DE2331245A1 - POLYARYLENESTERS, THE PROCESS FOR THEIR MANUFACTURING, THEIR USE AS ADHESIVES AND ADHESIVE COMPOUNDS CONTAINING THESE COMPOUNDS - Google Patents

Description

SUMITOMO CHEMICAL COMPANY, LIMITED
Osaka, Japan '

"Polyarylene esters, process for their preparation, their use as adhesives and adhesives containing these compounds »

Priority: June 19, 1972, Japan, No. 61 505/72

The invention relates to new polyarylene esters, processes for their Manufacture, their use as adhesives and these compounds containing adhesives. Thermosetting synthetic resins, especially phenolic and epoxy resins, are used as adhesives for Used to bond a wide variety of materials. These adhesives have the advantage that the bond is creep resistant even if a force is applied to the bonded material for a long period of time. Because of this beneficial Properties make them particularly suitable for bonding construction and building materials that have an unlimited Must be firmly glued together. Since thermosetting resins are relatively expensive, will Thermoplastic synthetic resins are in demand as adhesives that give the bonded materials a strong bond and high creep resistance to lend.

309883/1303

So far, however, there is no thermoplastic Kuvisfvharz bokai: -r> t that meets the:; e conditions. Polyvinyl acetate canoe 2v; ar Einei .klebenden paint film form, but its bonding force is relatively weak .. Furthermore, adhesives may be selected from a; thermoplastic resin not used for grounding v ^r Herateilung of Yerklcbungen, the high temperature aut en ^ ^ are -tzt, veil their V'äraestabilität and dimensional stability are unsatisfactory.

Despite these disadvantages, it is possible to use thermoplastic synthetic resins as adhesives, because they are easy to use. can be easily deformed, are unlimited and without -haltbar · mixing with ZV; used ei or more other components can ground v / '/ eiterhin no Aushärtungsir-edium and Av are hardening required, also contain no volatile components that damage the bonding could. In addition, they can form films or coatings that are less brittle and more elastic than the films formed from thermosetting synthetic resins. Finally, they are easy to colorize. A particular advantage is that the thermoplastic synthetic resins can be easily processed, for example softened by heating, and errors in the bonded construction or the material can thereby be corrected.

The object of the invention is to provide thermoplastic Polyarylenestor with excellent adhesive properties, good Xriechbeshändlgkeit and ^T ./ärmestabilität to create. This object is achieved by the invention.

309883/1303

ßAD ORiGiNAL

233174 5

The invention accordingly relates to polyarylene esters, those obtained by polycondensation of a dihydric phenol or its reactive derivative with at least one .aromatic Dicarboxylic acid or its reactive derivative can be prepared are. The invention also relates to a method of manufacture the polyarylene ester, which is characterized in that one in a manner known per se, 2.3. by Grenzflöieheii-Foiy condensation, Schiaelzpolykonden & ation or solutions olykondeij ^ ation, a dihydric phenol or its reactive derivative with at least one aromatic dicarboxylic acid or its responsive «! Polycondensed derivative.

The zv.-egg-valent phenol can by the general formula I

HO

-Ar I

CO «

(R)

Ar

OH

In which Ar is an aromatic radical, preferably the phenylene, diphenylene or naphthyl radical, R is a hydrogen atom, an alkyl radical, v / io is the methyl or ethyl group, a halogenated alkyl radical, an aryl radical, \. ^r ie the phenyl or kaphthyl group, a halogenated aryl group, an aralkyl group such as the benzyl or phenethyl group, a halogenated aralkyl group, an alkylated aryl group, an alkylated aryl group, an alicyclic group or a halogenated alicyclic group, X is an alkylene group, like the 'Ac- thy3 en, ethylene or propylene group, the gc -; - gcücncnfulli an ο · Λ - »: χ: several aryl rusts,

-K-, --O-, -CC-, -S-, -SO- and / or -no ^ groups in the chain al: -: yi

30988 3/1303 ^

may contain an alkyldene radical, such as the ethylidene, propylidene or isopropylidene group, which optionally contains one or more arylene radicals, -K-, -0-, -CO-, -S-, -30- and / or -SC ₀ -

ijen in the chain can contain: an alicyclic ring,

the group -K-, -0-, «CO-, -S-, -SC- or -SO ₂ -, Y is a Halo-

alkyl
gcnator;!, denotes a nitro group, the radical -R ¹ or -OR ¹ , where R ^{1 has} the same meaning as R, m is 0 or rv'.ne is an integer which is not greater than the largest number is the hydrogen atom in the remainder of X, η is the value 0 or an integer no greater than the largest number of hydrogen atoms in the group Ar, ρ is an integer with a value of at least 1, q is the value 0 or 1 and r has the value 0 or an integer with a value of at least 1, where r does not have the V.'ert 0 if q denotes;. ^T ert 1 has.

When the number of groups Y is 2 or more, they can Groups can be the same or different. In the same way, the radicals R and R 'can be identical or different if their number Is 2 or more. The position of the group Y can be in the o-, m- or p-position to the hydroxyl group on the aromatic nucleus.

