CA2033847A1 - Capped polyphenylene ethers - Google Patents
Capped polyphenylene ethersInfo
- Publication number
- CA2033847A1 CA2033847A1 CA 2033847 CA2033847A CA2033847A1 CA 2033847 A1 CA2033847 A1 CA 2033847A1 CA 2033847 CA2033847 CA 2033847 CA 2033847 A CA2033847 A CA 2033847A CA 2033847 A1 CA2033847 A1 CA 2033847A1
- Authority
- CA
- Canada
- Prior art keywords
- polyphenylene ethers
- carbon atoms
- capped
- capped polyphenylene
- ethers according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT
Capped polyphenylene ethers or mixtures thereof prepared by reacting polyphenylene ethers composed of the following units wherein Q1 and Q2 are hydrocarbyl radicals having 1 to 10 carbon atoms, Q3 and Q4 are hydrogen or hydrocarbyl radicals having 1 to 10 carbon atoms with from about 0.5 to about 10% by weight, relative to the polyphenylene ethers, of imides of the general formula
Capped polyphenylene ethers or mixtures thereof prepared by reacting polyphenylene ethers composed of the following units wherein Q1 and Q2 are hydrocarbyl radicals having 1 to 10 carbon atoms, Q3 and Q4 are hydrogen or hydrocarbyl radicals having 1 to 10 carbon atoms with from about 0.5 to about 10% by weight, relative to the polyphenylene ethers, of imides of the general formula
Description
, -- 1 -- . .
~~ 3 3 ~
CAPPED POLYPHENYLENE ETHERS :
.
The present invention relates to polyphenylene ethers which have been capped ln a novel manner and at the same time stabilized and to mixtures containing said polyphenylene ethers, to a process for their preparation and to moulding compositions which contain capped polyphenylene ethers of this type. ~ ~
Polyphenylene ethers (PPE) are a known category of ~`
polymers which have very good physical and chemical properties, in particular a high heat distortion temperature and very good resistance to hot water, acids and aqueous alkalis.
A disadvantage of these polyphenylene ethers is their deficient stability not only under heat stress but also on relatively long exposure to oxidlzing influences during process-ing or use. Thermal or oxidative damage o~ this type has an adverse effect not only on the colour oE the product but also on ;~
the mechanical properties and the processibility. Capping o~
the hydroxyl groups present in the polyphenylene ether prevents the oxidation of these groups giving a significant improvement ~i in the oxidative and thermal stability.
Various processes have hitherto been described for capping polyphenylene ethers, for example those in German Published Patent Applications 2,505,329, 2,822,857, 2,822,859 and 2,822,434. The processes described therein are all carried out in solution using a large excess of capping agent. The substrates chiefly used are acylating reagents such as, for example, acetyl chloride or acetic anhydride, i.e. aggressive and corrosive compounds. As a rule, the resulting acid must be ~-.. ,:
. .. .
. .
~ . ,.
: :.-, .. . . . - : , .
: .. ,:, . : . - , : . . . . , . - : .. ~, .
~~ 3 3 ~
CAPPED POLYPHENYLENE ETHERS :
.
The present invention relates to polyphenylene ethers which have been capped ln a novel manner and at the same time stabilized and to mixtures containing said polyphenylene ethers, to a process for their preparation and to moulding compositions which contain capped polyphenylene ethers of this type. ~ ~
Polyphenylene ethers (PPE) are a known category of ~`
polymers which have very good physical and chemical properties, in particular a high heat distortion temperature and very good resistance to hot water, acids and aqueous alkalis.
A disadvantage of these polyphenylene ethers is their deficient stability not only under heat stress but also on relatively long exposure to oxidlzing influences during process-ing or use. Thermal or oxidative damage o~ this type has an adverse effect not only on the colour oE the product but also on ;~
the mechanical properties and the processibility. Capping o~
the hydroxyl groups present in the polyphenylene ether prevents the oxidation of these groups giving a significant improvement ~i in the oxidative and thermal stability.
Various processes have hitherto been described for capping polyphenylene ethers, for example those in German Published Patent Applications 2,505,329, 2,822,857, 2,822,859 and 2,822,434. The processes described therein are all carried out in solution using a large excess of capping agent. The substrates chiefly used are acylating reagents such as, for example, acetyl chloride or acetic anhydride, i.e. aggressive and corrosive compounds. As a rule, the resulting acid must be ~-.. ,:
. .. .
