DE3521125C2 - - Google Patents

Description

Field of the Invention

The invention relates to phosphorus-containing polyarylene ethers which high-temperature resistant and flame-retardant materials Represent plastic properties, as well as a process their manufacture.

State of the art

DE-AS 32 03 186 are phosphorus-containing polyarylene ethers known, which contrasts with those of S. Hashimoto, I. Furukawa and K. Ueyama, Journal of Makromol. Sci. Chem. All (12) pages 2167-2176 (1977) described phosphorus-containing aromatic Differentiate polyethers in that they reduced a higher Viscosity, d. H. have a higher molecular weight and the masses of considerable strength and typical plastic properties with good self-extinguishing properties.

Those described in the examples of the above-mentioned DE-AS Polyethers produce test specimens when extruded or when cast Foils that are slightly cloudy, which reduce the Translucency leads. The reason for the cloudiness in the Plastic bodies from the phosphorus-containing polyarylene ethers unknown.  

Object of the invention

It was therefore the task of phosphorus-containing polyarylene ethers Manufacture no cloudy plastic during processing Give more body and this according to their optical Properties are translucent and transparent. This object is achieved in that the new phosphorus-containing polyarylene ethers other than those in the p-position bonds of the phosphorus-containing monomer to the P atom Building blocks of the polymer chain still have those that o- and keep running to the P atom. Surprisingly, ask they represent masses that give completely clear plastic bodies and further the known good properties of the above possess phosphorus-containing polyarylene ether.

The production of this new phosphorus-containing polyarylene ether is further carried out according to the invention so that the Polycondensation Mixtures of constitutionally isomeric compounds of the formula

are used, in which the functional groups X are in o-, m- and are in the p-position to the P atom. By using such Isomer mixtures is the preferred structure according to DE-AS 32 03 186 disturbed.  

Properties and applicability of the new substances

The new substances have a sufficiently high polycondensation degree, the at least a reduced viscosity of 0.25 dl / g corresponds to the desired plastic properties.

You can by pressing at high temperature or by forming in the thermoplastic state into shaped bodies deform all kinds. The plastic products, from the new ones Polycondensates are no longer cloudy and ent speaking their optical properties clearly translucent and transparent.

The polycondensates also have a high CR value and are considered such as well as in processed forms hardly combustible or incombustible if it has a phosphorus content of at least 2% by weight. In terms of their properties, they find Interest in the manufacture of plastic bodies which high thermal stability at high temperatures, good Transparency and difficulty or incombustibility are required.

Structure of the polyarylene ether according to the invention

The new polyarylene ethers are made by polycondensation bifunctional phosphorus-containing monomers I of the general structure

wherein the functional groups X halogen atoms and / or hydroxyl are groups and these in relation to the P atom at the free ones o-positions, at the m-positions and / or at the p-positions are, with a compound II of the structure

X- (ArO) _m-1 -Ar-X,

wherein the functional groups X are halogen atoms and / or Hydroxyl groups are obtained.

In the starting point I can be a mixture of the following six Isomeric compounds (1 to 6) are present:

In the mixture, the ratio of the positions of the functi nonal groups X to the P atom:

p: o: m ∼ (80 to 99): (20 to 1): (2 to 0)

When using compound I as a mixture of those described above Positional isomers are used in the polycondensation Compound II formed polymers in which the phosphorus building block in addition to p-linking to a limited extent also by o- or m linkage is built into the polymer chain. The Installation point of the phosphorus-containing building block in the polymer chain then depends on the specified type and amount of positional isomers used in polycondensation reaction and the polymers formed now contain in addition p-installation still o- and m-chain internals, which the well-known interrupt regular p-constitution and thus the Kri disrupt installation.

