CH641819A5 - Process for the preparation of segmented copolyesters - Google Patents

Description

The present invention relates to a method for producing segmented copolyesters.

The inventive method for the production of segmented copolyesters is characterized in that

(1) Dicarboxylic acid of the formula HC ^ CR ^ C ^ H, wherein R) denotes a divalent saturated aliphatic radical having 2 to 8 carbon atoms or a divalent aromatic radical, as such or in the form of an ester with a volatile alcohol or in acid chloride or Acid-anhydride form,

(2) Diol of the formula HOR2OH, in which R2 denotes a 1,4-cyclo-hexanedimethylene group or a divalent saturated aliphatic radical which has 2 to 12 carbon atoms, in the case where R] is a divalent aromatic radical, but 6 to 12 Has carbon atoms,

and additionally

(3) hydrogenated dilinoleic acid as a saturated dimeric acid, the molecules of which are ascribed the formula H02CR3C02H, and / or

(4) long-chain aliphatic diol with a weight-average molecular weight in the range from 200 to 4000, the molecules of which are ascribed the formula HOR4OH,

3,641,819

to a thermoplastic segmented copolyester. The crystallizable units can be set by the all, the formula of the formula consisting essentially of crystallizable ester units

O O

O O 5 II II

II II -cr, c-or2o-

-CR, C-0R20- (I)

and the amorphous ester units by the general and amorphous ester units of the formula formula

10th

0 0 0 0

II II II II

-CRaC-ORbO- (II) -CR3C-OR4O-

where in formula II Ra for R3 or R, and Rb for R4 or R2 represent 15,

and the combination Ra = Ri and Rb = R2 is excluded - where Rj is one after the removal of the carboxyl group sen, which are connected by ester bonds, in one or more dicarboxylic acids of the group aliphatic-which copolyester of the total weight of the crystallisable Dicarboxylic acids with 4-10 carbon atoms and egg and amorphous ester units of the formulas I and II 5 to nem acid residue of 2-8 carbon atoms and aromatic 75%, in the case that R] is a divalent aromatic residue, 20 dicarboxylic acids from the group terephthalic acid, Isophthalic, however 50 to 75%, are accounted for by the amorphous ester units of the formic acid, phthalic acid, 4,4'-benzophenone dicarboxylic acid, 4,4'-dimel II, and which copolyester is a DTA melt phenylmethane dicarboxylic acid, 4,4 '-Diphenylthioätherdicar temperature of 25 to 150 ° C, an inherent viscosity of bonic acid and 4,4'-diphenylamine dicarboxylic acid obtained at least 0.5 dl / g in solution in chloroform at 25 ° C and the rest.

at a concentration of 0.3 g copolyester per dl chloro- 25 r2 one after removal of the hydroxyl groups from form, an open time of at least 1/4 min. at 20 ° C, one or more saturated aliphatic diol (s) with 2 indicates essentially complete solubility in toluene at 25 ° C. to 12 carbon atoms, divalent radical obtained at a ratio of 10% by weight of copolyester and 90% by weight,

Solvent, a tensile strength of 100-400 kg / cm2, an R3 has the meaning of R2 or R5,

Elongation at break of 400-1000 percent, a T-peel strength 30 R4 has the meaning of R2 or R6,

versus polyvinyl chloride of at least 0.9 kg / cm width R5 one after removing the carboxyl groups from and a DTA glass transition temperature, Tg, under saturated aliphatic dimeric acids (i.e. the polymeric

- 25 ° C. . hydrated and hydrogenated product from 2 molecules of an ethyl

With the copolyesters prepared according to the invention, niche unsaturated fatty acid with about 12 to 26 carbon atoms can be used for solid, reliable bonds, the dimeric acid being saturated and 24 to 52 atoms in which the bonded substrate has no high temperature carbon atoms) is exposed to divalent radical with doors, and wherein no volatile constituent means 22 to 50 carbon atoms and parts are involved. R6 one after removing the hydroxyl groups

The bonds or adhesive bonds can be made to long-chain aliphatic diols with a weight average by adding 40 of the molecular weight from 200 to 4000, preferably 400

(1) A solid, relatively highly thermoplastic polymer, which means divalent residue obtained until 2000, with the solvating agent-free, including solvent, that at least one of the residues R3 and R4 in each means and plasticizers, and an open time at 20 ° C. of amorphous ester unit has the meaning of R5 or Rß, has at least 1/4 minute, melts, provided that if Rj is an aromatic radical, R2 6

(2) the polymer cools below its melting temperature, has 45 to 12 carbon atoms and the amorphous content