Preferred examples of dihydric phenols of the general formula I are bis - (^ - hydroxyphenyl) methane, 5is- (4-hydroxy-3-metliy! Phenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) - methane, bis- (A-hydroxy-3,5-dibromophenyl) -methane, bis- (4-hydroxy-3,5-difluorophenyl) -methane, ice- (4-hydroxyphenyl) -ketone, Birj- (4- iiydrcxyphonyj) -sulphide, ice- (^ .- hydroxyphenyl) -sulph on, A, q '-dihydro.-.:../·- diphrnylether, 1,1 -Bis - (-' j-hydroxyphonyl) ~ ethane, 2, T-BiS- ( ⁷ I -] --- droxyrV.:-nyl )-propcine, 2.? _A -SiA> «C / w!> V ^]« _il K '^ - ^' ³ : - ;; ₁ r!: Hylphfcnyl) -propene,

309883/1303

2,2-Bi3- (4-hydroxy-3-chlorophenyl) -propane, 2,2-bis- (4-hydroxy-3,5-dichlorophenyl) -propane, 2,2-bis- (4-hydroxynaphthyl) -propane, bis- (4-hydroxyphenyl) -phenylmethane, bis- (4-hydroxyphenyl) -diphenylmethane, Bis- (4-hydroxyphenyl) -4'-methylphenylmethane, 1,1-bis- (4-hydroxyphenyl) -2,2,2-trichloroethane, bis- (4-hydroxyphenyl) - (4'-chlorophynyl) methane, 1,1 ~ bis (4-hydroxyphenyl) cyclohexane, Bis- (4-hydroxyphenyl) -cyclohexylmethane, 4,4, '- dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, Hydroquinone, resorcinol, 2,6-dihydroxytoluene, 2,6-dihydroxychlorobenzene and 3,6-dihydroxytoluene.

Specific examples of reactive derivatives of the divalent

• »

The phenols of the general formula I are the diesters, such as the dialkyl esters and diphenyl esters.

The aromatic dicarboxylic acids which can be used according to the invention can have the general formula II or III

HOOC-Ar'-COOH or HOOC-Ar "-Z-Ar" -COOH

(II) '(III)

in which Ar * and Ar "each denotes an arylene radical, preferably an o-phenylene, m-phenylene, p-phenylene or naphthylene group, which can be substituted by one or more alkyl radicals and / or halogen atoms an alkylene radical, such as the methylene or ethylene group, an alkylidene radical, such as the ethylidene, isopropylidene or isobutylidene group, the -0-, -CO-, -S- or -SO ₂ - group.

309883/1303

Specific examples of the reactive derivatives of the aromatic Dicarboxylic acids of the general formula II or III are the acid halides, such as the dichlorides, and the diesters, like the dialkyl esters and diphenyl esters.

The polyarylene esters of the invention, hereinafter referred to as APC for short, can also contain functional groups in the molecule, such as the amido group (-CONHp), substituted amido groups (-CONR ^ Rp), where R _{1 and R 2 are} each Y / hydrogen atoms, optionally substituted alkyl or Denotes phenyl groups, but both radicals do not represent hydrogen atoms at the same time, contain amino groups, (-NH ₀ ), carboxyl groups (-COOH), chlorocarbonyl groups (-COCl) or cyano groups (-CN). The introduction of these functional groups can lead to an increase in the adhesive properties.

To produce the APC with the appropriate functional groups, a dihydric phenol can be used with the appropriate functional group or its reactive derivative with the aromatic dicarboxylic acid of the general formula II or III or its reactive derivative polycondensed v / ground.

As the dihydric phenol having a functional group, preferably a compound of the general formula IV

T ¹ «

(IV)

309883/1303 BATH ORIGINAL

-7- 23312A5

can be used in which R _{1 is} a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, Rp is an alkylene group with 1 to 10 carbon atoms and R is a hydroxyl group or an alkoxy group with 1 to 18 carbon atoms or a group of the general formula -NR ^ Rc , in which R ^ and R ₁ - each represent a hydrogen atom or an alkyl radical having 1 to 10 carbon atoms.

Specific examples of dihydric phenols of the general formula IV are: A, A-bis- (4'-hydroxyphenyl) -pentanecarboxylic acid, 5,5-bis- (A-hydroxyphenyl) -pentanecarboxylic acid, A, A-bis- (A ' -hydroxyphenyl) -hexanecarboxylic acid, A, A-bis- (A '- "hydroxyphenyl) -heptanecarboxylic acid, h _t A-bis- (A'-hydroxyphenyl) -octanecarboxylic acid, A, A-bis- (A ^f -hydroxyphenyl) - nonanecarboxylic acid, A, A-3is- (A'-hydroxyphenyl) -decanecarboxylic acid, 5,5-bis- (A'-hydroxyphenyl) -hexanecarboxylic acid, 5,5-bis- (4'-hydroxyphenyl) -heptanecarboxylic acid, 5.5 -bis- (A'-hydroxyphenyl) -nonancarbonsäure, 5, 5-bis- (A'-hydroxyphenyl) -decancarbonsäure and 6,6-bis (A'-hydroxyphenyl) -decancarbonsäure.

Specific examples of derivatives of the dihydric phenols of the general formula IV are the esters, such as the butyl, amyl, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl esters and the amides.

The polycondensation is preferably carried out at relatively low levels Temperatures in a manner known per se, e.g. by

carried out.

"Interfacial polycondensation or Lsung.s-polycondensation". Atl on, / JT " ^L " 30988371303

BADORiQlNAL

The APC with functional groups can also be produced by polycondensation using a monofunctional phenol or a monofunctional carboxylic acid with . the corresponding functional group or its reactive derivative carried out as a molecular weight regulator. Polymers with the functional group in the end position are obtained.

As a monofunctional phenol, for example, compounds of the general Formula V

(ν)

in the R / - either a single bond or an alkylene radical

/ Hydrogen atom, an e with 1 to 10 carbon atoms or the -NH group and Ry a / hydroxyl group, an alkoxy radical with 1 to 18 carbon atoms or a group of the general formula -NRiRc, where R ^ and Rr are each hydrogen atoms or alkyl radicals with 1

represent to 10 carbon atoms, or their derivatives are used will.

