DE2210348A1 - Block copolymer and process for its preparation - Google Patents

Description

Imperial Chemical Industries Limited Lonaon (Great Britain)

block copolymer and process for its preparation

The invention relates to polymeric substances, in particular to block copolymers.

Aromatic polymers, especially aromatic polyamides and polyesters, are substances with a high mociul and more potentially useful as reinforcing fillers for thermoplastic and other substrates. The aromatic Polyamides can be incorporated in bulk, which are spun or prepared from film, fiber or coatings can be used for application to a thermoplastic material. Lin special application area Tier mass is the preparation of fibers that are used as reinforcing materials to be used for laminates.

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The preparation of aromatic polyamides is in the UK Patents 901 159, 1 008 854, 1 198 081, 1 198 082 and 1198 083 are described. On the content of these publications is expressly referred to here. However, with most reinforcing fillers, lining up stands an aromatic polyamide into a thermoplastic material generally with an increase in modulus (brittleness or rigidity), but associated with a reduction in impact resistance (toughness). This deficiency is in some Felling by surface treatment of the reinforcing material to overcome. Another method consists in the production of a block copolymer, which units of the reinforcing Material and units of the material to be reinforced

According to the invention, a block copolymer is now used created, characterized ourch 1 to 99% units of an aromatic polymer with a high modulus, which among aromatic Polyamides and aromatic polyesters is selected, and 99 to 1% linear units, which differ from a thermoplastic Condensation polymer, which is defined below.

The invention includes a Llock copolymer 1 to 99k units of an aromatic polymer with a high modulus, selected from polyamides and polyesters

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99 to 1% kinetics, which differ from a thermoplastic Derive condensation polymers.

According to the invention, the high molecular weight polymer is an aromatic polyamide or polyester or a copolymer which has aromatic polyamide and polyester units. The polymers can be obtained by polymerizing an amino or a hydroxyaromatic carboxylic acid or by substantially equimolecular proportions an aromatic diane is polymerized into or uiol, specifically with an aromatic dicarboxylic acid, optionally with an amino or hydroxyaromatic carboxylic acid. The dicarboxylic acid can be used in the form of one of its functional derivatives, for example as an ester or acid chloride. The monomers therefore have the general formula XQX ¹ , in which λ and X ^{1 are} -Oh, -Mio ^ocier COOK, which, as described above, can be the same or different; and Q is a divalent aromatic radical such as:

wouei ώ a direct tie; -O-; -S-; -CO-; -SO.,-;

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₃ J ₂ -Y-SO-; -CO.Nh-i -NH.CO-; -O.CO-; -CO.Oi • NH.SO-- or -SO ₂ NH-. Preferred monomers are:

COOH

It is preferred that the high modulus polymer consists of aromatic groups which are in the 4-position are substituted, fcs should not be substituted more than a lot in the 3-position. Preferred polymers are therefore those having repeating units of the form

The aromatic rings can carry one or more substituents such as halogen atoms, lower alkyl, lower aryl, alkoxy, thioalkoxy, provided uaß aie substituents do not affect the block copolymerization or the modulus of the polyamide or polyester significantly reduce. The aromatic rings are preferably unsubstituted.

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The thermoplastic polymer can be any cone ionic polymer, provided that it is compatible with the polymer with which the block copolymer of Invention is to be mixed to create a reinforced mass, and provided that it contains a group which is capable of condensation with a monomer of the high modulus polymer. The polymer can also be aromatic Be a polycondensate such as a polysulfone or polyketone, an aliphatic polyamide, a polyester, for example polyethylene terephthalate, or an aromatic polycarbonate, provided the polymer was thermoplastic is. The polymer can also be a polyolefin (i.e. a polymer which, upon free radical polymerization, is ethylenic Unsaturated compounds is generated), provided that aas polyolefin contains a group which condensation with a monomer capable of the high modulus polymer (e.g. a styrene / methacrylic ester copolymer with a content of at least one carbonyl chloride group).

Suitable aromatic polysulfones and polyketones which have aromatic ether or thioether groups in the polymer chain Contain in ortho- or para-position to at least one -SOy- or -CO- group and processes for their manufacture, are in British patents 971 227, 1 016 245, 1 O6O 54b, 1 078 234, 1 102 679, 1 109 842, 1 122 192, 1 124 200, 1 133 561, 1 153 035, 1 153 528, 1 164 817, 1 177 183, 1 234 301, 1 246 035 and 1 255 588,

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Described in the Belgian patent specification 741 965, in the Canadian patent specification 647 963, in the USA patent specification 3 432 468, in the Dutch patent specification 70 11346, in the German patent specification 1 9 30 806 and in the Swiss patent specification 491 981. Express reference is made here to the content of these publications. The term "aliphatic polyamide" is to be understood here as meaning a product which contains regularly recurring amide groups as integral parts of the main polymer chain, such products being generally known as types of nylons. These can be obtained by polymerizing a monoaminomonocarboxylic acid or an inner iiactam of this η with at least two carbon atoms between the amino and carboxylic acid groups, or by essentially equimolecular proportions of a diamine which contains at least two carbon atoms between the amino groups and a dicarboxylic acid , polymerized, or by polymerizing a monoaminocarboxylic acid or internal lactam, as defined above, together with substantially equimolecular proportions of a diamine and a dicarboxylic acid. The dicarboxylic acid can be used in the form of one of its functional derivatives, for example as a solvent.