(3) the polymer is at a temperature below its 50-75% by weight. These copolyesters have DTA melting temperature in the open state with a sub-melting temperature (differential thermal analysis) of strat and 25 to 150 ° C and an inherent viscosity of at least

(4) the polymer and the substrate so long in contact 0.5 dl / g. This and the other inherent viscosities last until the polymer has returned to its solid, non-sticky 50 in solution in chloroform at 25 ° C and in a capable state. Concentration of 0.3 g copolyester per dl chloroform

Using this process, surfaces can match each other. In general, the inherent viscosities are glued or adhesive coatings on substrates of the copolyester can be at most 1.5 dl / g at 25 ° C.

be applied. The copolyesters produced according to the invention are

To carry out this method, the inventions can initially only be bonded if they are heated to or above the segmented copolyester produced according to the melting temperature. However, they have been used as a solid, non-sticky, highly cohesive, remarkable property that they are solvent-free thermoplastic polymers for a certain time, from a few seconds to many minutes after they show no cold flow under themselves and below them their melting temperature and normal room temperature,

Melting temperatures have no undesirable sticking (non-block 60, i.e. 20 to 25 ° C or even below, cooled, king), which, however, is aggressively sticky "open" when melting, i.e. sticky and sticky, stay. The of-and be bondable. These copolyesters exist in the open period of the individual polymers, which depends heavily on their essential chemical composition of about 5 to 75 percent by weight of an amorphous mixture. During their open time, ester units and 95 to 25 weight percent crystallize the polymers firmly to substrates, the normal temperature ester units, which are linked to one another via ester bonds and thus often temperatures that are far below the bound. The term “crystallizable” means that the melting temperature of the polymer is below. The crystalline ester units, as well as those ester units open at the time of the copolyester, is at least 1/4 minute, which can become crystalline. 20 ° C and generally not more than 1 hour at 20 ° C.

641819

At the end of the open time or waiting time, a tight bond forms, which can be removed by heating.

The copolyesters produced according to the invention preferably have melting points of at least 40 ° C. Polymers with melting points down to 25 ° C are valuable for certain applications, for example as a temporary binder in the simulation of molds for the production of short-lived molds. For most applications as adhesives, adhesive strips, permanent binders and coatings, the polymers preferably have melting temperatures of about 65 to 150 ° C. This class of copolyesters is particularly preferred. The open time depends on the composition of the individual copolymers.

Small amounts of other materials may be present as long as they do not interfere with the polymerization reaction to form the segmented copolyesters. In order to increase the open time and / or the solubility of the copolyesters in which it is completely aromatic, they contain at least 50 percent by weight of amorphous ester units. In any case, the residues Rb R2, R3 and R4 and the other building blocks should be selected such that the segmented copolyesters produced according to the invention have a melting temperature in differential thermal analysis (DTA) of about 25 to 150 ° C., preferably 65 to 150 ° C. have an inherent viscosity of at least 0.5 dl / g and an open time of at least 1/4 minute at 20 ° C.

The open time is measured by heating a polymer strip measuring 2.5 cm × 7.5 cm × 300 μm on a 2 mm thick slide on a hotplate to the melting point of the polymer, removing the slide from the hotplate and immediately using the Polymer side after. above at about 20 ° C on a heat-insulating surface, for example on a paper block. The open time is the time that elapses from placing the heated slide on the heat-insulating surface until the time when a paper strip that has come into contact with the copolyester surface no longer adheres. The melting temperature is determined by differential thermal analysis (DTA) and determined at the peak of the endothermic maximum. It is measured in a helium atmosphere at 98 420 Pa (740 Torr) and a temperature rise of 30 ° C / min. The measurement is generally carried out in a temperature range from approximately -140 to + 200 ° C. Details of this process can be found, for example, at C.B. Murphy in “Differential Thermal Analysis-sis”, ed. R.C. Mackenzie, Academic Press, New York, 1970, Vol. I, pp. 643 to 671.

The copolyesters made according to the invention are substantially linear, have a relatively high molecular weight and strength and adhere well to a variety of substrates including porous materials such as wood and paper, glass, ceramics, metals such as anodized aluminum, and others Polymers such as polyesters, polycarbonates, vinyl plastics and polystyrene.

The copolyesters produced according to the invention have the following properties:

(1) tensile strength of 100 to 400 kg / cm2;

(2) elongation at break from 400 to 1000 percent;

(3) T-peel strength against vinyl of at least 0.9 kg / cm width;

(4) DTA glass transition temperature, Tg, below -25 ° C;

(5) essentially complete solubility in toluene at 25 ° C at a ratio of about 10 weight percent copolyester and 90 weight percent solvent.