Specific examples of monofunctional phenols of the general formula V are 4-hydroxybenzoic acid, 4-hydroxyphenylescetic acid, 3- (4 · hydroxyphenyl) propionic acid, 4- (4'-hydroxyphenyl) butyric acid , 5- (4'-hydroxyphenyl) valeric acid, 4- (4'-hydroxyphenyl) valeric acid and 4-hydroxyacetanilide.

Examples of derivatives of monofunctional phenols in general Formula V are the alkyl esters and amides.

309883/1303

S ORIGINAL

The monofunctional carboxylic acids can, for example, the general Formula VI '

-NH-CR ₀

"j ⁸ (VI)

HOOC-

have, in which Rg is an alkyl radical with 1 to 8 carbon atoms or represents an optionally substituted phenyl group.

When carrying out the polycondensation in the presence of the aforementioned Hol ekulargev / i chtsregelers can use the process of edge surface polycondensation, Solution polycondensation or polycondensation with transesterification can be used. The molecular weight regulator can be added to the reaction system at the beginning or during the polycondensation.

The preparation of the APC with functional groups can also be achieved thereby achieves v / earth that the corresponding functional groups during the polycondensation, e.g. of a divalent Phenol with an aromatic dicarboxylic acid dichloride after surface polycondensation or solution polycondensation trains. By adding ammonia or an amine to the reaction system during or towards the end of the polycondensation reaction one obtains amide groups in the molecule.

Examples of amines that can be used are alkylamines, alkylenediamines and aniline derivatives of the general formula VII

^ V (VII)

309883/1303

used in which Rg and R ^ q each represent a hydrogen atom, an alkyl radical, an aralkyl radical, a carboxyl group, an alkoxy radical, a haloalkyl radical, an amino group or the group -CR ¹ or -NIiC-R ', where R' an alkyl

Il I)

0 0

represents remainder, and χ is an integer from 1 to 5. Specific examples of aniline derivatives of the general formula YII are aniline, p-toluidine, p-anisidine, m-anisidine, m-aminobenzoic acid, p-aminoacetophenone, p-aminobenzophenone, p-aminoacetanilide, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine , p-aminodiphenylamine, 4,4'-diaminodiphenyl methane and h _t h * -diariinodiphenyl ether.

The preparation of the APC with functional groups can also be achieved thereby be achieved that the ester bond of an APC is subjected to aminolysis, an amide bond being formed. For example, one can film the APC with a solution of an amine such as a monoamine, diamine, triamine or Treat tetramins in hot water or an alcohol and in this way amidate the surface of the film.

The APC produced according to the invention combines excellent adhesive properties with the advantageous properties of thermoplastic synthetic resins. It can therefore be used as an adhesive. For common purposes, the APC have no functional groups. For particularly strong bonds, an APC with functional groups is preferred used.

309883/1303

The polyarylene esters of the invention preferably have a specific viscosity of at least about 0.35 ^ ,, - / C, preferably

^B P

of at least about 0.4 V. _e _ / C, determined in chloroform at

sp

a concentration of 0.5 g / dl at 25 ⁰ C, for use as adhesives.

Compared with conventional adhesives based on polyhydroxyethers and polycarbonates, the polyarylene esters of the invention have superior thermal stability. Some physical properties of the polyarylene of the invention, the following formula (A) ₁ of the bisphenol-A-polyhydroxyäther of formula (B) and the bisphenol-A-polycarbona4> s of the formula (C) are summarized in Tables I and II. From these tables it is apparent that APC can be used as the adhesive at a temperature up to about 174 ° C, while the Polyhydroxyäther and the polycarbonate are used only below etv / a 85 ⁰ C BZV /.- below about 131 ⁰ C as the adhesive can:

CH.

The molar ratio of group _ (j is 1: 1;

to group -C

OH

0-CH ₂ -CH-CH ₂

(B)

309883/1303

(C)

Table I.

APC Polyhydroxy
ether Polycar
bonat 645 Specific viscosity ^ _<r , / C
(starred in CKCl ₇ " ^p
at 0.5 g / dl and ^J 25 C) 0.601 j ■
0.574: 0.540
- j
i 150 Tensile strength,
kg / cm- 698 560 131
i Einiri ^ temperature
(Tg), ⁰ C 214 .. 100 Dimensional stability, ⁰ C, -
at 18.6 kg / cm ¹¹ load 174 85

Table II

Tp.,. ⁰ C Tensile Strength, kg / cm Polycarborate 100
125
150
170 AFC 360
265
20th
softening 396
355
270
223

In Table III are the adhesive properties of a polyarylene ester (APC) of the invention with basic building blocks of the general formula

CH 0 0

/ = \ I / = \ Il / = \ Il

OH,

specified. The molar ratio of the urupj) e -C-

309883/1303

BAD ORfGlNAL

to the group -,

- is 1: 1. The terminal one

functional group is given in Table IiI. From the table it can be seen that in the tearing test in all Cases the glued aluminum strips used for testing broke. ^

Table III

terminal functional group

Press gmp.,

Average height of shear

because strength, kg / cm

time,

min

at 18CTC

OOH

OCl

ONH

ONH

280 280 280 280 280 280

fracture

fracture

90

82

The polyarylene esters (APC) or adhesives that make up these compounds can be applied in solution to a wide variety of base materials in a conventional manner, e.g. by spraying, dipping or brushing. You can also use it as a Melt onto the base materials, e.g. by extrusion, powder coating, Flame spraying or coating in the 7 / irbelb 'tt,

309883/1303

be applied. It is particularly noteworthy that they can be applied as a film.

