevent this reaction. The first method of operation is to neutralize the reaction mixture with any convenient acidic compound, the use of gaseous, liquid or solid carbon dioxide being often preferred.

The second mode of operation is one in which the alcohol in contact with the product is removed as quickly and completely as possible by conventional means, typically including a subsequent drying step.

The following examples illustrate the preparation of polyphenylene ethers with epoxy triazine end groups, in which all parts and percentages are by weight unless otherwise indicated.

The proportion of epoxychlorotriazine is expressed as a percentage of polyphenylene ether. The following polyphenylene ether was used.

In PPE-chloroform at 25°C, constant 0.40
Poly(2,6-dimethyl-1) with an intrinsic viscosity of dl/H
, 4-phenylene ether) VV-PPE - approximately 260-320°C with evacuation to a maximum pressure of approximately 20 Torr.
PP extruded in a twin screw extruder within the temperature range of
ELN - poly(2,6-dimethyl-
(1,4-phenylene ether) The proportion of epoxy triazine in a polymer with an end group added is determined by the relative area of the peaks derived from the hydrogen atoms in the epoxy moiety and the hydrogen atoms in the aromatic moiety in the nuclear magnetic resonance spectrum. It was measured from

The percentage proportion of chlorine was determined by quantitative X-ray fluorescence analysis.

Examples 4-14 Polyphenylene ether 40 in 2500 ml toluene
Adding various amounts of pyridine to 0 g of solution under stirring,
Various amounts of epoxychlorotriazines were then added in small portions. The ratio of the number of equivalents of pyridine to the number of moles of epoxychlorotriazine was 1°04:1. The solutions were heated under reflux for various periods, after which the products were precipitated with methanol in a blender, filtered, washed with methanol and dried in vacuo. The necessary related parameters and analysis results are shown in Table 1.

Examples 15-25 Polyphenylene ether 4 in toluene 250 On+1
To 00 g of solution were added various amounts of epoxy chlortriazines dissolved in a small amount of methylene chloride. Then 48 g of a 10% solution of commercially available methyltrialkylammonium chloride containing 8 to 10 carbon atoms in the alkyl group dissolved in toluene and 1.3 equivalents of sodium hydroxide per mole of epoxychlortriazine were added. A corresponding amount of 10% aqueous sodium hydroxide solution was added.

These mixtures were stirred vigorously at 25-40° C. for various periods, after which the products were precipitated with methanol in a blender, the precipitate was immediately filtered, washed with methanol and dried in vacuo.

The results are shown in Table ■. The chlorine content was below 200 ppI11, the lowest value measurable by quantitative X-ray fluorescence analysis.

Any polyester comprising units of formula (1) may be used in making the polyphenylene ether-polyester copolymers of the present invention. These include thermoplastic polyesters, examples of which include poly(alkylene dicarboxylates), elastomeric polyesters, polyarylates and polyester copolymers such as copolyester carbonates. It is highly preferred that the polyester has a relatively high concentration of carboxylic acid end groups since the primary reaction that occurs with the epoxy groups in the end-grouped polyphenylene ether involves the carboxylic acid groups of the polyester. Approximately 5-25 per gram
Concentrations in the range of 0 microequivalents are generally suitable, preferably 10 to 100 microequivalents ffi/g, more preferably 30 to 100 microequivalents ffi/g, particularly preferably 40 to 80 microequivalents/g.

The polyester may contain structural units of the formula: %%( ), where R4 is as defined above, R5 is a polyoxyalkylene group, and A2 is a trivalent aromatic group. The A1 group in formula (I) is often a p- or m-phenylene group or a mixture thereof and the A2 group in formula (X) is usually derived from trimellidic acid and has the structure:

The R4 group is, for example, a C2-10 alkylene group, a C6-10
It can be an alicyclic group, a C6-20 aromatic group, or a polyoxyalkylene group containing about 2 to 6 carbon atoms, often 4 carbon atoms in the alkylene group. As mentioned above,
This group of polyesters includes poly(alkylene terephthalates) and polyarylates. Poly(alkylene terephthalate) is often preferred, with poly(ethylene terephthalate) and poly(butylene terephthalate) being most preferred.