In general, those made according to the invention

Copolyester acid values of 5 or less. The end groups of the copolyesters are either carboxyl or hydroxyl groups or simple derivatives of these groups, such as esters, acid chlorides or anhydrides.

5 The tensile strength and the elongation at break are measured in accordance with ASTM D 882 and the T-peel strength in accordance with ASTM D 1876-69 at a separation speed of 30 cm / min. The tensile strength, the elongation at break and the T-peel strength are determined at room temperature from 20 to 25 ° C 10. The glass transition temperature (temperature range in which an amorphous polymer changes from a brittle glassy state to a flexible, rubbery state) is measured by differential thermal analysis according to the method given above for the determination of the melting temperature. The acid number is defined by the amount of potassium hydroxide in mg that is required as an indicator when titrating 1 g of polymer against bromothymol blue.

The copolyesters preferably contain only carbon, 20 hydrogen and oxygen.

The dicarboxylic acid precursors with the radical Rj are also referred to as short-chain dicarboxylic acids, the diol precursors with the radical R2 as short-chain diols, the dicarboxylic acid precursors with the radical R5 as long-chain dicarboxylic acids and the 25 diol precursors with the radical R $ as long-chain diols. The relative amount of crystallizable and amorphous units is determined by the amount of precursor compounds presented. Very often, the copolyester are reaction products of a long-chain and a short-chain precursor with one functional group and a short-chain precursor with the other functional group. In the case of such a stoichiometrically balanced feed with three monomers, the percentages by weight of amorphous and crystallizable units can be calculated exactly. This also applies if more than three monomers of only three different types are used, for example two short-chain dicarboxylic acids, one short-chain and one long-chain diol, but no long-chain dicarboxylic acid. If the feed contains all four types of monomers, the relative amounts of amorphous and crystallizable units cannot be calculated exactly. However, a very narrow range can be specified in which these values fall. To calculate the minimum amorphous content in such a copolyester, it is assumed that the maximum possible conversion takes place between the short-chain diol and the short-chain dicarboxylic acid. The proportion of crystallizable units is maximized. To calculate the maximum amorphous fraction, it is assumed that the maximum possible reaction first takes place between the short-chain dicarboxylic acid and the long-chain diol and the short-chain diol and the long-chain dicarboxylic acid, with the remaining reaction participants, which may still be present, then together

40

45

55

react.

The amorphous and crystallizable copolyester units can alternate in the polymer chains or appear in the form of blocks of the same type. This can be influenced to some extent by the manufacturing process. For example, prepolymers can be prepared separately from crystallizable and / or amorphous units, which results in larger blocks of one type or the other. Usually, however, the monomeric precursors are introduced directly and simultaneously into the reaction vessel.

65 It was found that these changes, if any, lead to only slight differences in the polymeric end products and that the polymeric products largely depend on the ratios and chemical nature of the individual crystallizable and amorphous units, the above

5 641 819

are defined, and by the molecular weight of the copolyesters provided, advantageously as binding or adhesive

near polymers are influenced. medium can be used include protective coatings. The amorphous copolyester blocks are very often made from old surface basecoats (for example on polyesters such as long-chain diol and short-chain dicarbon-polyethylene terephthalate), heat-activatable adhesives (composed of acid residues. This does not have to be used, however as such or in heat-activated transfer

be the case. tapes and fiber-reinforced adhesive films), permanent binders

Preferred short-chain diols are 1,5-pentanediol and (for example in various film-like products,

Cyclohexane-1,4-dimethanol, which is a mixture of ice and magnetic tapes) and temporary or provisional binding

trans isomers, for example as a mixture with about 30 percent.

zent ice and 70 percent trans-cyclohexane-l, 4-dimethanol, 10 Certain copolyesters produced according to the invention can. are preferably used as binders in magnetic

The chemical structure of the long chain diols is not drawing media, which is a non-magnetizable base critical. Any substituents that do not interfere with the polymeric binder with a coating of magnetizable particles in a cation reaction to form the copolyester can be used. The binders in these tigen be present. The chain can contain from a single 15 objects Çopo-divalent, acyclic or alicyclic hydrocarbon esters produced according to the invention, which essentially consist of about 25 to 75 weight percent residue, poly (alkylene oxide) residue, polyester residue or a cent amorphous ester unit and 75 to 25 Weight percent mixture of these residues are formed. The hydroxyl groups are crystallizable ester units, where Rt is preferred of the long-chain diols as far as possible as terminal tetramethylene and / or phenylene and the Codige groups are present. The long chain dicarboxylic acids 20 polyesters have a DTA melting temperature of about 65 to include dimerized and hydrogenated ethylenically unsaturated 150 ° C and a DTA glass transition temperature, Tg, un-Ci2-C26 fatty acids; see. U.S. Patent 3,538,009. Ter 0 ° C.