The polyarylene esters of the invention have several advantages as adhesives. Because the adhesive only consists of a single component no mixing with other compounds is required. The shelf life is practically unlimited. To the The use of liquid components is not absolutely necessary. The connections are easy to handle. To have to no volatile components are used. Processing is safe. Priming is unnecessary. Long curing times are not required. Gluing is easy and strong bonds can be achieved. The layer thickness the adhesive layer can be easily controlled. Holes are not formed. Laminates of small thickness can be used getting produced. There is no need to use expensive materials. The glue is cheap. A non-woven carrier for a film-like adhesive is not required. A uniform and stable bond can be achieved without any significant Achieve change depending on the hardening or drying time and storage. The adhesive is suitable for gluing of base materials of any shape. The adhesive can be used not only for gluing but also for coating will.

While there are some known thermosetting adhesive films, these are the adhesive films made from the polyarylene esters clearly inferior to the invention. The well-known adhesive ones Films made of the thermosetting resins require chemical

309883/1303

Implementation for gluing while the polyarylene esters of the invention only the use of heat to make it flowable and the use of pressure to bring it together well with the base materials require.

To connect base materials with the help of a thermoplastic adhesive, making the base material flowable or liquefied is of crucial importance. In the case of the polyarylene esters of the invention, liquefaction can be achieved by heating a base material and then pressing on the polyarylene ester. Liquefying can
can also be achieved by the polyarylene ester

heats and then presses a base material onto it. Finally, you can also heat powdered polyarylene ester and then spray it onto a base material and thereby liquefy it. Usually v / ird through
Brief baking at a suitable temperature improves the bond when coating with a solution of the polyarylene ester. The application of pressure is also effective in achieving a good bond.

Examples of base materials to which the polyarylene esters of the invention can be applied are metals, glass,
Proteins, skin, cellulose, natural resins, synthetic organic polymers and non-metallic materials. That with the
Basic material to be bonded material can, for example, in the form of
Plates, foils, powder, cookies or pellets, fibers, threads, cables, fabrics and nonwovens are present. Furthermore, the base material and the material to be bonded to it can be porous or

309883/1303 _ßAD original

not be porous, hard or soft.

The basic metallic materials used are e.g. aluminum, chrome, Cobalt, copper, gold, iron, lead, magnesium, nickel, platinum, silver, tin, titanium, tungsten, vanadium, zinc, steel, brass, Bronze, carbon steel, cast iron, corrosion-resistant steel, nickel-chromium alloys and any other alloys in Question. The metallic base material can be powder, platelets or pellets, foil, plate, rod material, or something else Semi-finished products are available.

The basic material made of glass can be made of glass itself, a ceramic material, clay or an enamel, for example. Examples for base materials based on cellulose are wood, plywood, sawdust, sugar cane, bamboo and paper. As natural Resins come, for example, asphalt, bitumen, plant slime, varnish, pitch, rosin, rubber, shellac, tar and varnish in question. Examples of synthetic organic polymers are phenol-aldehyde condensates, phenol-urea condensates, Epoxy resins, polyolefins, polystyrene, polycarbonates, polyformaldehyde, Vinyl polymers, synthetic rubber-like polymers, polyamides and acrylonitrile-butadiene-styrene polymers.

Other examples of base materials that can be bonded are dyes such as aniline dyes, azo dyes and Stain dyes, pigments such as aniline black, soot, ash, iron gray and cadmium yellow, minerals such as bauxite, carbon, Clay, coal, coke, graphite, gypsum, peat, mica, silica,

309883/1303

Talc, vermiculite, chalk, lava, limestone, marble and quartz, as well as building materials such as bricks, plasterboard, tiles, wall panels and cement, fabrics such as cotton cloth, canvas, cotton textiles, polyester, felt, fiberglass cloth, textiles made of Polyamides, polyacrylonitrile, rayon, silk and wool, fibers and threads e.g. from flax, glass, hemp and i'anila hemp, as well Leather.

As the polyarylene of the invention have a very good heat resistance, adhesives prepared are especially valuable for production of adhesive bonds, the high temperatures of these polymers are exposed to above 150 ⁰ C _1, for example. You can for example. for gluing in turbine engines, air-cooled gasoline engines, lines for hot liquids, reaction vessels, electrical housings and ovens and / or. Flocks are used.

The examples explain the invention. The specific viscosity of the polymers is in chloroform at a concentration of 0.5 g / dl at 25 ° C.

example 1

Production of a polyarylene ester by interfacial polar condensation;

167.793 g (0.735 mol) of 2,2-bis (A'-hydroxyphenyl) propane ( ¹¹ BPA "), 63 g (1.575 Hol) sodium hydroxide and 1 liter V / ater vorgel.gt.

30988 3/1303 BAD ORfGINAL.

500 ml of methylene chloride and 0.5 g of benzyltrimethylammonium chloride are then added. The mixture is stirred at 25 ° C. and a solution of 76.1325 g (0.375 mol) of isophthalic acid chloride ("IPC") and 75.1325 g (0.375 mol) of terephthalic acid chloride ("TPC") in 500 ml of ethylene chloride is added dropwise . After 3 hours 9.411 g (0.1 Hol) phenol, 4.0 g (0.1 mol) sodium hydroxide and 100 ml Waseor are added, and the resulting mixture is stirred for 4 hours. When the reaction has ended, the methylene chloride layer which contains the polymer formed is separated off, washed with water and mixed with acetone. The precipitated polymer is filtered off and dried. Yield 256 g APC, which consists of the basic building blocks of the following general formula

? yV?