. .
~ . ,.
: :.-, .. . . . - : , .
: .. ,:, . : . - , : . . . . , . - : .. ~, .
~3443-444 2~3384~ ~
bound by an added base, this complicating the course of the ; process and the working-up.
Capping in the melt gives a considerably increased space-time yield. A process of this type is described in U. S.
Patent 3,375,228; the capping agents used are acid chlorides, acid anhydrides or ketenes. Owing to the severe corrosion problems which occur in this process, and to the use of toxico-logically harmful reagents, this process has remained industrially insignificant.
Another method of capping in the melt is described in European Published Patent Application 0,283,775. In this procedure, the polyphenylene ethers are treated in the melt with salicylic aaid or anthranilic aoid derivatlves. rrhe linear polysalicylates and salicyl carbonate are said to be particularly efficient for this purpose. However/ virtually complete capping is only achieved using large amounts of capping agent (10% by weight relative to PPE), this being associated with a pronounced but inconvenient reduction in the glass transition temperature (see the examples in Table II in the above-cited document).
Furthermore, in the reaction with salicylic acid derivatives a hydroxyl-free product is invariably not obtained, since OH groups are formed by reactions of the capping agent. However, or some applications, the absence of OH groups is desirable.
Finally, European Published Patent Application 0,232,716 describes a process for stabilizing polyphenylene ethers , .
in which the reaction is carried out using a laxge excess of an NH-containing compound. Examples of compounds of this type are amidines, amides, cyclic imides, sulphonamides and amino acids, .
''.' :
:. , .. . :
, ~: .:,. ~ :
. , : , . . : ::::
.::: . : ~ : - :
, - 3 23~43-4442 ~338 preference being given to ~-caprolactam. As is shown by the examples, in this procedure considerable amounts of these compounds are used, this subsequently necessitating a troublesome purification pr~cess. Moreover, the "stabLlized" po~yphenylene ether which has been prepared in this manner is only stable up ~ -to 290C however, this temperature is often exceeded under compounding and processing conditions.
The object of the present invention is thereore to provide a simple-to-operate process which allows the capping of 10 polyphenylene ethers using substances which are not aggressive or corrosive, the resulting capped polyphenylene ethers having increased oxidative and thermal stability. In particular, the significant increase in molecular weight on first melting the freshly prepared polyphenylene ether must be suppressed.
This object i5 aahieved by a process in whiah the polyphenylene ether is treated with certain imides at tempera-tures of 230 to 330C. The invention also provides the stahilized polyphenylene ethers according to the invention which have been prepared in this manner and moulding compositions based thereon.
.: .. .
The starting materials for the process according to the invention are polymers which are composed of the following units:
-0~
~2 Q4 ;",~ .
:' ~;
. . .
., .
,~ . : ,- . . . . . , - :
. . . . . ~.: .
~, 2~3~8~7 In this formula, Ql and Q2 are alkyl radicals having l to 10 carbon atoms, which are preferably primary alkyl radicals, cyclo-alkyl radicals having 5 to 10 carbon atoms J benzyl radicals having 7 to 10 carbon atoms or aryl radica:Ls having 6 to 10 carbon atoms. Q3 and Q4 may have the same meaning as Ql and Q2;
however, they are preferably hydrogen.
These polyphenylene ethers can be prepared by any appropriate prior-art process. Normally the phenols are oxidat-ively coupled in the presence of a catalyst complex using an oxygen-containlng gas such as, for example, air. If a para-halogenated phenol is used, an adequate amount of acid acceptor must be present. The catalysts used are preferably copper-amine complexe3 or manganese-conkaining systems ~German Published Patent Applications 3,224,691 and 3,224,692 and also U. S.
Patents 3,306~874, 3,306,875 and 4,028,341). ~he visaosity numbers J, determined in accordance with DIN 53 728 in chloroform at 25C are within the range of from 20 to 80 cm3/g (concentra-tion S gJl), preferably in the range of from 40 to 70 cm3/g.
Depending on the preparation, the polyphenylene ethers contain at least one phenolic terminal group.