The polyarylene ether according to the invention has the following structure III:

wherein Ar is a phenylene or naphthylene group or the group

R each represents a hydrogen atom or R --- R taken together represents an oxygen atom or one of the groups mentioned under R ″,
R ′ is an alkyl, chloromethyl, aryl, alkoxy or aryloxy group,
R ″ is a single covalent bond, an oxygen atom, a sulfur atom, a sulfonyl, carbonyl, methylene or isopropylidene bridging group,
E same or different end groups, consisting of hydrogen, halogen, alkyl or alkoxy, aryl or aryloxy, acyl or acyloxy
m an average value in the range from 0 to 10,
n = a + b + c 10,
in which
a 0.8 to 0.99
b 0.01 to 0.2
c 0 to 0.02
q 0 or 1
mean.

The values a, b and c say nothing about the sequence of the o-, m- and p-junctions in the polymer molecule. It is assume that these are statistically distributed, where Sequences with repeating p, p′ internals because of the high p, p'-content of 80% in the phosphor containing raw material predominate.

The bifunctional phosphine oxide or phosphine output ver Bonds can be pure positional isomers, e.g. B. p, p'- or  o, o'-derivatives or mixed positional isomers, e.g. B. o, p'- or p, m'-derivatives, each of the two substituted aromatic rings contains only one of the possible functions.

Production of the polyarylene ether

It was found that polyarylene ether containing phosphorus Structure III are formed when mixtures of position isomers of a bifunctional phosphine or phosphine oxide of formula I with a bifunctional compound of formula II be polycondensed, and that the poly condensates compared to the known polyarylene ethers distinguish improved properties.

The ones to be used for the production of the new polyarylene ethers Polycondensation conditions with the various Options are those for the production of polyarylene ether according to DE-AS 32 03 186 or according to US 44 92 805 analog. Preferably, the compounds I and II are exactly interfering chiometric ratio 1: 1 implemented, especially I with X = F and II with X = OH.

The phosphine or the phosphine oxide

Among the phosphorus-containing starting components of structure I are derivatives of methyl-diphenylphosphine and in particular of triphenylphosphine and here in general those of Triphenylphosphine oxide preferred. It was found that already with bifunctional proportions of about 1 mole%, none p, p′-bifunctional derivatives of the starting component I are the polycondensates after processing. Plastics with noticeable give less turbidity, and that this by even higher Incorporation of o- or m-functional I-derivatives completely disappears.  

The preferred proportion of non-p, p'-phosphor monomers is at 2 mol% and particularly preferably from 3 to 6 mol%. It has surprisingly been found that this particularly preferred o- or m-functional part the technically interesting syntheses of dihalotri- phenylphosphine oxide and dihalomethyldiphenylphosphine oxide after Friedel-Crafts from halobenzene and methane or benzene di chlorophosphine sulfide co-arises alongside the p, p'-main product. Corresponding to the information on the above given together Settlement of the isomer mixture contains the Crafts synthesis obtained bifunctional phosphorus-containing Monomers are the isomers with a decreasing proportion from (1) to (6). A preferred mixture of isomers can also be obtained by mixing the pure isomers can be obtained in appropriate amounts. The Functions X in I can also optionally contain hydroxyl groups be.

Preferred representatives of compound I are isomeric di- (mono fluorophenyl) phenyl phosphine oxides and di (monofluorophenyl) - methyl phosphine oxides.

The bifunctional aromatic compound II

represented by the formula X- (Ar-O) _m-1 -Ar-X, is preferably used with X = OH. The two functions X in the molecule can optionally also be halogen atoms, in particular fluorine atoms. Examples of preferred representatives of the compound II are hydroquinone, resorcinol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, the compounds known as bisphenol A and F, and 4,4'-difluoro and 4, 4′-dichlorobenzophenone. 4,4'-Dihydroxydiphenyl ether is particularly preferred.

The end groups

can have unreacted halogen atoms or hydroxyl groups be in turn with alkylation, arylation or Acylating agents are converted into stable end groups can.

Examples

The following examples show manufacturing processes of phosphorus-containing polyarylene ether according to the invention.  