The molar ratio of the groups -G- \ AO- to the groups

0 0 · ■

is 1: 1. Most of the terminal

Groups are phenyl ester groups.

Example 2

Production of a polyarylene ester by solution polycondensation;

36.607 g (0.1 mol) of 2,2-bis- (4'-hydroxy-, 3 ', 5 ^l - dichlorophenyl) propane, 10.151 g (0.05 mol) IPC and

309883/1303 BATH ORIGINAL

10.151 g (0.05 mol) TPC submitted. Then 200 ml
o-dichlorobenzene added. The solution obtained is with
20 mg of tetra-n-butyl titanate are added and the mixture is gradually heated with stirring and refluxed for 3 hours. After the addition
of 0.47 g (0.005 mol) of phenol, the mixture becomes another
Stirred for an hour, then cooled and treated with 300 ml of acetone. The precipitated polymer is filtered off, washed with acetone and dried. Yield 35.4g of APC.

Application example A

Two aluminum strips with the dimensions 2 χ 10 cm v / earth cleaned and glued together in such V / else that the one Stripes on top of the other stripes at a width of 1.0 cm

with the adhesive in a layer thickness of 20 microns
is glued. The glued product is clamped in between aluminum plates that are protected with aluminum foil
a heating press is set at a certain temperature and then placed in a cold press to cool to room temperature. The shear strength is measured at 25 ^° C. and 180 ^° C.

The results are shown in Table IV. The APC, the Polyhydroxyether and the polycarbonate are the same compounds as in Table I. The polysulfone is a thermoplastic Polysulfone with basic building blocks of the formula

and a specific viscosity of 0.450 77 / C.

309883/1303

Table IV

adhesive Specific
Viscose
activity Press
pergtur, Stay-
Time,
min average
Shear strength, at 18O ⁰ C APC
Polycarbonate
Polysulfone
Polyhydroxy
ether
Polystyrene 0.601
0.540
0.450
0.574
0.650 280
280
280
200
200 5
5
5
5
5 at 25 ° C 82
0
6th
0
0 90
30th
29
25th
5

From the table it can be seen that APC has an excellent bond strength at room temperature, which - ^{even at 180 °} C. - is still sufficiently retained. The other 'adhesives do not have these advantageous properties.

Application example B

Two aluminum strips are laid one on top of the other in such a way that that the one on the other strip at a width of 4 cm and with a layer thickness of the APC adhesive of Example 1 of 50 microns is glued.

The creep resistance is determined according to MIL-A-509OD.

After a six-day load of 100 kg / cm ² at 23 ° C, no creep can be detected with an instrument with an accuracy of 1 χ 10 ~ ⁴ cm. Further, no creep may be determined at a bonded product, which is heated at 10 days a load of 50 kg / cm at 15O ⁰ C. When using a known thermosetting adhesive with good creep resistance, the bonded product shows under constant stress

309883/1303

BATH ORIGINAL

with 100 kg / cm ² at 23 ° C a creep value of 2.0 10 ""'cn. It follows that the creep resistance of the APC is excellent.

Example 3

According to Example 1, 167.793 g (0.735 mol) of BPA _f 63 g (1.575 mol) of sodium hydroxide and 1 liter of v / water are initially introduced. 500 ml of methylene chloride and 0.5 g of benzyltrinethylammonium chloride are then added. The mixture obtained is v; ied at 25 ° C. A solution of 76.1325 g (0.375 mol) of IPC and 76.1325 g (0.375 mol) of TPC were added dropwise with stirring. After 3stUndiger reacting 5.625 g (O _t O375 mol) of p-aminoacetanilide are added and ^ the resulting mixture is stirred for another 4 hours. The methylene chloride layer containing the polymer is then separated off, washed with water and mixed with methanol. The precipitated polymer is filtered off and dried. Yield 251 g of APC with a specific viscosity of 0.687 * £ sr / ** * ^ ³⁵ ! ^ - absorption spectrum shows characteristic bands at 1690 cm "(aromatic amide) and at 1660, 1540 and 1320 cm" ¹ (acetanilide).

Examples 4 to 8.

The reaction is carried out as in Example 3, but other compounds are used to introduce the functional groups used as p-aminoacetanilide. The results are in the table V summarized.

Table V

example Link to the introduction Lot, specific of the functional groups Mole viscosity 4th aniline 0.075 0.706 5 p-phenylenediamine 0.075 0.702 6th o-phenylenediamine 0.075 1.122 7th Phthalimide 0.075 0.788 8th Ethanolanine 0.075 0.570

Example 9

The reaction is carried out according to Example 2, but v / ground 21.916 g (0.096 mol) of BPA instead of 2,2-bis (4'-hydroxy-3 ^l, 5'-dichlorophenyl) propane used. The polymer is isolated from the reaction mixture by cooling without adding phenol. Yield 35.4g. The specific viscosity of the polymer is 0.636 ¹ W “/ C. In the IR absorption spectrum, the characteristic

- 1
ristic band at 1800 cm "(acid chloride).