Examples of monomers which aan be used to prepare these polyphenylene ethers are: 4-bromo-2,6-dimethylphenol, 2-methyl-; 6-ethylphenol, 2,6-diethylphenol, 2-methyl-6-tert-butylphenol, 4-bromo-2,6-diphenylphenol, 2-benzyl-6-methylphenol, 2,6-dibenzylphenol, 2,3,6-trimethylphenol or preferably 2,6-dimethyl-phenol. Obviously, it is also possible to use mixtures of -; phenols of this type.
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2~338~
The capping of the phenolic groups of the polyphenylene ether is carried out uslng saturated, aliphatic, aromatic or mixed aliphatic-aromatic imides which are fully substituted at -~ the nitrogen atom, i.e. have no NH groups. In this procedure, use is made of substances of the general formulae ~O R o ~ ~O 0 ~ R ~ C - N - C - R )n and/or R ~ C - N - J_ R )n ' ; in which Rl - aromatic or saturated aliphatic radical having l to 20 carbon atoms; R2 and R3 = aromatic or preferably saturated allphatic radical havlng 1 to 12 carbon atoms; R4 - ~CH2)m where m = 3 to ll; n = l to 3; preferably l or 2.
Examples of suitable substances of this type are N-benzoyl-N-methylacetamide, N-acetyl-~-caprolactam, N-ben~oyl-~-caprolactam, N-benzoyllaurolactam, N,N'-isophthaloylbis-E-caprolactam or N,N'-terephthaloylbis-6-caprolactam and N,N'-isophthaloylbislaurolactam or N,N'-terephthaloylbislaurolactam.
Preference is given to the use of N-benzoyllaurolactam, N-benzoyl-~-caprolactam, N,N'-terephthaloylbislaurolactam and - N,N'-terephthaloylbis-~-caprolactam~
These imides can be prepared by various prior-art processes (see M. K. Akkapeddi et al. in "~ecent Advances in Anionic Polymerization", T. E. Hoegen Esch and J. Smid ~Ed.), ; Elsevier 1987, pp. 318-328).
Although in pursuit of a completely different object, ~ `
European Published Patent Application 0,223,115 has already disclosed the reaction of polyphenylene ethers with (meth)acryl-oyllactams such as, for example, N-methacryloyl-~-caprolactam.
:.' j: :.. . , ~ ` . . , , .,; , ` , , ~'! .
'; ''`'' ` .: . ` "' , ~' "`' , ' " '' ` '' ' :' ` ' ; ~ ' ' ' ~ ' `,, '` ` ' ' ` " ' ` ' :,` ~ ,: ' ,` :
: ' '. ` . , ' ` : . ' _~ - 6 -~38'~7 `
However, it is not apparent from this document that the poly-phenylene ethers which have been treated in this manner would be in any way stabilized. On the contrary, according to the above-cited document relatively highly to fully cross-linked products are obtained, in particular in the absence of styrene polymers.
A person skilled in the art is given no inclication in this document that cross-linking of this type, even in polystyrene-free polyphenylene ethers, is not only suppressed using the lmides according to the invention but, on the contrary, even the molecular weight increase at elevated temperatures can be effectively inhibited.
Precisely this prevention of the molecular weight increase on initially meltlng the xeshly prepared polyphenylene ether is an essential aspeat of the present lnvention. Normally, this molecular weight increase is associated with the formation of branch points; however, this is inconvenient with regard to the mechanical properties of moulded articles produced from the material. In the capped polyphenylene ethers according to the invention, not only the OH terminal groups, as ln known masking reactions, but also the reactive defects of the polymer which are present in the freshly prepared polyphenylene ether, depending on the preparation, seem to have reacted with the capping agent.
The products according to the lnvention have signifiaantly fewer branch points, a feature which can be inferred from the increased crystallizability from dilute toluene solution.
The amount of capping agent used is naturally dependent on the number of hydroxyl groups which are present and the r ' `' .
'...... , ~ , .. . ' ~ . ' ' ~
~' ~"'.. "" ~ ' ' . ''' ' ;' ' " - ' ' ' ' :: , .' : ' ': . ' .
~, . , . , ~ 1-.
.