The copolyesters can be prepared by conventional polycondensation.

tion process for the formation of polyesters are preferably prepared in mixable, pressure-sensitive bands together with the presence of catalysts. The implementation 25 with a number of different foil-like documents,

tongue is generally carried out in the melt. It like films made of polyester, polyethylene terephthalate, cellulose

however, a solvent for azeotropic removal can be acetate, ethyl cellulose, polyvinyl chloride, vinyl acetate-vinyl

of the condensation by-product can be used. chloride copolymers, polyolefins, e.g. Polyethylene, and the choice of catalyst depends on the starting material - polyurethanes, with fibrous substrates, such as paper and materials. The short chain dicarboxylic acid can be found in some textile goods, with metal foils, e.g. Aluminum foils, and with

Cases used for this alone. Foams such as urethane, polyvinyl chloride and polyolefin are preferably

but a connection with an ionization constant of foams can be used.

more than about 10 ~ 3, e.g. p-tert-butylbenzenesulfone. The copolyesters can be thermally pressed into films using acid. For esterification by transesterification or as hot melts or by extrusion, a transesterification catalyst is usually used. Examples 35 Layering flexible or non-flexible substrates

Manganese (II) acetate, calcium acetate, zinc acetate are used for this. They can also be used to manufacture

Sodium methylate, antimony oxide, antimony glycoxide, tetraalcides from solutions can be used or can be deformed into various kyltitanates and complex titanates, such as magnesium healkyl forms, for example by extrusion

titanate. molding, pressing or casting. Copolyester films can

For the transesterification, for example, the dimethyl ester can be further processed by cold stretching and heat curing a short-chain dicarboxylic acid with a short-chain one. In general, they are coated on suitable substrates with diol and a long-chain diol in the presence of a catalyst which is suitable for the production of tapes by coating in solution Temperatures of 150 to 180 ° C or by extrusion. When heated directly. After about 3 hours, the copolyesters are generally turnable as adhesives in the form of 75 to 90 percent of the theoretical amount of methanol - hot melts as coatings on the Substrates to be manufactured and the copolyester prepolymer has an inherent bond adhesion at the time of use of less than 0.5 dl / g and an acid value of less than 10. The need for a low adhesion Un more than about 10 The pressure in the reaction vessel is background on the Back or from less sticky exclusion reduced to about 665 Pa (5 Torr). One heats clothes in the band-like products of the invention for a further 1 to 2 hours at about 200 ° C. Finally, the temperature (which makes it easier to unwind the tapes from which the pressure is reduced to less than 133 Pa (1 torr) and roll) is largely avoided by the specially heated at about 210 ° C for a further 3 to 5 hours. The copoly used copolyesters.

The polymerization reaction is complete when the inherent vis-transfer adhesive tapes, which have an auxiliary cosmetic copolyester value of at least 0.5, in the low-adhesion laminate pad and a copolyester general of about 1, and the acid value of about 555 films of the invention can be stored in roll form or less. Preferably the conversion will be. At the time of use, they are warmed to temperature of the prepolymer for the copolyester product in counter temperature above the melting temperature of the copolyester of an antioxidant, such as sym-di-β-naphthyl-p-pheny. As long as the copolyester is still open, it is applied to lendiamine or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl) on one surface and the auxiliary pad is removed. 4-hydroxybenzyl) benzene or a hindered polyp- 60 distant. Then bring it with a second sticky Co-nol, such as "Irganox 1010" or "1076" (products of the Ciba polyester layer to which another surface adheres, in Be-Geigy). emotion. At the end of the open time of the copolyester, an additional extension, for example a chain, is firmly glued to both surfaces. With another extension, one achieves using a different kind of product, a nonwoven web is incorporated as an internal isocyanate or dihalosilane, such as diphenyl-dense network of a copolyester layer, whereby the lorsilane or by reaction with epoxysilane, such as ß- ( 3,4- film strength is considerably increased. Likewise, epoxycyclohexyl) ethyltriethoxysilane. There are unclad transfer tapes in which the areas in which the copolyester film produced according to the invention is used directly (without underlay serving as an auxiliary layer

641 819 6

would be rolled up. With such objects, care must be taken that the tape roll is not heated above the melting temperature of the polymer in order to prevent the windings from melting together.