The expression "essentially equimolecular proportions" (of biamin and dicarboxylic acid) is intended here to be both precise equimodal Proportions as well as the slight deviations from it

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with include, the latter in conventional techniques for Stabilizing the viscosity of the resulting polyamides are involved.

As examples of the monoaminomonocarboxylic acids mentioned and their lactams, those compounds may be mentioned which between the amino and carboxylic acid groups 2 to 16 carbon atoms contain, whereby u these carbon atoms in the case of a lactam form a ring with the -CO.Nh group. As particular examples of aminocarboxylic acids and lactams are mentioned: £ -aminocaproic acid, butyrolactam, pivalolactam, Caprolactam, caprylic lactam, lnantholactam, undecanolactam and Dodecanolactan ;.

Examples of the diamines mentioned are diamines of the general formula II ₅ N (CH ₀ ) Hh,., In which η is a whole kiahl from 2 to 16, such as, for example, trimethylene amine, tetramethylene amine, pentamethylene amine, octamethylene amine, uecamethylene amine, boaecamethylene amine, liexadecamethylene amine amine and in particular Hexamethylenediamine. C-alkylated diamines, for example 2,2-biiuethylpentamethylenediamine and 2.2.4- and 2.4.4-trimethylhexamethyleneuiamin are further examples. Other diamines, which may be mentioned as examples, are aromatic diamines, e.g. 1.3-diaminobenzene, 1.4-biaminobenzene, bis (4-amino-phenyl) -sulfone, bis (4-aminophenyl) -ether and bis (4-aminophenyl) - methane; and cycloaliphatic diamines, for example diaminodicyclohexyl methane.

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Suitable dicarboxylic acids are aliphatic and have the formula IiOOC.Y.COOH, where Y is a divalent aliphatic Means radical with at least 2 carbon atoms. Examples Such acids are sebacic acid, the dicarboxylic acid derived from octadecane, suberic acid, azelaic acid, uie uicarboxylic acid, glutaric acid, derived from Unuecan, Pimelic acid, and especially adipic acid. Oxalic acid is also a suitable acid.

The following polyamides in particular can be incorporated into the inventive thermoplastic polymer blends are incorporated

Polyhexamethylene adipamide (nylon 6: 6)

Polypyrrolidone (nylon 4)

Polycaprolactam (nylon 6)

Polycaprylic lactam (nylon 6)

l'olyunoecanolactam (nylon 11)

Polydodecanolactam (nylon 12)

Polyhexamethylene azelaiamia (nylon 6: 9)

Polyhexairethylene sebacamide (nylon 6:10)

Polymutaxylylene adipamide (nylon MXU: 6)

Polyamide of hexamethylenediamine and (nylon 6:12) aer ucarboxylic acid of n-dodecane

Polyamide of dodecamethylenediamine (nylon 12:12) una der üicarbonsäure des
n-Doaecans

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Nylon copolymers can also be used for example copolymers of the following:

Hexamethylene adipamide / caprolactam (nylon 6: 6/6)

Triijiethylhexamethylene-oxamid / (nylon-trimethyl-

Hexamethylene oxamide 6: 2/6: 2)

Hexamethylene adipamide / hexa- (nylon 6: 6/6: 9) methylenazelaiamid

Hexamethylene adipamide / hexa- (nylon 6: 6/6: 9/6) methylenazelaiamid / caprolactam

Suitable aromatic polycarbonates are described in British Patent 772,627.

The block copolymers according to the invention can 1 contain up to 99% (preferably 1 to 10% and desirably 1 to 5%) units of an aromatic polyamide high modulus,

2 Under the high module there is a module of at least 7 GN / m

to understand.

According to the invention, there is also a method of production the block copolymers created, in which the polyamide or the polyester high modulus in the presence of a preformed thermoplastic polymer is formed, the thermoplastic polymer having an end group or pendant Has group which with a polymer-forming group aes monomers, which in aer formation of the polymer fetched module is used, can react. The high modulus folyamide is formed, for example, by the reaction

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an amino group with a carlonyl halo group and therefore should be thermoplastic for the block copolyir.eren to be formed Polymers either an amino group or a carbonyl halogen group contain; wherein aas the total ratio of amino groups to carbonyl halide groups is essentially that same is. For example, when the high modulus polymer is a polyester it can include hydroxyl or carboxylic acid groups used weraen. The selection of the groups which used depends on the thermoplastic polymer, the high modulus polymer, and the susceptibility of the linking groups of the thermoplastic polymer against cleavage under the conditions of block copolymerization used. The following reaction schemes show examples of some ways of block copolymerization, which can be used:

Formation reactions for polymers with high modulus.