2 ~ ~ 3 ~
concentration of defects, but varies between 0.5 and 10% by welght, relative to the polyphenylene ether used, preferably between 2 and 6% by weight.
The capping according to the invention can be applied not only to pure polyphenylene ethers but also to polyphenylene ether-containing mixtures. Customary ingredients are, for example, polystyrene, impact-resistant polystyrene, styrene-butadiene copolymers (in the form of random, tapered or block copolymers~ which may optionally have been h~drogenated, poly-' 10 octenamers and/or polyole~ins. Components o~ this type do notnoticeably interfere with capping, but the proportion of polyphenylene ether must advantageously be at least 20% by -~
weight.
The process is carried out at 230 to 330C, preEerably in the melt in a mlxer having a good kneading action. However, it is also possible to operate in the presence of an inert :
solvent, for example diphenyl ether or toluene, optlonally under pressure. ~
The process according to the invention is a method ;~ -which requires a lesser amount of capping agent in comparison with the known processes. If a stoichiometric excess of the capping agent is used, this does not need to be subsequently separated off, since there is no significant reduction in the glass transition temperature Tg. Furthermore, the capping agents ~
used in the said process are easy to handle and toxicologically ~;
harmless. There are no corrosion problems.
The capped polyphenylene ethers according to the . . .
.,' ; ~;
';" ;`:
' .
- `
2~338~
invention are used as components of mouldlng compositions. The other components used can be all those which are customarily used according to the prior art in polyphenylene ether-containlng moulding compositions. These moulding compositions according to the invention also have improved thermal and oxidative stability and also, owing to the stabilization of the molecular weight, , improved processibility. They can be used to produce the identical moulded articles for which known polyphenylene ether- ~-based moulding compositions are used.
The invention is explained in detail in the examples which follow.
Example 1 Preparation o a polyphenylene ether 30 kg of 2,6-dimethylphenol in 30 kg of toluene are added with aeration over a period of 30 minutes to a stirred mixture of 260 kg of toluene, 42.0 kg of methanol, 6.0 kg of :
morpholine, 153 g of CuC12 2H2O (dissolved in 850 g of methanol) ; and also 153 g of di-tert-butylethylene-diamine. After a ..... .
reaction time of 130 minutes, the reaction is terminated by adding a mixture of 75 kg of water, 9 kg of methanol and 300 g of triethanolamine and passing through a stream of CO2. The organic phase is washed twice using on each occasion 125 kg of water and 300 g of triethanolamine at 80C. The product is precipitated using 350 kg of methanol, washed twice with, on ,:, each occasion, 180 kg of methanol and then dried. Yield:
25.8 kg; J = 51 cm3/g . ' . .
.~ .
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:, ~ ~, .: , . . . . . , . ~ . . : :
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- : . :
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Exam les 2 to 6 and A and B ~ 03 3 ~ 4 P ~ _ A Berstorff ZE 25*33 D twin screw extruder is used to melt, mix and granulate, at a set temperature of 290C, the proportions by weight of polyphenylene ether from Example 1 and capping reagent, as given ~ the table. The extrusion is carrled out with degassing in the final zone of the extruder; in every case, the material temperature exceeds 300C.
The Examples A and B are not according to the invention;
they are given only for the purposes of comparison.
The degree of masking is determined using FT-IR
spectroscopy. Reference values are determined from untreated PPE
and rom a product which has been fully capped using acetic anhydrlde.
The glass transition temperature Tg is determined on a ~ Mettler TA 3000 instrument at a heating rate of 10 K/min.
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., O ~ u~ o a) ~ c~ , :'. q) ~ A
.
~'', ,.,,. 4 O
~l ~
bound by an added base, this complicating the course of the ; process and the working-up.
Capping in the melt gives a considerably increased space-time yield. A process of this type is described in U. S.
Patent 3,375,228; the capping agents used are acid chlorides, acid anhydrides or ketenes. Owing to the severe corrosion problems which occur in this process, and to the use of toxico-logically harmful reagents, this process has remained industrially insignificant.