Polyester generally contains 60% by weight phenol and 1.
1. 2. It has a number average molecular weight in the range of about 20,000 to 70,000 as measured by intrinsic viscosity (IV) at 30°C in a mixture of 40% by weight 2-tetrachloroethane.

Either solution or melt mixing methods can be used for the production of polyphenylene ether-polyester copolymers.

Typical reaction temperatures range from about 175-350°C. Therefore, for solution reactions, relatively high boiling point solvents such as 0-dichlorobenzene or 1,2,4-trichlorobenzene are preferred.

Melt reaction methods are often preferred due to the availability of melt mixing equipment in commercial polymer processing facilities. Conventional equipment of this type may be suitably used, and the use of extruders is generally convenient and therefore often preferred.

The main reaction that occurs between polyphenylene ethers and polyesters having epoxy triazine end groups is generally the opening of the epoxide ring by the carboxylic acid end groups of the polyester to form hydroxy ester groups. Accordingly, one preferred embodiment of the present invention is of the formula: Zl is an OH group and 23 is 10-0-, or Zl is 10-C- and 23 is an OH group] A polyphenylene ether-polyester copolymer containing a molecule containing at least one polyphenylene ether-polyester bond.

Another possible reaction is the reaction between the hydroxy end groups of the polyester and the epoxy groups of the end-grouped polyphenylene ether. Therefore, the composition of the invention has the formula (XI)
The present invention is not limited to compounds containing a bond of z2 or Z3, but may include compounds having a bond of a similar structure containing an ether moiety in place of the carboxylate moiety of z2 or Z3.

The proportions of polyphenylene ether and polyester used in making the compositions of this invention are not critical and these proportions can be varied over a wide range to provide compositions with desired properties. Often each polymer will be about 5 to 50% of the composition.
It is used in an amount of 95% by weight, preferably in the range of about 30-70%.

In many cases, the compositions of the invention contain, in addition to the copolymers, various proportions of the respective homopolymers of polyphenylene ether and polyester. This may be the result of excess polyester or unfunctionalized polyphenylene ether being present in the composition, or incomplete addition of end groups to the polyphenylene ether, or the combination of end-grouped polyphenylene ether and polyester. This may be the result of an incomplete reaction. In any case, the molded articles made from the compositions are generally more ductile and better than those made from simple polyphenylene ether-polyester blends, which, as mentioned above, are incompatible and often delaminate. It also has high impact strength.

Experimental data suggested that certain other factors are important in producing compositions with the highest impact strength. One of these factors is the proportion of chlorine in the polyphenylene ether with epoxy triazine end groups. Compositions of the present invention made from end-grouped polyphenylene ethers with high chlorine content obtained by solution processes such as those described above often have lower impacts than compositions made from materials with lower chlorine contents obtained by interfacial processes. Have strength.

Another factor is the proportion of unneutralized amino nitrogen in the polyphenylene ether. If this ratio is high, side reactions may occur, including opening of the epoxide ring, detachment of the epoxide group from the cyanurate molecular moiety, and cleavage of the ester bond. Such side reactions can be suppressed to a minimum by evacuation of the polyphenylene ether as described above.

The third factor is the molecular structure of the polyphenylene ether-polyester copolymer, and this is due to the molecular structure of the capping agent used (the molecular structure of BGCC or MGCC is DG).
(considerably different from that of CC) and their proportions (achieving the addition of end groups to one or both ends of the polyphenylene ether). For example, the following schematic structure of a copolymer can be shown. In the formula, PPE and PE represent polyphenylene ether and polyester, respectively.

(Xll) PPE-PE (Xm)
The structure represented by the PE-PPE-PE formula (Xv) can theoretically be obtained by capping, for example, polyphenylene ether having hydroxyl groups at both ends of the polymer chain in at least a stoichiometrically equivalent proportion (for example, using DGCC). You can get it by doing this.