Dimethyl

<b) nhO

(c) nNaO — V /

COOH

CO. Nl

w ^at

^X ^ OC1 interface

co-e Vco--

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(d) nhO ~ V / - ° ^{H +} nClCO

Warmth

J η

2. Block copolymerization reaction. (a)

+ nClCO

COCl

(hylon 66 with
Aminenoe)

Wylon 66

Dimethyl acetamide _{lithium chloride}

NH_L η

(b) polysulfones

OK

+ nClCO

Polysulfone

or 1.1.2-trichloroethane

NIi

Polysulfone ........... 0

-. η

(c) polyketone

Polyketone

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CH ₀ -CH-CH ₉ -Ch ^ -CH ₅ -CH-CH ₀ -Ch- * ι * · ^J m * I * ι

COOMe / Λϊ, COCl

+ nClCO

£ CH., - CIi-CH .j -C
'1 ²

COCl

· M COOH

-CH-CH ₂ -Ch-

The block copolymerization reaction is preferably carried out in the presence of a solvent. In the case of acidic chloride, the solvent should be an acid acceptor, but not so strong, as the reaction is impaired. Suitable solvents are plienols such as m-cresol _r chloral hydrate, dimethylacetamine and methanol / calcium chloride. a suitable acid acceptor is lithium hyaroxide; Pyridine is generally not suitable. The acid chloride / Phenolatoaer amine polymerization reaction is preferably used

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a temperature of less than 30 C, more preferably of less than 20 ° C. The reaction is preferably carried out in an inert atmosphere such as nitrogen. The block copolymer can be extracted from the reaction mixture, for example by pouring into methanol, washing, filtering off and drying.

Furthermore, the invention provides a process for the preparation of copolymers, which consists in that one at least one compound, which under polyamide, polysulfonamiü and lactam is selected, with an aromatic sulfon, as defined below, in the presence of one alkaline catalyst converts.

The aliphatic polyamides are supposed to be among the polyamides include those listed above as nylons, as well as the aromatic polyamides defined above, which are produced by self-condensation of aminoaromatic carboxylic acids such as 4-aminobenzoic acids, and by aie condensation of aromatic diamines with aromatic dicarboxylic acids such as, for example, isophthalic acids and terephthalic acids. Suitable aromatic polyamides are, for example:

Aromatic polyamides can also be used such as polybenzamide, ie polymer with an external unit (-NH-C ₆ H _4, preferably para

Polyamide of 1,4-diaminobenzene and terephthalic acid

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Polyamide of 1,4-diaminobenzene and Isophthalic acid.

A polysulfonamide should be understood here as meaning a polyamide as defined above in which -CO.NH- groups have been replaced by -SO ₂ -NH- groups .

The aromatic sulfone has the structure:

X-Ph-SO ₂ -I-Ar-SO ₂ 4-R

in which X is a group which under the process conditions is displaceable and which is typically a halogen atom (preferably chlorine or fluorine) or an alkoxy, Is aryloxy or nitro group,

Ph is a phenylene group, which is preferably free of electron-donating substituent groups with a negative 6 value, as described by J.F.Bunnett in Chem. Rev. (1951), 49, 273 and quart. Rev. (1958), 12, 1, is, preferably p- or o-phenylene,

Ar is a divalent aromatic radical, η is equal to zero or an integer from 1 to 10, and R is a monovalent aromatic or aliphatic caustic which can contain ethylenically unsaturated groups, provided that such groups are not in Cc - or β- Position to the -SO ₂ group.

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Preferred aromatic sulfones are:

(i)

in which X can be the same or different,

(ii)

(iii) X ^ (/ \

\\ _ Q_Z

^Y n

where δ is hydrogen, alkali metal or a monovalent alkyl aryl radical and (if η is greater than 1) some of the linearities with the formula:

in different proportions by units of the formulas

may be replaced.

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The method according to the invention can be carried out inueni man uie respondents either in presence or in the absence of a diluent. Any diluent present should be used against anionic Genera be inert and should preferably be a solvent or swelling agent for the aromatic sulfone or polysulfone be. Examples of such solvents are those of the formula:

R-S-R

O '

in which R is an alkyl group free of ethylenic unsaturation, an aryl group (the R groups can be the same or different); and y is an integer which has the Vvert 1 or 2. R can therefore be lower alkyl such as methyl, ethyl, propyl, butyl, or aryl such as phenyl, alkylphenyl, or the R groups can be linked to one another via a divalent alkylene bridge such as - (Cl ^) ₄ ". Preferred diluents are dimethyl sulfoxide, dimethyl sulfone , Diphenylsulfon and 1,1-Dioxothiolan (SuIfolan).