Another method of capping in the melt is described in European Published Patent Application 0,283,775. In this procedure, the polyphenylene ethers are treated in the melt with salicylic aaid or anthranilic aoid derivatlves. rrhe linear polysalicylates and salicyl carbonate are said to be particularly efficient for this purpose. However/ virtually complete capping is only achieved using large amounts of capping agent (10% by weight relative to PPE), this being associated with a pronounced but inconvenient reduction in the glass transition temperature (see the examples in Table II in the above-cited document).
Furthermore, in the reaction with salicylic acid derivatives a hydroxyl-free product is invariably not obtained, since OH groups are formed by reactions of the capping agent. However, or some applications, the absence of OH groups is desirable.
Finally, European Published Patent Application 0,232,716 describes a process for stabilizing polyphenylene ethers , .
in which the reaction is carried out using a laxge excess of an NH-containing compound. Examples of compounds of this type are amidines, amides, cyclic imides, sulphonamides and amino acids, .
''.' :
:. , .. . :
, ~: .:,. ~ :
. , : , . . : ::::
.::: . : ~ : - :
, - 3 23~43-4442 ~338 preference being given to ~-caprolactam. As is shown by the examples, in this procedure considerable amounts of these compounds are used, this subsequently necessitating a troublesome purification pr~cess. Moreover, the "stabLlized" po~yphenylene ether which has been prepared in this manner is only stable up ~ -to 290C however, this temperature is often exceeded under compounding and processing conditions.
The object of the present invention is thereore to provide a simple-to-operate process which allows the capping of 10 polyphenylene ethers using substances which are not aggressive or corrosive, the resulting capped polyphenylene ethers having increased oxidative and thermal stability. In particular, the significant increase in molecular weight on first melting the freshly prepared polyphenylene ether must be suppressed.
This object i5 aahieved by a process in whiah the polyphenylene ether is treated with certain imides at tempera-tures of 230 to 330C. The invention also provides the stahilized polyphenylene ethers according to the invention which have been prepared in this manner and moulding compositions based thereon.
.: .. .
The starting materials for the process according to the invention are polymers which are composed of the following units:
-0~
~2 Q4 ;",~ .
:' ~;
. . .
., .
,~ . : ,- . . . . . , - :
. . . . . ~.: .
~, 2~3~8~7 In this formula, Ql and Q2 are alkyl radicals having l to 10 carbon atoms, which are preferably primary alkyl radicals, cyclo-alkyl radicals having 5 to 10 carbon atoms J benzyl radicals having 7 to 10 carbon atoms or aryl radica:Ls having 6 to 10 carbon atoms. Q3 and Q4 may have the same meaning as Ql and Q2;
however, they are preferably hydrogen.
These polyphenylene ethers can be prepared by any appropriate prior-art process. Normally the phenols are oxidat-ively coupled in the presence of a catalyst complex using an oxygen-containlng gas such as, for example, air. If a para-halogenated phenol is used, an adequate amount of acid acceptor must be present. The catalysts used are preferably copper-amine complexe3 or manganese-conkaining systems ~German Published Patent Applications 3,224,691 and 3,224,692 and also U. S.
Patents 3,306~874, 3,306,875 and 4,028,341). ~he visaosity numbers J, determined in accordance with DIN 53 728 in chloroform at 25C are within the range of from 20 to 80 cm3/g (concentra-tion S gJl), preferably in the range of from 40 to 70 cm3/g.
Depending on the preparation, the polyphenylene ethers contain at least one phenolic terminal group.
Examples of monomers which aan be used to prepare these polyphenylene ethers are: 4-bromo-2,6-dimethylphenol, 2-methyl-; 6-ethylphenol, 2,6-diethylphenol, 2-methyl-6-tert-butylphenol, 4-bromo-2,6-diphenylphenol, 2-benzyl-6-methylphenol, 2,6-dibenzylphenol, 2,3,6-trimethylphenol or preferably 2,6-dimethyl-phenol. Obviously, it is also possible to use mixtures of -; phenols of this type.
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- : . ~ : : - :: . . : .:
.: .. ., .: . : : . .. :
: : . .: , , ::. . . . .
-:. , : :: . .