For example, a polyphenylene ether having a number average molecular weight of about 20,000 containing at least about 1.9% by weight epoxy triazine would be expected to provide a copolymer of formula (XV). In the copolymer of formula (XV), the PPE part of the molecule is probably obscured by the PE part,
Therefore, because the effect for compatibilization of polyphenylene ether-polyester blends is low,
It has reduced physical properties compared to copolymers with structures represented by -(XIV).

Also, compositions containing "high chlorine content" end-grouped polyphenylene ethers tend to have higher ductility and higher impact strength when using polyphenylene ethers containing a lower proportion of unneutralized amino-type nitrogen. The reason for this is currently unknown.

The compositions of the present invention may contain other ingredients besides polyphenylene ether, polyester and copolymers. Examples of such other components are elastomeric impact modifiers that are compatible with either or both polyphenylene ethers and polyesters.

Suitable impact modifiers include a variety of elastomeric copolymers, examples of which are unfunctionalized and (for example) ethylene-propylene-diene polymers (E) functionalized with sulfonate or phosphonate groups. PDM polymers); carboxylated ethylene-propylene rubber; polymerized cycloalkenes; polymerizable olefins or dienes of alkenyl aromatic compounds such as styrene and polymerizable olefins or dienes, including butadiene, isoprene, chlorobrene, ethylene, propylene, and butylene. and a core-shell elastomer comprising a poly(alkyl acrylate) core bonded to a polystyrene shell by interpenetrating network bonds (more specifically, U.S. Pat. No. 4,681;
915)).

Preferred impact modifiers are block copolymers (typically diblock, triblock or radial teleblock copolymers) of alkenyl aromatic compounds and dienes. Often at least one block is derived from styrene and at least one other block is derived from at least one of butadiene and isoprene. Particularly preferred are triblock copolymers with polystyrene end blocks and a central block derived from a diene. It is often advantageous to remove (preferably) or reduce the aliphatic unsaturation present in the copolymer by selective hydrogenation. The weight average molecular weight of the impact modifier typically ranges from about 50,000 to 300,000. Block copolymers of this type are commercially available from Shell Chemical Company under the registered trademark "Kraton" and are known as Kraton DIIOI.
.

G1650. G1651. G1652. Includes G1657 and G1702.

The presence of polymers such as polycarbonates, copolyester carbonates or polyarylates has the effect of improving the impact strength of molded articles under harsh molding conditions such as high molding temperatures and/or long molding cycle times. may have. For the same purpose, at least one compound containing multiple epoxide molecular moieties (hereinafter referred to as "polyepoxide") is generally used in an amount of about 0.1% to 3.0%, preferably about 0% to 3.0% of the composition. This is often achieved by compounding. Examples of compounds of this type are homopolymers of compounds such as glycidyl acrylate and glycidyl methacrylate, as well as copolymers thereof; preferred co-11mers are lower alkyl acrylates, methyl methacrylate, acrylonitrile and styrene.

Epoxy-substituted cyanurates and in cyanurates such as triglycidyl isocyanurate are also suitable for a.

The polyepoxide can be introduced by combining with the other ingredients in a single operation. However, its effectiveness is limited by premixing with polyester, typically by dry blending,
It can then be maximized by extrusion treatment. Such premixing often increases the impact strength of the composition. The reason for the effectiveness of polyepoxides is not completely understood, but it is believed that it increases the molecular weight, melt viscosity, and degree of branching of the polyester by reaction with some of the carboxylic acid end groups of the polyester molecule.

Finally, conventional ingredients such as fillers, flame retardants, pigments, dyes, stabilizers, antistatic agents, crystallization aids, mold release agents, etc., as well as resin ingredients not mentioned above, can be added to the compositions of the invention. can be caused to exist.

In the following examples illustrating the preparation and properties of polyphenylene ether-polyester copolymer compositions of the present invention, the types of polyesters and impact modifiers used are as follows.