Example 1 (comparative example)

22.8 g (0.1 mol) of bisphenol A and 31.4 g (0.1 mol) of pure 4,4′-difluorotriphenylphosphine oxide (by Grignard reaction were produced) in a 500 ml round-bottom flask with KPG stirrer, Reflux condenser, dropping funnel and argon transfer with 150 g N-methylpyrrolidone and 50 g of chlorobenzene combined. It was heated to reflux and an acetrop from reaction water and chlorobenzene are removed. Escaped at the same time CO₂. When almost no water passed over (after about 2 hours) were a further 50 g of chlorobenzene at the reaction temperature added dropwise within an hour and the chlorobenzene together distilled off with the residual water. Then that was Reaction mixture at about 180 ° C for 16 hours under an argon atmosphere heated. The polycondensation was carried out by 30 minutes Introduced methyl chloride at 160-180 ° C canceled.

After cooling, the viscous reaction mixture was diluted with 50 ml of N-methylpyrrolidone, the inorganic precipitate was filtered off and the polyether in the filtrate was precipitated with a methanol / water mixture. The precipitate was filtered off, washed with water-methanol, dissolved in dichloromethane and precipitated again. The mixture was then dried to constant weight at 120 ° C. in the past.
Yield: 39 g (78% of theory)

Both a test specimen obtained therefrom by extrusion and a cast film was also cloudy.  

Example 2

The procedure is as in Example 1, but with one difference: Instead of the one synthesized via Grignard reaction a 4,4′- prepared by Friedel-Crafts reaction Difluorotriphenylphosphine oxide. This product contained after P-31 NMR spectroscopy 95% of 4,4'-isomers.

The polycondensate produced from this gave after forming extruded bodies or after casting into foils none Cloudiness.

Examples 3 to 6

Polycondensates were synthesized from various bisphenols and 4,4'-methyldi (fluorophenyl) phosphine oxide corresponding to that in Example 1 given experimental description. In Table I are the bisphenols used, information on the purity of the Phosphorus compound, the polyether yield and optical Appearance of foils made from it is specified.  

Table 1

Claims (7)

1. Phosphorus-containing polyarylene ethers of the general structure wherein
Ar is a phenylene or naphthylene group or the group R each represents a hydrogen atom or R --- R taken together represents an oxygen atom or one of the groups mentioned under R ″,
R ′ is an alkyl, chloromethyl, aryl, alkoxy or aryloxy group,
R ″ is a single covalent bond, an oxygen atom, a sulfur atom, a sulfonyl, carbonyl, methylene or isopropylidene bridging group,
E same or different end groups, consisting of hydrogen or hydroxy, halogen, alkyl or alkoxy, aryl or aryloxy, acyl or acyloxy,
m an average value in the range from 0 to 10,
q 0 or 1
n as the sum of the mean values a, b and c mean a mean value of at least 10,
and for the ratios of a: b: c the information
a: b = (0.8 to 0.99): (0.2 to 0.01)
a: c = (0.8 to 0.99): (0.02 to 0)
b: c = (0.2 to 0.01): (0.02 to 0)
be valid. 2. phosphorus-containing polyarylene ether according to claim 1, characterized in that R 'is a methyl or Is phenyl group. 3. phosphorus-containing polyarylene ether according to claim 2, characterized in that R --- R is a covalent Symbolize single bond or an oxygen atom. 4. phosphorus-containing polyarylene ether according to claim 2, characterized in that R is a hydrogen atom symbolizes and q = 1. 5. A process for the preparation of phosphorus-containing polyarylene ether according to claims 1 to 4 by polycondensation of a bifunctional phosphine or phosphine oxide I, optionally together with a bifunctional compound II, in the presence of an alkali at least half equivalent to the groups X at elevated temperature wherein R, R ′, Ar and q have the meaning given in claim 1, characterized in that I is used as a mixture of positional isomers which contain the substituents X in the ortho, meta and para position to the phosphorus atom. 6. The method according to claim 5, characterized in that the mixture of positional isomers in one contains such a ratio that the polycon formed densate are constructed according to claim 1. 7. The method according to claims 5 and 6, characterized records that in the formulas I and II with X be half of the groups drew from halogen atoms, especially fluorine atoms, and the other half Hydroxyl groups exist.