2~338~
The capping of the phenolic groups of the polyphenylene ether is carried out uslng saturated, aliphatic, aromatic or mixed aliphatic-aromatic imides which are fully substituted at -~ the nitrogen atom, i.e. have no NH groups. In this procedure, use is made of substances of the general formulae ~O R o ~ ~O 0 ~ R ~ C - N - C - R )n and/or R ~ C - N - J_ R )n ' ; in which Rl - aromatic or saturated aliphatic radical having l to 20 carbon atoms; R2 and R3 = aromatic or preferably saturated allphatic radical havlng 1 to 12 carbon atoms; R4 - ~CH2)m where m = 3 to ll; n = l to 3; preferably l or 2.
Examples of suitable substances of this type are N-benzoyl-N-methylacetamide, N-acetyl-~-caprolactam, N-ben~oyl-~-caprolactam, N-benzoyllaurolactam, N,N'-isophthaloylbis-E-caprolactam or N,N'-terephthaloylbis-6-caprolactam and N,N'-isophthaloylbislaurolactam or N,N'-terephthaloylbislaurolactam.
Preference is given to the use of N-benzoyllaurolactam, N-benzoyl-~-caprolactam, N,N'-terephthaloylbislaurolactam and - N,N'-terephthaloylbis-~-caprolactam~
These imides can be prepared by various prior-art processes (see M. K. Akkapeddi et al. in "~ecent Advances in Anionic Polymerization", T. E. Hoegen Esch and J. Smid ~Ed.), ; Elsevier 1987, pp. 318-328).
Although in pursuit of a completely different object, ~ `
European Published Patent Application 0,223,115 has already disclosed the reaction of polyphenylene ethers with (meth)acryl-oyllactams such as, for example, N-methacryloyl-~-caprolactam.
:.' j: :.. . , ~ ` . . , , .,; , ` , , ~'! .
'; ''`'' ` .: . ` "' , ~' "`' , ' " '' ` '' ' :' ` ' ; ~ ' ' ' ~ ' `,, '` ` ' ' ` " ' ` ' :,` ~ ,: ' ,` :
: ' '. ` . , ' ` : . ' _~ - 6 -~38'~7 `
However, it is not apparent from this document that the poly-phenylene ethers which have been treated in this manner would be in any way stabilized. On the contrary, according to the above-cited document relatively highly to fully cross-linked products are obtained, in particular in the absence of styrene polymers.
A person skilled in the art is given no inclication in this document that cross-linking of this type, even in polystyrene-free polyphenylene ethers, is not only suppressed using the lmides according to the invention but, on the contrary, even the molecular weight increase at elevated temperatures can be effectively inhibited.
Precisely this prevention of the molecular weight increase on initially meltlng the xeshly prepared polyphenylene ether is an essential aspeat of the present lnvention. Normally, this molecular weight increase is associated with the formation of branch points; however, this is inconvenient with regard to the mechanical properties of moulded articles produced from the material. In the capped polyphenylene ethers according to the invention, not only the OH terminal groups, as ln known masking reactions, but also the reactive defects of the polymer which are present in the freshly prepared polyphenylene ether, depending on the preparation, seem to have reacted with the capping agent.
The products according to the lnvention have signifiaantly fewer branch points, a feature which can be inferred from the increased crystallizability from dilute toluene solution.
The amount of capping agent used is naturally dependent on the number of hydroxyl groups which are present and the r ' `' .
'...... , ~ , .. . ' ~ . ' ' ~
~' ~"'.. "" ~ ' ' . ''' ' ;' ' " - ' ' ' ' :: , .' : ' ': . ' .
~, . , . , ~ 1-.
.
2 ~ ~ 3 ~
concentration of defects, but varies between 0.5 and 10% by welght, relative to the polyphenylene ether used, preferably between 2 and 6% by weight.
The capping according to the invention can be applied not only to pure polyphenylene ethers but also to polyphenylene ether-containing mixtures. Customary ingredients are, for example, polystyrene, impact-resistant polystyrene, styrene-butadiene copolymers (in the form of random, tapered or block copolymers~ which may optionally have been h~drogenated, poly-' 10 octenamers and/or polyole~ins. Components o~ this type do notnoticeably interfere with capping, but the proportion of polyphenylene ether must advantageously be at least 20% by -~
weight.