“Example 10

According to Example 2, the reaction is carried out as in Example 9, but with the addition of 2 ml of water after refluxing for 3 hours in order to saponify unreacted acid chloride. The specific viscosity of the polymer formed is

i 0.601 ^ s

Example 11

According to Example 2, 22.601 g (0.099 hol) of bisphenol A, 0.33 g (0.001 mol) of 2,2-bis (4'-hydroxyphenyl) valeric acid,

309883/1303

8.4 g of sodium hydroxide, 0.5 mg of sodium hydrosulfite and 100 ml of water / water were initially taken and 50 ml of methylene chloride and 0.1 g of benzyltrimethylammonium chloride were added. Kräftigern under stirring, a solution of 14.211 g (0.07 mol) of IPC and 6,091 g (0.03 mole) of TPC is added dropwise in 70 ml of methylene chloride in a nitrogen stream at 25 ⁰ C. After 3 hours, 1.88 g (0.02 mol) of phenol, 1.0 g of sodium hydroxide and 10 ml of water are added and the reaction is carried out for another 4 hours. The methylene chloride layer containing the polymer formed is then separated off, washed with water and treated with 150 ml of acetone. The precipitated polymer is filtered off and getrock net. APC is obtained with a specific viscosity of

Application examples C to F
Zv / ei aluminum strips with the dimensions

10 cm χ 2 cm χ 0.08 cm are laid one on top of the other in such a V / eise, that one strip is arranged on the other at a width of 1 cm. Fine powder of the example 1 or 2 of the APC produced is applied between the two strips. The bonded product is pressed together by metal plates measuring 20 cm 20 cm heated for some time in an electrically heated press under a certain pressure. Then the bonded product placed in a cold press and under a certain pressure cooled down. The shear strength is measured at a rate of 5 inm / min. The results are summarized in Table VI.

'jf \ C | J ·; ^T. '· ■: ■ *' ι. ι Η τ-, λ; ι. .

Table VI

Anv / en-
manic
at-
spiol Manuf
ment of
APC
(Example) specific
Viscose
ity of ■
AFC
W ^c) Cladding
exercise
temp.,
⁰ C Verv / urgent
Time,
min Disguise
exercise ;; -
drucv:,.
kg / cir; ^ by
cut
liche
Jokes -
stigVc:. ·!:, C. 1 0.601 350 3 30th OO D. 1 0.601 280 5 10 E. 1 0.729 350 3 50 90 F. 0.555 280 5 10 86

Application examples G to R

According to Example 25 to 6, two aluminum strips are grounded with the deiu APC produced in Example 3 to 11 bonded. The shear strength the bond is determined ". The results are: in Table VII summarized:

309883/1303

e ^ Z 0P.K3iNAL

Table VII

co

to

CD

O 33

lung
Dei-
game Creation
/ on AF
(Example) - final function
neile group Speci !.
Viscosity ■ temperature,
⁰ C • Ver
because-
Time,
Min. Cladding
exercise
clruck. average
borrowed shears G 9 -COCl 0.636 280 5 , 10 fracture K 11 -COOH 0.601 280 5 10 102 I. 4th 0.706 270 15th 50 fracture K 4th -CONH-v '^> 0.706 350 3 50 Il 5 0 _T 702 280 15th 100, Il ΊΊ 5 -CO ₁₁ H- ^ MH ₂ 0.702 350 3 100 Il H ₂ N
Λ Λ ν: 6th // Vv 1.122 400 1 30th Il

ro CO CO to cn

Table VII - continued

BAD OR Application "■
manic
fcei-
game "first" ll-ung
from AFC
(Example) terminal function
nell group viscosity gluing ·
temperature, -Ver- -
. £ _. ■ ^ * ^ <- ■ «
"•" ir. / clothe-
os- - by
sectional:
Scheri estig- ■ 0 8th -CO-NHCH ₂ CH ₂ OH 0.570. 280 5 30th £ 860 CD
CO P. 3 -CO-NH-V V-NHCOCH ^
\ - / 3 0 _; 687 280 15th 30th 11 1303 Q- 3
7th -CO-NH - </ ^N
/ CO ^
-CO-Nf T
^ co> 0 _; 687
O ₇ 778 \ . 330
280 5
⁵
j 50
10
I. It
98 J) -NHCOCH ₅

Application examples S to V

The APC prepared in Example 1 or 3 is dissolved in methylene chloride to form a 25 percent solution. This solution is applied with a doctor blade to 2 aluminum strips with the dimensions 10 χ 2 cm and a thickness of 0.5 mm. The paint is dried in the air and then heated ^{to 100 ° C. for 15 minutes.} The aluminum strips are then placed on top of one another at a distance of 1 cm and glued. The bonded product is placed between two metal plates measuring 20 cm χ 20 and pressed for 5 minutes at a pressure of 10 kg / cm and a temperature of 280 ⁰ C and then allowed to cool in another press under pressure. The shear strength of the bond is determined. The results are summarized in Table VIII:

Table VIII

To whom-
manic
at-
game Manuf
ment of
APC,
example specific
Viscose
ity of
APC
ty sp / ^C > Cladding
exercise
terape-
rature,
C. Stay
Time,
min Disguise
exercise s-
pressure.
kg / cm ^ Shear strength;
speed, ₂ !
kg / cm S.
T
U
V. 1
1
3
3 0.601
0.601
0.687
0.687 310
280
280
350 3
5
5
1. 20th
10
10
10. 86 y
90
fracture

Application example YJ

Two of the aluminum strips used in Application Example A. are placed on top of each other at a distance of 1 cm. An APC film is placed between the aluminum strips, made according to example 3 to 8 has been produced. The bonded strips are then placed in an electrically heated press.