PET one poly(ethylene terephthalate PBT-approximately 50,0 as determined by gel permeation chromatography)
Poly(butylene terephthalate) with a number average molecular weight of 00 PATME - commercially available elastomeric polyterephthalate PTME obtained from a mixture of tetramethylene glycol, hexamethylene glycol and poly(tetramethylene ether) glycol (50,000) and PTME (54゜0
00) - obtained from a mixture of tetramethylene glycol and poly(tetramethylene ether) glycol, ()
commercially available elastomeric polyterephthalate PIE-1,4- having a number average molecular weight as shown in Table 1 and having about 20% by weight and about 20% by weight of tetramethylene glycol units and poly(tetramethylene ether) glycol units, respectively. Copolyester 5EBS-29 prepared from butanediol and a 0.9141 (weight ratio) mixture of diimide-diacid reaction products of dimethyl terephthalate and trimellidic acid with polyoxypropylene diamine having an average molecular weight of about 2000, Commercially available triblock copolymer CS consisting of polystyrene end blocks with a weight average molecular weight of 1,000 and a hydrogenated butadiene center block with a weight average molecular weight of 116,000 - US Pat. No. 4,684,696 A core-shell type material P containing a 75% crosslinked poly(butyl acrylate) core and a 25% crosslinked polystyrene shell prepared in accordance with the specification P - polyoctenylene in a cis-trans ratio of 20:80 with a weight average molecular weight of about 55,000 The resin formulation is dry mixed and heated at 190-255°C.
, 400 rpm on a twin screw extruder. These extrudates were quenched in water, pelletized and shaped into specimens at 280°C. These specimens were tested for notched isot impact strength and tensile properties (ASTM test methods D256 and D, respectively).
638) and heat distortion temperature at 0.455 MPa (according to ASTM test method D648).

In the following examples, all parts and percentages are by weight. The proportions of bound polyphenylene ether shown in the table were determined by extracting uncopolymerized polyphenylene ether with toluene and measuring the proportion of polyphenylene ether in the residue by nuclear magnetic resonance spectroscopy. This number is a general guide to the amount of copolymer in the composition.

Examples 26-35 Compositions containing epoxy triazine terminated polyphenylene ether prepared as described in Examples 4-14, various polyesters, and 5EBS in various proportions were prepared and molded. Related parameters and test results are shown in Table ■.

Examples 36-47 Compositions were prepared and molded from the epoxy triazine terminated polyphenylene ethers of Examples 15-25, PBT and 5EBS. Related parameters and test results are shown in Table ①.

Examples 48-49 Compositions similar to those of Examples 18 and 24 were prepared and molded, except that 18 parts of PPE were replaced with an equal weight of polyphenylene ether with epoxy triazine end groups. The relevant test results are shown in Table V.

Table V Example No.

End-grouped polyphenylene ether Izot impact strength, Joule 7 m Tensile strength, MPa Yield point Tensile elongation at break, % Example 18 44.7 35.1 Example 24 44, Z 36.8 Examples 50-57 Polyphenylene ether with epoxy triazine end groups, PET and (in the case of Examples 50-55) SEBS
A composition was prepared and molded.

In one particular case, the 'PET was previously extruded and dried at 271°C to increase the proportion of carboxylic acid end groups. The following PET was used.

“Kodapak 7352'
(Manufactured by Eastman Kodak Company) °Vltuf' 1001A= (
Manufactured by Goodyear Chemical Co.) “Rohm &! Iaas) 5
202 A" recycled bottle scrap, number average molecular weight approximately 40,000. Relevant parameters and test results are shown in Table 2.

Examples 58-61 Polyphenylene ether with epoxy triazine end groups of Example 18, PBT, bottle scrap PET and (
For Examples 58-60) Compositions containing SEBS were prepared and molded. Related parameters and test results are shown in Table ①.

Table ■ Example No.

End group-added polyphenylene ether, part polyester, part PBT PET SEBS % Izot impact strength, Joule 7 m Tensile strength, MPa Yield point Tensile elongation at break, % 43.9 41.6 44.5 4B, 142. 3 4
0.8 39. B40. [1 Example 62-64 Same as Example 18, epoxy triazine 0.75
A composition containing -0.85% of epoxy triazine terminated polyphenylene ether, PBT and CS or PO was prepared and molded. Related parameters and test results are shown in Table ①.