The process is carried out at 230 to 330C, preEerably in the melt in a mlxer having a good kneading action. However, it is also possible to operate in the presence of an inert :
solvent, for example diphenyl ether or toluene, optlonally under pressure. ~
The process according to the invention is a method ;~ -which requires a lesser amount of capping agent in comparison with the known processes. If a stoichiometric excess of the capping agent is used, this does not need to be subsequently separated off, since there is no significant reduction in the glass transition temperature Tg. Furthermore, the capping agents ~
used in the said process are easy to handle and toxicologically ~;
harmless. There are no corrosion problems.
The capped polyphenylene ethers according to the . . .
.,' ; ~;
';" ;`:
' .
- `
2~338~
invention are used as components of mouldlng compositions. The other components used can be all those which are customarily used according to the prior art in polyphenylene ether-containlng moulding compositions. These moulding compositions according to the invention also have improved thermal and oxidative stability and also, owing to the stabilization of the molecular weight, , improved processibility. They can be used to produce the identical moulded articles for which known polyphenylene ether- ~-based moulding compositions are used.
The invention is explained in detail in the examples which follow.
Example 1 Preparation o a polyphenylene ether 30 kg of 2,6-dimethylphenol in 30 kg of toluene are added with aeration over a period of 30 minutes to a stirred mixture of 260 kg of toluene, 42.0 kg of methanol, 6.0 kg of :
morpholine, 153 g of CuC12 2H2O (dissolved in 850 g of methanol) ; and also 153 g of di-tert-butylethylene-diamine. After a ..... .
reaction time of 130 minutes, the reaction is terminated by adding a mixture of 75 kg of water, 9 kg of methanol and 300 g of triethanolamine and passing through a stream of CO2. The organic phase is washed twice using on each occasion 125 kg of water and 300 g of triethanolamine at 80C. The product is precipitated using 350 kg of methanol, washed twice with, on ,:, each occasion, 180 kg of methanol and then dried. Yield:
25.8 kg; J = 51 cm3/g . ' . .
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Exam les 2 to 6 and A and B ~ 03 3 ~ 4 P ~ _ A Berstorff ZE 25*33 D twin screw extruder is used to melt, mix and granulate, at a set temperature of 290C, the proportions by weight of polyphenylene ether from Example 1 and capping reagent, as given ~ the table. The extrusion is carrled out with degassing in the final zone of the extruder; in every case, the material temperature exceeds 300C.
The Examples A and B are not according to the invention;
they are given only for the purposes of comparison.
The degree of masking is determined using FT-IR
spectroscopy. Reference values are determined from untreated PPE
and rom a product which has been fully capped using acetic anhydrlde.
The glass transition temperature Tg is determined on a ~ Mettler TA 3000 instrument at a heating rate of 10 K/min.
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Claims (14)
1. Capped polyphenylene ethers and mixtures thereof prepared by reacting polyphenylene ethers composed of the following units:
wherein Q1 and Q2 are hydrocarbyl radicals having 1 to 10 carbon atoms, and Q3 and Q4 are hydrogen or hydrocarbyl radicals having 1 to 10 carbon atoms, with from about 0.5 to about 10% by weight, relative to the polyphenylene ethers, of imides of the general formulae and/or in which R1 is aromatic or saturated aliphatic radical having 1 to 20 carbon atoms; R2 and R3 is aromatic or saturated aliphatic radical having 1 to 12 carbon atoms; R4 is (CH2)m where m is an integer from 3 to 11; n is an integer from 1 to 3.
wherein Q1 and Q2 are hydrocarbyl radicals having 1 to 10 carbon atoms, and Q3 and Q4 are hydrogen or hydrocarbyl radicals having 1 to 10 carbon atoms, with from about 0.5 to about 10% by weight, relative to the polyphenylene ethers, of imides of the general formulae and/or in which R1 is aromatic or saturated aliphatic radical having 1 to 20 carbon atoms; R2 and R3 is aromatic or saturated aliphatic radical having 1 to 12 carbon atoms; R4 is (CH2)m where m is an integer from 3 to 11; n is an integer from 1 to 3.
2. Capped polyphenylene ethers according to claim 1, wherein Q1 and Q2 are primary alkyl radicals, cycloalkyl radicals having 5 to 10 carbon atoms, benzyl radicals having 7 to 10 carbon atoms or aryl radicals having 6 to 10 carbon atoms.