3 09883/1303

BATHROOM 0RH3INAL

After 5 minutes of pressing at a pressure of 10 kg / cm at 280 ⁰ C, the bonded strip be cooled in another press under pressure. The adhesive strength is determined for each product. In all cases the aluminum strips break.

Application examples X to Z

Various metal strips with the dimensions 10 cm × 2 cm × 0.05 cm are ^{pretreated for 5 minutes at 70 °} C. with an alkaline cleaning agent in water. The metal strips are then bonded with a 0.1 mm thick APC film with a specific viscosity of 0.66 n \ _sr / ^c. The APC was produced according to Example 5. The metal strips are placed on top of one another at a distance of 1 cm. The bonded product is placed cm between two metal plates measuring 25 cm χ 25 and pressed in an electrically heated press for 10 minutes at a pressure of 50 kg / cra and at a temperature of 290 ⁰ C. The bonded product is then cooled in a cold press under pressure. The shear strength is determined. The results are shown in Table IX. in summary.

Table IX

Metal strips 1 2 Shear strength Application zinc plated
iron zinc plated
iron speed, kg / cm ^ example cold rolled
stole copper 170 X cold rolled
stole Korror-icnsbeständ.i.-
ger steel 120 Y 160 Z

309883/1303

Application example I

Three glass plates measuring 10 cm × 10 cm × 0.3 cm are cleaned with methylene chloride and placed one on top of the other. A 20 percent methylene chloride solution from APC with a specific viscosity of 0 _t 66 ^ _sp / ^c , which was prepared according to Example 1, is used as the intermediate layer. The assembly is dried for about 2 hours at room temperature and under a load of 4 kg. The structure is then heated to 290 ° C. in an electrically heated press and then allowed to cool under pressure. The shear strength is determined. The only thing that happens is that the glass plates break.

Application example II

According to application example I, but using an APC film a thickness of 0.2 mm instead of the APC solution the gluing of the glass plates is carried out. The shear strength the bond obtained is just as strong as in application example I.

Application example III

According to application example I, but using a film the glass plates are glued from the APC, which was produced according to Example 3, instead of the APC solution. The shear strength the bond obtained is just as good as in the application example I.

309883/1303

" ³⁰ " 2331M5

Application example IV

A solution of the APC prepared according to Example 3 in methylene chloride is applied to a surface of a plywood sheet with the dimensions 15 cm × 15 cm × 0.4 cm. Another plywood panel with the same dimensions is placed on this surface and pressed for 10 minutes at a pressure of 20 kg / cm in a press with a heating plate temperature ^{of 180 ° C.} After cooling, a 2 cm wide piece is sawn out. The piece is sawn in half and then broken. The break occurs in the plywood panels, but not in the bond.

Application example V

The APC solution used in Application Example I is applied to the surface of a leather strip with the dimensions 10 cm χ 2 cm χ 0.3 cm applied. Another strip of leather with the same dimensions is pressed on under a pressure of 10 kg / cm at 180 ° C. for 10 minutes. After cooling down the leather strips peeled off from each other. However, there is no tearing at the bond point, but rather in the leather strips self.

Application example VI

A 5 percent methylene chloride solution of the APC prepared according to Example 3 with a specific viscosity of 0 »55 ^ _sp / C is applied to a surface of a 2 cm wide strip of kraft paper. A 2 cm wide strip of APC, 0.15 cm thick and with a specific viscosity of 0.50 ^? £ _sp / C pressed on. The obtained shift

3 09883/1303

OWIGlNAL JNSPECTED

fabric is dried at room temperature. When the APC film is peeled off, only the Kraft paper strip tears.

Application example YII

A 25 percent methylene chloride solution of the APC prepared in Example 9 is mixed with molybdenum disulfide powder in such an amount that the APC content, based on the weight of the molybdenum disulfide, is 10 percent by weight. The mixture is compressed for 1 hour at 100 ° C and then dried to a 2 mm thick sheet at a pressure of 1000 kg / cm at 300 ⁰ C. The tensile strength of a 2 cm wide strip

this plate is 143 kg / cm ...

From this example, the high adhesive force of the APC to powder! Fabrics. It can be self-lubricating Plain bearings with excellent physical properties can be produced.

Application example VIII

According to application example VII, but using polytetrafluoroethylene powder instead of molybdenum disulfide powder, a plate with excellent properties is obtained.

Application example IX

According to Application Example VII, but using iron oxide powder instead of molybdenum disulfide powder, a Plate made. The tensile strength of a 2 cm wide.

Strip from this plate is 200 kg / cm.

3098-83 / 1303 ORIGINAL INSPECTED

From this example it can be seen that with the APC as an adhesive Magnets can be made.

Application example X

A 25 percent methylene chloride solution of the APC prepared according to Example 11 is mixed with aluminum oxide powder in such an amount that the APC content, based on the weight of the aluminum oxide, is 10 percent by weight. The mixture is dried and slightly deformed for 20 minutes at a pressure of 1000 kg / cm "at 33O ⁰ C. The molded body is heated in an oven at 130 ⁰ C under reduced pressure. The tensile strength of the product is excellent.

From this example it can be seen that APC can be used as an adhesive 2 for making abrasive grits.

Application example XI

A 25 percent methylene chloride solution of the APC prepared according to Example 3 is coated with electrically conductive carbon black in such Amount mixed that the APC content based on the weight of the

Soot, /

/ 25 percent by weight. The mixture is ^{dried at 100 °} C. for 1 hour. The product obtained is ground and the powder is pressed for 5 minutes at a pressure of 120 kg / cm at 310 ° C. to form a 0.3 cm thick plate. A 2 cm wide strip from this plate shows an electrical resistance of 7.5 Ω. . cm and has excellent tear resistance.