Table ■ Examples Target end-grouped monomethyl polyphenylene, part PBT, part impact modifier, part CS PO Izod impact strength, Joule 7 m Tensile strength Yield point Breaking point 4B, 7 44.7 41.9 40 .8 41.4 34.9 Tensile elongation, % 134 135 70
Heat Distortion Temperature, 'C-156162 Examples 65-74 Polyphenylene ethers functionalized with epoxy triazine end groups, various elastomeric polyesters and
In the case of Examples 65-71) 5E as impact modifier
A composition containing BS was prepared and molded. Related parameters and test results are shown in Table ①.

Examples 75-80 Epoxytriazine terminated polyphenylene ether of Example 18, containing mixtures of PBT and various elastomeric polyesters and (in the case of Examples 75-79) 5EBS as impact modifier A composition was prepared and molded. The relevant parameters and test results are shown in Table X.

Claims (1)

[Claims] 1. Polyphenylene ether with an epoxy citriazine terminal group and the formula: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^4 is a divalent aliphatic or alicyclic group. or an aromatic hydrocarbon group or a polyoxyalkylene group, and A^1
is a divalent aromatic group). 2. Polyphenylene ether has the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, each Q^1 is independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, carbonized Hydrogenoxy or a halohydrocarbonoxy group having a structure in which a halogen atom and an oxygen atom are separated by at least two carbon atoms; each Q^2 is independently hydrogen, halogen, primary or secondary 2. The composition of claim 1, comprising a number of structural units having a lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy group as defined for Q^1. 3. Formulas: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(X I) (In the formula, Q^1 and Q^2 have the above meanings; R^1
is a divalent aliphatic, alicyclic, heterocyclic, or unsubstituted or substituted aromatic hydrocarbon group; ▼And; and Z^
2 is OH and Z^3 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or Z^2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and Z^3
3. The composition of claim 2, comprising at least one polyphenylene ether-polyester bond, wherein is OH. 4. The composition according to claim 3, wherein A^1 is a p- or m-phenylene group or a mixture thereof. 5. The composition according to claim 4, wherein R^1 is a lower alkylene group. 6. The composition according to claim 5, wherein the polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene ether). 7. The composition according to claim 6, wherein R^1 is a methylene group and A^1 is a p-phenylene group. 8. The composition according to claim 7, wherein Z^1 is a lower alkyl group or an aromatic hydrocarbon group. 9. The composition according to claim 8, wherein Z^1 is an n-butyl group or a 2,4,6-trimethylphenyl group. 10. The composition according to claim 7, wherein Z^1 is a group ▲, which has a mathematical formula, a chemical formula, a table, etc. 11. The composition according to claim 7, wherein R^4 is an ethylene group. 12. The composition according to claim 7, wherein R^4 is a tetramethylene group. 13. The composition according to claim 7, wherein R^4 is a polyoxytetramethylene group. 14. The composition of claim 7 further comprising an elastomeric impact modifier. 15. The composition according to claim 14, wherein the impact modifier is a triblock copolymer comprising end blocks derived from styrene and a central block derived from at least one of isoprene and butadiene. 16. The composition of claim 15, wherein aliphatic unsaturation in the central block is removed by selective hydrogenation. 17. Polyester further has the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(X) (In the formula, R^4 has the above meaning, R^5 is a polyoxyalkylene group, and A^2 is 8. The composition according to claim 7, which also contains a structural unit of trivalent aromatic group. 18, Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^4 is a divalent aliphatic, alicyclic or aromatic hydrocarbon group or a polyoxyalkylene group, and A^ 1
is a divalent aromatic group) and at least one polyphenylene ether in the presence of a basic reagent under reactive conditions. ▼(IX) (wherein, cyclic, heterocyclic, or unsubstituted or substituted aromatic hydrocarbon group)
A composition comprising a polyphenylene ether-polyester copolymer prepared by contacting the composition with an epoxychlorotriazine. 19, A^1 is p- or m-phenylene group or a mixture thereof and polyphenylene ether is poly(2
, 6-dimethyl-1,4-phenylene ether). 20. The composition according to claim 19, wherein R^1 is a methylene group and A^1 is a p-phenylene group. 21. The composition of claim 20 further comprising an elastomeric impact modifier.