The inventive method is preferably used at carried out at a temperature which is higher than that Melting point of at least one of the respondents because generally a more homogeneous mixture is achieved. As with most chemical reactions, there is a compromise to be made conclude between winning essentially a single

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- · 17 -

gen product, the reaction being carried out at a temperature of about 50 ° C. for a long period of time, and between carrying out the reaction at higher temperatures for a shorter reaction time with the associated risk of a large number of products and product decomposition. The preparation is desirably at a temperature above 12O ⁰ C, but below 40O ⁰ C, preferably below 350 C, performed. The reaction temperature should be lower (below 350 ° C.) if, instead of a lactam, preformed polyamide is reacted, a catalyst should be present to accelerate the copolymer formation. The catalyst to be used is a compound which is capable of forming an anionic site on the amide nitrogen atom of a polyamide or polysulfonamide by withdrawing a proton from the amide group. Any of the known catalysts for the so-called "alkaline" polymerization of lactams can be used. Typical catalysts are alkali metals and alkali metal hydrides. Preferred catalysts are sodium metal and sodium hydride. Any of the various cocatalysts, for example N-acetylcaprolactam, which are known for "alkaline" polymerisation, can also be used.

The copolymer can be obtained from the reaction mixture by breaking up the cooled reaction product and grinds, neutralized with acetic acid, with water and / or Alcohol washes and dries in an oven,

2 0 9 8 3 Ο / ΙΙ1Γ!

The structure of the process according to the invention copolymers formed, can by infrared and n.m.r. techniques (nuclear magnetic resonance spectrum) can be determined. These Analysis shows that the copolymer formed as the product of the process is not a mere mixture of aromatic sulfone with the polyamide or polysulfonamide, but a new compound in which aromatic sulfone units are chemically bonded within and / or on the polymer chain. The n.m.r. results indicate that

(i) an aromatic polysulfone into smaller units

is dismantled,

(ii) where an aliphatic polyamide or lactam is reacted, aromatic protons with a tertiary one or secondary amide group, i.

H-

or -C-UÜ- & Il

are associated
(iii) a noticeable concentration of the phenolic

hydroxyl group is present, the concentration being too high for the group to only be connected to the Lnüe to be placed in the main polymer chain (concentration determined by infrared).

Therefore, copolymers produced by this process shy away from it PfΑ ~ ορίcopolymere ^ .u be, which is a substrate made of polyamide

? O9B38 / 11O2

or polysulfonamia or polyamide / aromatic sulfone or Have polysulfonamia / aromatic sulfone, as well as a superstrate, which is an aromatic sulfone.

The copolymers or their mixtures, mixed with any desired fillers or reinforcing materials, lubricants and stabilizers, can be used as thermoplastic raw materials for the manufacture of articles which require good impact resistance. Their toughness, coupled with high strength and high softening point, can be considered an advantage. For example, the masses can be extruded into islattforni or tubular shape and the sheet can be deformed, for example by pressing or drawing, if necessary. The masses can also be compression molded and injection molded. Examples of articles so made using the compositions of the present invention include paneling and exterior enclosures for machines (such as automobiles, office machines, and household appliances), crash helmets, piping for conveying fluid, and telephone receivers. The use of inventive masses with superior tensile strength, coupled with ability and rigidity, can allow a saving in material in comparison with commonly used products, as all pieces would serve the same purpose. The beneficial one. physical properties of the masses allow them to be used in mechanical engineering.

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The copolymers according to the invention can be used either alone or in admixture with other polymeric material as adhesives for glass, metal and wood.

The block copolymers according to the invention can be used as Use powder or you can dry them or spin them out For example, spin sulfuric acid solution into fibers and fiber material, or cast into film, which can then be drawn. They can be used as fibers directly However, in recent years these forms can be used as reinforcing fillers for thermoplastic polymers,

which is mixed by any mixing technique for thermoplastics, such as grinding, coating, coating. The reinforced thermoplastic polymer can also be deformed in external heat. Other additives such as dyes, Fillers, UV stabilizers, and antioxidants can be incorporated into the dlock copolymers and / or thermoplastic polymers. The fibers are also reinforcing Materials for masses, which are useful for mechanical rubber goods such as belts and aids.

The solution is illustrated by the following exemplary embodiments.

The reduced viscosities of the copolymers are given at 25 C on solutions of the copolymer in a Solvent determines which 0.5 g or 1.0 g of the poly

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contains mers in 100 cm solution (i.e. 0.5 or 1%, weight / Volume).

Sodium hydride is used as a dispersion in oil containing 50 g of sodium hydride in 100 cm dispersion.