3. Capped polyphenylene ethers according to claim 1, wherein Q3 and Q4 are hydrogens.
4. Capped polyphenylene ethers according to claim 1, wherein Q1 = Q2 = CH3 and Q3 = Q4 = H.
5. Capped polyphenylene ethers according to claim 1, 2, 3 or 4, wherein the polyphenylene ether has a viscosity number J of from about 20 to about 80 cm3/g.
6. Capped polyphenylene ethers according to claim 5, wherein the polyphenylene ether has a viscosity number J of from about 40 to about 70 cm3/g.
7. Capped polyphenylene ethers according to claim 1, 2, 3 or 4, wherein the amount of capping agent is from about 2 to about 6% by weight, relative to the polyphenylene ethers.
8. Capped polyphenylene ethers according to claim 1, 2, 3 or 4, further comprising polystyrene, impact-resistant poly-styrene, styrene-butadiene copolymers which may have been hydrogenated, polyoctenamers and/or polyolefins.
9. Capped polyphenylene ethers according to claim 1, 2, 3 or 4, wherein the reaction is carried out in the melt.
10. Capped polyphenylene ethers according to claim 1, 2, 3 or 4, wherein the imide used is N-benzoyllaurolactam or N-benzoyl-.epsilon.-caprolactam.
11. Capped polyphenylene ethers according to claim 1, 2, 3 or 4, characterized in that the imide used is N,N'-tere-phthaloylbislaurolactam or N,N'-terephthaloylbis-.epsilon.-caprolactam.
12. Process for the preparation of capped polyphenylene ethers according to clalm 1, 2, 3 or 4, which comprises reacting the components at a temperature of from about 230 and about 330°C.
13. Process according to claim 12, wherein the reaction is carried out in the melt.
14. Moulding compositions comprising capped polyphenylene ethers according to claim 1, 2, 3 or 4, or prepared by a process according to claim 12 or 13.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4000644.1 | 1990-01-11 | ||
| DE19904000644 DE4000644A1 (en) | 1990-01-11 | 1990-01-11 | CAPPED POLYPHENYLENE ETHER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2033847A1 true CA2033847A1 (en) | 1991-07-12 |
Family
ID=6397892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2033847 Abandoned CA2033847A1 (en) | 1990-01-11 | 1991-01-09 | Capped polyphenylene ethers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0436802A3 (en) |
| JP (1) | JPH04211425A (en) |
| CA (1) | CA2033847A1 (en) |
| CS (1) | CS4591A2 (en) |
| DE (1) | DE4000644A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670537A (en) * | 1986-01-14 | 1987-06-02 | General Electric Company | Polyphenylene ether containing amino-alkyl substituted end groups reacted with N--H compound |
| DE3813354A1 (en) * | 1988-04-21 | 1989-11-02 | Huels Chemische Werke Ag | THERMOPLASTIC MOLDING MATERIALS BASED ON FUNCTIONALIZED POLYPHENYLENE ETHERS AND POLYAMIDES |
| NL8801914A (en) * | 1988-07-30 | 1990-02-16 | Stamicarbon | CONVERSION PRODUCTS OF LACTAM-BLOCKED DIISOCYANATES AND POLYLACTAM-BLOCK COPOLYMERS DERIVED THEREFROM. |
| NL8900001A (en) * | 1989-01-02 | 1990-08-01 | Stamicarbon | ACYLLACTAM FUNCTIONAL COMPOUNDS AND POLYLACTAM BLOCK COPOLYMERS DERIVED THEREFROM. |
-
1990
- 1990-01-11 DE DE19904000644 patent/DE4000644A1/en not_active Withdrawn
- 1990-11-14 EP EP19900121758 patent/EP0436802A3/en not_active Withdrawn
-
1991
- 1991-01-09 CA CA 2033847 patent/CA2033847A1/en not_active Abandoned
- 1991-01-10 JP JP159391A patent/JPH04211425A/en not_active Withdrawn
- 1991-01-10 CS CS9145A patent/CS4591A2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS4591A2 (en) | 1991-08-13 |
| EP0436802A3 (en) | 1991-11-21 |
| EP0436802A2 (en) | 1991-07-17 |
| JPH04211425A (en) | 1992-08-03 |
| DE4000644A1 (en) | 1991-07-18 |
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