309883/1303

~ 33 -

Application example XII

A strip of "polyvinyl chloride film with the dimensions
10 cm χ 2.0 approx χ 0.3 cm is applied to a strip with the dimensions 1.0 approx χ 2.0 approx χ 0.3 approx from the A.PC produced according to Example 3 twice and with a width of 1 cm hung up. The end of the APC strip is activated with methylene chloride. The strips are 15 minutes at 95 ° C and a pressure of
35 kg / cm »pressed together. The shear strength of the bonded part is 14 kg / cm ² .

Application example XIII

The bonding is carried out according to Application Example XII, but using a polystyrene film instead of the polyvinyl chloride film. The shear strength of the bonded part is 14 ²

30S883 / 1303

Claims (12)

-34- 2 3 31 ° A 5 claims 1. Polyarylene ester, produced by polycondensation of a dihydric phenol or its reactive derivative with at least one aromatic dicarboxylic acid or its reactive Derivative. 2. polyarylene ester according to claim 1, characterized gor.ennz.eiebnet, that the dihydric phenol has the general formula I. HO-f-Ar -} - -X- -Ar- -OH (D has, in which Ar has an aromatic radical, R a hydrogen γα tem, an alkyl radical, a halogenated alkyl radical, a / tryl radical, a halogenated aryl radical, an aralkyl group, a halogenated aralkyl group, an alkylated aryl group, a haiogenierten alkylated aryl group, an alicyclic group or a halogenated alicyclic radical, X is an alkylene group having optionally one or more arylene, -N-, -0-, -CO-, -S-, -SO- and / or SO ₂ - alkyl
Groups in the chain, an alkylidene group, optionally one or more arylene-, -N-, -0-, -CO-, -S-, -SO- and / or alkyl
S0 ₂ groups in the chain, Y a halogen atom, a nitro group, -R ¹ or -OR ¹ , where R ^{1 has} the same meaning whole> as R, m is 0 or a / number that is not larger than the largest number of hydrogen atoms that can stand on the reading X, η is 0 or is an integer which is not greater as the greatest number of hydrogen atoms that can be attached to the group Ar , ρ is an integer with a value of 309883/1303 is at least 1, q is 0 or 1 and r is 0 or an integer with a value of at least 1, where r is not 0 if q is fourth 1. 3. polyarylene ester according to claim 1, characterized in that the aromatic dicarboxylic acid has the general formula HOOC-Ar • -COOH or HOOC-Ar "-Z-Ar" -COOH (II) (III) in which Ar ¹ and Ar "each represent an arylene group , one or more
which is optionally substituted by / alkyl radicals and / or halogen atoms, and Z is an alkylene group, the group -0-, -CO-, -S- or -SO ₂ -. 4. Polyarylene ester, produced by the polycondensation of a dihydric phenol of the general formula IV _ f 1 χ / -? ΛΧ ^(IV) HO I OH f ² in which R ₁ denotes a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, Rp denotes an alkylene group with 1 to 10 carbon atoms and R ₃ denotes a hydroxyl group, an alkoxy group with 1 to 18 carbon atoms or a group of the general formula -NR ^ Rc, in which R ^ and R ^ each represent hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms, or their derivatives, with an aromatic picarboxylic acid or its derivatives. 309883/130 3 5. Polyarylene ester, produced by polycondensation of a dihydric phenol or its derivative with an aromatic one Dicarboxylic acid or its derivative in the presence of a monofunctional phenol of the general formula V. Il
R ₆ -CR ₇ in the Rg either a single bond or an alkylene radical with 1 to 10 carbon atoms or the -NH group and R «a Hydroxyl group, an alkoxy radical having 1 to 18 carbon atoms or a group of the general formula -NR ^ Rc in which R ^ and Rc each hydrogen atoms or alkyl radicals with 1 to Represent 10 carbon atoms, or its derivative, or a monofunctional carboxylic acid of the general formula Vi , NH-C-R, HOOC ^l 8 0 (VI) in which R _Q - denotes an alkyl radical having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group, or a derivative thereof. 6. Polyarylene ester, produced by polycondensation of a dihydric phenol or its derivative with an aromatic one Dicarboxylic acid or its derivative in the presence of ammonia or an amine. 309883/1 303 7. polyarylene ester according to claim 6, characterized in that the amine is an alkylamine, alkylenediamine or an aniline derivative of the general formula vil (VII) in which Rg and R ^ ₀ each represent a hydrogen atom, an alkyl radical, an aralkyl radical, a carboxyl group, an alkoxy group, a haloalkyl group, an amino group, the group -CR ¹ or -NHC-R *, in which R ^{1 is} an alkyl radical is and Il It 0 0 χ is an integer with a fourth from 1 to 5. 8. Polyarylene ester, prepared by polycondensation of a dihydric phenol or its derivative with an aromatic one Dicarboxylic acid or its derivative, and subsequent aminolysis of the Sster bond in the product obtained to form an amide bond. 9. polyarylene ester according to claim 1 to 8, characterized by a specific viscosity of at least about 0.35? Z _S _ / C, measured in chloroform at a concentration of 0.5 g / dl at 25 ° C. 10. polyarylene ester according to claim 9, characterized by a specific viscosity of at least about 0.4 7 / C. c sp 11. Use of the polyarylene ester according to claim 9 as an adhesive. 309883/1303 12. Adhesive, characterized by a content of a poly Arylene ester according to claim 9. 309883/1303