EXAMPLE 1

800 g of caprolactam are introduced into a flask equipped with a stirrer, flushing nitrogen inlet, condenser and thermocouple equipped and heated to 150 ° C. 200 g aromatic polysulfone with repeating units of the formula:

and with a reduced viscosity of 0.44, measured at 25 C on a solution in dimethylformamide, which contains 1 g of poly

contains meres in 100 cm solution are added and the The melt is stirred for 0.75 hours. The temperature of the melt falls to 145 ° C. and 40 g of sodium hydride dispersion are used slowly with gentle stirring to the reaction mixture. Hydrogen and the temperature of the reaction mixture evolve rises to 205 ° C. within two hours, after which time the reaction mixture solidifies. Man lets "the reaction temperature drop to 150 ° and holds 1.5 hours at this temperature, after which the mixture is allowed to cool. The dark red product is washed with it Water and dry it. There are 995 g of polymer product

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with a reduced viscosity of 0.60 (0.5%, weight / volume, in m-cresol).

The n.m.r. analysis shows that the product is a chain

with -j-Uh CO-f units, which possibly

are interrupted by occasional units derived from the polysulfone and that it is grafted on Branches from units of the formula:

m, where m is approximately 1 to 5.

EXAMPLE 2

Copolymers are prepared from caprolactam and the aromatic polysulfone of Example 1 using the procedure of Example 1 with the exception that 1/100-Nengen and that the concentration of caprolactam in the initial charge is 60, 60, 85, 90 and 95% by weight, respectively. amounts to. The polymer is extracted by breaking the cooled reaction product, three times with boiling Vvasser washes and dries in an oven at 90C.

Copolymer Reduced Viscosity (0.5% w / v, m-cresol)

2.0 1.4 1.4 1.3

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% Caprolactam in the
initial batch yield G ys 8.0 G 90 ß, 5 G 85 7.0 G 80 6.0 G 60 5.0

EXAMPLE 3

400 caprolactam are melted and 100 g of the aromatic polysulfone and the method of Example 1 are used, resulting in a clear melt solution. The temperature of the melt is reduced to 100 ° C. and 20 g of sodium hydride dispersion are added. The temperature rises within a period of from 10 minutes to 125 ° C after which _r oie temperature to 1OO ° C drops. After it has been held at 100 ° for 2 1/2 hours, the reaction mixture solidifies. It is cooled, broken up, washed with water and found to contain 490 g of a yellow-orange polymer material with a reduced viscosity of 0.80 (0.5%, weight / volume, in m-cresol).

A similar polymerization is carried out at 80 ° C using 1/50 of the above amounts. after the After seven hours of the reaction, the reaction mixture has become viscous and cloudy, indicating that a some polymerization has taken place.

Analysis by n.m.r. shows that the product has chains of - £ -NIi ..... CO-j} - units, which possibly is interrupted by occasional units derived from the polysulfone with appended, grafted Uweigen from units of the formula

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in which m is approximately 1 to 5.

EXAMPLE 4

A series of copolymers is prepared by fusing 8 g of caprolactam in a glass tube at 150 ° C. with 2 g of (i) diphenyl sulfone, Ui) bis (4-chlorophenyl) -β sulfone, (iii) bis (4-phenoxyphenyl) ) -sulfone, (iv) 4.4 ¹ -bis- (4-chlorophenyl-sulfonyl) -liphenyl, (v) 4-fluoro-diphenyl-eulfone, (vi) 4-chlorophenylsulfonyl - *> enzene, (vii) 4-phenoxydiphenylsulfone , (viii) 4-methoxy-dihenyl-sulfone.

0.1 g of sodium is added to the homogeneous melts hydii dispersion added. Ls develops hydrogen and the The color of the melt is noted. The melts are left for 0.5 hours at 150 ° C. and all mixtures, with the exception of Mixture (i) solidifies after 5 to 10 minutes. After adding more N-acetylcaprolactam (0.1 cm) to (i) and after 15 minutes of heating at 150 ° C., the melt (i) also becomes solid, the solid polymers are pulverized, exe ^ 'ned with chloroform, filtered and dried.

2 0 9 w 0 2

: 25 -

grafted part (superstrate)

I diphenyl sulfone

II bis (4-chlorophenyl) eulfone

ill BiB (4-phenoxyphenyl) sulfone

Iv 4,4'-bis (4-chlorophenyl-sulfonyl) biphenyl

ν 4-fluorodiphenyl sulfone

Vi 4-chlorophenylsulfonyl-benzene

vli 4-phenoxydiphenyl-8ulfon

viii 4-methoxydiphenyl sulfone

Coloring of the melt

light yellow

^p olymeres

Yield Reduced viscosity 0.5% w / v m-cresol

7.3 g

orange-yellow 7, O g

bright
yellow

Brown

yellow orange yellow yellow

6.5 g

6.4 g

0.80

0.91

2.0

0.98

not measured

8.8 g

8.2 g

2.2 g

1.0

0.8

0.01

The n.m.r. analysis shows that the polymer chain is about 1 wt. * Contains units which are derived from the sulfones (ii to viii). Finds no sign of reaction one in the case of the suIfon (i).

E) LISPIEL

The procedure of Example 1 is repeated on the scale χ 0, Ql with the exception that the melt heated for one hour at 150 ° C. The reaction mixture yields polymeric material with a reduced viscosity of 8.2 1.08 (0.5%, weight / volume, in m-cresol).

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Analysis by nmr shows that the product is a chain of -frNH CO;} · units, possibly interrupted by occasional units which are derived from the polysulfone, as well as appending grafted twos of units of the formula:

has, wherein in is approximately 1 to 5.

The procedure is repeated with the exception that instead of the aromatic polysulfone of Example 1, a sample of "Polysulfone" P.1700 from Union Carbide Corporation used which repeating units of the formula:

should have. The solid reaction product is orange-yellow and 7.2 g of polymeric material are obtained from it with a reduced viscosity of 1.0 (0.5% weight / volume, in m-cresol).

EXAMPLE 6

8 g lauryl lactam and 2 g 4-chlorophenylsulfonylbenzene, are fused together in a nitrogen atmosphere. 1 g of sodium hydride dispersion is added and the mixture is stirred at a temperature of 150 ° C. After 10 minutes The mixture solidifies and the heating is continued for an additional 0.5

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- 27 - 221034 '

Hours fo ¹ ■. The mixture is dark brown. Extraction according to the methodology 1 results in 6.5 g of polymeric material with an reduced viscosity of 2.5 (0.5% lg, weight / volume, in esol).

For Vergleichszwec ^J a similar polymerization rd in the absence of 4-Chlorph>. j.sulfonylbenzene and the result is 1.5 polymeric material with a reduced viscosity of 0.38 (0.5%, 2 weight / volume, in m-cresoi).

BLISPLAY 7

50 g of powdered nylon 6: 6 { 'Maranyl ^ O · Imperial Chemical Industries Limited), one merges i>. "* .J g of diphenyl sulfone forms a round bottom flask of 500 cc capacity, wherein ε is. ^ Nearly homogeneous solution for 1.5 hours with stirring at 150 ⁰ C, in the four-solution are added 1 g hatriumhyuriddispersion added, 50 g of aromatic polysulfone of Example 1 with a reduced viscosity of 0.44, it is melted with 100 g of diphenylsulfone in a round bottom flask with a capacity of 250 cm and stirred for 0.75 hours. This melt is slowly added to the nylon 6: 6 / diphenylsulfone nozzle. The resulting solution is stirred for one hour and held at 150 ° C, resulting in a purple mixture. The reaction mixture is poured onto an aluminum boa and allowed to cool. The solid mass is broken up, pulverized and the polymeric material extracted by washing with water and methanol and then dried.

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- 2Θ -

EXAMPLE 6

300 g of caprolactam and 200 g of the aromatic polysulfones described in Example 1 are swollen and the mixture is stirred for 1.5 hours at 150 ° C. in order to ensure homogeneity of the melt. 0.25 g of sodium metal chips are slowly added to the melt. The temperature the melt is increased to 160 °. After a further 2.5 hours, the melt is allowed to cool and the polymer Material is extracted following the procedure of Example 2. This is found to have a reduced viscosity of 0.14 possesses (0.5%, weight / volume, in m-cresol).

Analysis by n.m.r. shows that the product has a chain of {nh CO jf · units, «rich is possibly interrupted by occasional units, uie derive from the polysulfone, and the product also has attached grafted branches from units of the formulaχ

in which m is about 1 to 5.

EXAMPLE 9

90 g of nylon 6 ('Maranyl' F114) are melted in one Round-bottomed flask with 250 cm capacity and heated for about 2 hours, during which a flowable melt forms. Man adds 0.5 g of sodium hydride dispersion. After * the foaming has stopped, 10 g of aromatic polysulfone

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of Example 1, but with a reduced viscosity of 0.41 added. A deep purple color is formed. The mixture is further heated for 2 hours at 25O ⁰ C under a nitrogen atmosphere. Upon cooling, the polymer product is extracted according to the procedure of Example 2 and is found to have a reduced viscosity of 0.70 (0.5%, weight / volume, in m-cresol).

EXAMPLE 10

Copolymers are prepared according to the method of Example 2 with the exception that capryllactam is used and the type of aromatic sulfone converted is varied.

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% Caprylic lactam in
the initial
Batch Aromatic sulfone % in the other
cl§ 4e ^chen? Copolymer Coloring of the
Reaction
product i) 100 *
ii) 99 * (+ 1% N-
Acetylcapryllactar
iii) 80%
iv) 99%
v) 80%
vi) 80% Art 20%
1 %
20%
20% yield light brown
light brown
light brown
Brown
light brown
light brown )
4-chlorodiphenyl
sulfone
4-chlorophenyl
sulfonyl benzene
Aromatic poly
sulfon of example .1
Polysulfone P1700
LJnipn Carbide
Corporation (as in
Example 5) 6.0 g
7.2 g
10.0 g
5.7 g
8.8 g
7.0 g

" ^w "

Analysis only shows that the product of (v) has a chain of £ * »! ..... COj- units, which may be interrupted by occasional units derived from the polysulfone with attached grafted branches from units of the formula

/ r ~ \. I r. —Ν r— ι I Λ-? »

WHERE

in which η is about 1 to 5.

EXAMPLE 11

A series of polymerizations after Methooe ties Example 1 was conducted except that one carries out the reaction at 15O ⁰ C and the graft polymer resulting by extrusion at 270 to 29o ° C with nylon b ( 'Marany1' F114, trade mark) * The content of aromatic sulfone in the graft polymer is determined by nuclear magnetic resonance spectroscopy.

The mixtures become disks at 240 to 250 ° C 12 cm in diameter and 3.2 mm in thickness. The discs have an excellent surface gloss and are evaluated for hardness and impact resistance, showing results which are shown in the following table.

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No. * Polysulfone
in the copolymer reduced
viscosity
(0.5%,
Weight / volume)
with cresol weight
int
mixture Weight nylon 6
in the mixture - 825 g Moldings 0.5 mm notch
impact resistant
ability -
(kg / πΤ 1 - - - 1500 g 750 g Rockwell
Hardness M 3.36 2 15% 0.9 15OO g - 60.5 0.38 3 13 * 0.78 1500 g 78 0.47 4th 49% 0.35 300 g 76.5 l; 60 5 13%
i 0.78 750 g 80.0 2.02 80.0

In the notched impact strength test, v / elcher at 20 ° C is carried out, a sample 51 mm long, 6.3 mm wide and 3 mm thick is given a 45 ° notch 2.8 mm deep (Tip radius 0.25 mm) in the middle of an edge. The sample is held between two carriers which are spaced apart by 38 mm apart, and it is struck centrally on the edge opposite the notch by a pendulum, which of 305 mm falls with more than the energy sufficient to break the specimen. From the residual energy of the Pendulum, the energy required to break the specimen is calculated and this is determined by the cross-sectional area the sample divided at the notch. The resulting

¹ 2

Value (expressed in kJ / m) represents the energy which

is required to break the material.

EXAMPLE 12

A solution of nylon 6: 6 (82.68 g; 78 amine end groups / 10 g; 0.007 equivalents) and dimethylacetamide (28.71 g; 0.33 equivalents) in 400 cm of m-cresol becomes a solution at 25 ° C of 1,4-diaminobenzene (17.46 g; 0.323 equivalents) in 100 cm of m-cresol was added. The reaction mixture is cooled to 18 ° C. and then a solution of 33.49 g (0.330 equivalents) of terephthaloyl chloride in 100 cm of m-cresol is added over the course of 5 minutes with vigorous stirring. The reaction mixture is allowed to stand at room temperature (about 20 ° C) before 13.66 g (0.330 equivalents)

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Adding lithium hyaroxide. After 6 hours the mixture becomes Macerated in methanol, washed with water and dried in an oven. The resulting block copolymer possesses a reduced viscosity of 1.49, measured at 25 ° C on a solution in concentrated sulfuric acid, which 1 g Contains polymer in 100 cm solution (1%, weight / volume).

A spinning solution is prepared by placing a sample of the block copolymer in a concentrated (98%) Dissolves sulfuric acid (11 percent by weight) at room temperature. The solution is clear, but gels after 15 hours Standing, although the solution is reformed by heating to 40 ° C. The solution is then extruded through a Platinum spinneret with 20 holes (diameter of each hole 100 µm) and immersed in a water coagulating bath fall, the water of which is continuously replaced. The resulting threads are allowed to fall freely into the bath (about 60 cm), so that they are coagulated enough to be taken over guides and getting wound up. The results of the physical test are shown in the table below.

The threads are drawn after spinning, but before drying, by letting them go directly from the coagulating bath onto a drawing frame, where they are passed over rollers rotating at different speeds. The ratio of the peripheral speeds of the rollers is taken as the draw ratio of the threads. The strings

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Facien

Drawing temperature

( ⁰ C)

initial modulus (g dtex " ¹ )

strength
(g dtex " ¹ )

Elongation at break

Block copolymer

not drawn - 1.2: 1 25th 1.2: 1 150 1.7: 1 170 2.0: 1 180 1.3: 1
2: 1 then 170
210 Nylon fa : 6

not drawn 3: 1

110

17th , 6 0.30 22nd , 7 0.45 21st , 5 0.48 23 , 9 0.57 33 , 5 0.64 43 , 3 0.99

4.3
10.4

0.3
1.1

3.1 9.0 13.0 11.9 11.9 17.2

162.6 17.7

are also drawn by passing them over a heated drawing plate lets go, which is arranged between the rollers. After pulling, the threads are washed with water and opened dried by the take-up reel.

For comparison, a (11% by weight) solution of nylon 6: 6 polymer in concentrated (98%) sulfuric acid is spun as described above, but drawn at 110.degree. The results of the physical test are given in the table above.

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The filamentary block copolymer can be used for reinforcing composite materials, fan belts and tire cord can be used. The threads can also be easily made with nylon 6: 6 be mixed.

The results show that the elongation at break of the threads when drawn shows a five-fold increase and that the initial modulus is a factor of 4 times that of Nylon 6 »6 is.

BLISPLAY 13

A solution of 5.075 g (0.05 equivalents) Terephthalo} lchlorid in 25 g of m-cresol, are employed at a temperature of less ale 20 ⁰ C in a nitrogen atmosphere to a solution of nylon 6: 6 (68 amine per 10 g; 56.69 g, containing 0.005 equivalents of amine end groups in 200 g of m-cresol. This mixture is stirred vigorously while 2.43 g (0.045 equivalents) of 1,4-aminobenzene in 15 g of m-cresol are added. The reaction mixture is held for 2 hours with stirring at 20 ° C. 2.1 g of lithium hydroxyci are added to the reaction mixture and, after 30 minutes, the reaction mixture is poured into methanol, the resulting precipitate is washed with methanol and water and dried. The resulting polymer has a reduced viscosity of 1.30, measured at 25 ° C. on a solution in concentrated sulfuric acid which contains 1 g of polymer in 100 cm ^{3 of} solution (ie 1%, weight / volume).

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The nylon 6: 6 has a reduced viscosity of 0.74 (1%, weight / volume, at 25 ° C in concentrated sulfuric acid) .

EXAMPLE 14

The procedure of Example 13 is followed except that the following amounts of starting materials are used can be applied:

Nylon 6: 6 28.35 grams (0.0025 equivalents)

1,4-diaminobenzene 6.70 g (0.1225 equivalents) Terephthaloyl chloride 12.69 g (0.1250 equivalents)

The resulting polymer has a reduced viscosity of 0.88 (measured at 25 ° C on a 1% Solution, weight / volume, in concentrated sulfuric acid). Nuclear magnetic resonance spectroscopy shows that the Concentration of terephthalamide is about 30 percent by weight

EXAMPLE j.5

4.0 g of pyridine are added under a nitrogen atmosphere at a temperature of 10 ° C. to a solution of nylon 6: 6 (88 amine groups per 10 g, 31.25 g; containing 0.003 equivalents of amine end groups). A solution of 5.075 g (0.05 equivalents) of terephthaloyl chloride in 25 g of m-Kreeol is added, followed by a slow addition of 2.046 g (0.038 equivalents) of p-phenylenediamine. the

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The reaction temperature is kept at less than 10 C. One leaves the temperature of the reaction mixture rise to 20 C, holds for two hours at this temperature, and then poured into methanol. The polymer is according to the procedure of Examples 12 extracted. The polymer is shown by infrared analysis to contain the original nylon 6: 6 at a small amount of di-m-tolyl terephthalate.

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Claims (3)

Claims 1. Block copolymer characterized by 1 to 99% units of aromatic polymer with a high modulus, viz of polyamides and polyesters, and 99 to 1% units which are derived from a thermoplastic condensation polymer derive. 2. Block copolymer according to claim 1, characterized in that the aromatic polymer is a polyamide. 3. Block copolymer according to claim 1 or 2, characterized characterized in that the aromatic polymer contains units which are derived from terephthalic acid. 4. Block copolymer according to claim 2 or 3, characterized characterized in that the aromatic polymer contains units which are derived from 1,4-Oiaminobenzene. 5. Block copolymer according to claim 1 to 4, characterized in that the thermoplastic condensation polymer is an aliphatic polyamide. 6. Block copolymer according to claim 1 to 5, characterized in that it is in the form of a designed object is located. 209838/1102 7. Block copolymer according to claim 6, characterized in that it is in the form of threads. 8. Block copolymer according to claim 7, characterized in that the threads are drawn. 9. Process for the preparation of a block copolymer according to claim 1 to 8, characterized in that the aromatic polyamide or the polyester with the thermoplastic Condensation polymers in the presence of a solvent and an acid acceptor at a temperature of less than 30 ° C. 10. The method according to claim 9, characterized in that that the solvent used is m-cresol. 11. The method according to claim 9 and 10, characterized in that there is used as the acid acceptor lithium hydroxide. ^ 2 J Process for the preparation of copolymers according to one of the preceding works, characterized in that at least a compound which among the polyamides, polysulfonamides and lactams are selected with an aromatic sulfone in the presence of an alkaline catalyst to react. 209838/1102 13. The method according to claim 12, characterized in that that a polyamide is used. 14. The method according to claim 12 and 13, characterized in that an aromatic sulfon is used which at least one complies with the formula contains. 15. The method according to claim 12 and 13, characterized in that that an aromatic sulfon is used which has at least one unit of the formula CH., CH ₃ contains. 3 0/1! 02 OR! GINAL INSPECTED