Assuming that a reasonably high molecular weight is reached (which is indicated by an inherent viscosity of at least about 0.5 dl / g), the physical properties of the copolyesters, such as the melting temperature, the glass transition temperature, the tensile strength, the elongation at break , the adhesive properties and the open time, generally controlled by the amount and type of components. In general, as the percentage of the weight of the amorphous units in the copolyesters increases, the open time is extended and the melting temperature is lowered. In addition, the copolyesters of longer chain aliphatic dicarboxylic acids (such as azelaic acid and sebacic acid) tend to have lower melting temperatures than copolyesters of longer chain dicarboxylic acids (such as adipic acid). Since the combination of the desired properties strongly depends on the intended use, different chemical production methods are preferred for different products.

The copolyesters can be modified by adding fillers, pigments, dyes and other modifiers if the products are to be opaque, colored or particularly strong for 2 seconds or if other effects are desired.

The examples illustrate the invention. The part and percentages relate to the weight, unless stated otherwise. 30th

The test procedures given in the examples have been explained above. Unless otherwise stated, the following conditions are used for the T-peeling and lifting test: Strips of anodized aluminum (1.25 cm x 15 cm x 0.002 cm) are placed on blocks of smooth polyvinyl chloride resin (5 cm x 13 cm x 0.4 cm) with a coating of about 0.00125 cm of the copolyester to be examined. The polymers of the invention generally elongate at constant tensile strength until a yield strength of about 200 percent elongation is reached, 40 after which the tensile strength increases, which suggests crystallinity and orientation. The T-peeling and lifting test and the elongation test are carried out at room temperature with a clamping speed of the clamping clamp of about 30 cm per minute. All of the polymers 45 of Examples 1 to 40 are essentially completely soluble in toluene at 25 ° C. in a ratio of about 10 percent by weight copolyester to 90 percent by weight solvent.

The following abbreviations are used in the examples. The subscript index numbers following the abbreviations for the glycols indicate the approximate molecular weight of the materials specified.

AA adipic acid

SA sebacic acid

DA dimeric acid (hydrogenated dilinoleic acid)

CHD 1,4-cyclohexanedimethanol

PTMEG poly (oxytetramethylene) glycol

PCLD polycaprolactone diol

PEG poly (oxyethylene) glycol

PBD polybutadiene

PECG polyoxyethylene carbonate glycol

example 1

Copolyester with 52.0 percent crystallizable blocks and 48.0 percent amorphous blocks

One with a mechanical stirrer, a Dean-Starke-

55

60

65

Cold trap, a thermometer and a gas inlet for maintaining an inert atmosphere of three-necked flasks are loaded as follows:

30.7 parts adipic acid 27.2 parts 1,4-cyclohexanedimethanol 42.1 parts poly (oxytetramethylene) glycol (molecular weight 2000)

0.021 part of antimony glycoxide.

Inert gas is introduced into the flask. The contents of the flask are then brought to 170 ° C. using an oil bath. The mixture is stirred at the temperature mentioned for about 3 hours. During this time, the water formed by the condensation is collected in the trap. The temperature is then reduced to about 145 ° C and the pressure is then reduced to 665 to 33.25 Pa (5 to 0.25 Torr). These conditions are maintained for approximately 1 hour to remove additional volatile material. About 1 part of sym-di-β-naphthyl-p-phenylenediamine (as an antioxidant) is then added, the inert atmosphere being maintained. The temperature of the mixture is increased to 200 to 220 ° C and the pressure is reduced to 19.95 Pa (0.15 Torr). These conditions are maintained for about 4 hours.

The polymer solidifies as a tough, flexible, colorless, opaque material with an inherent viscosity of 0.8 dl / g, a melting temperature (Tm) of about 90 ° C, a glass transition temperature (Tg) of - 82 ° C and an acid number (or Acid value) of 2.0. The product has an open time of 4 minutes, a tensile strength at room temperature of 135 kg / cm2 and an elongation at break of 650 percent. The polymer's T-peel strength (vinyl) is 2.9 kg / cm wide. Strips of anodized aluminum, which are glued to the polymer on polystyrene and lexan, have a T-peel strength of 1.6 and 2.1 kg / cm. A polyester made in a similar manner using only adipic acid and 1,4-cyclohexanedimethanol has an open time of less than 1 minute. This product does not wet vinyl, polystyrene, or lexan resins to a sufficient extent to produce a bond. __

Example 2

In essentially the same way, 24.9 parts of adipic acid, 24.3 parts of hydrogenated dilinoleic acid, 29.4 parts of 1,4-cyclohexanedimethanol, 21.4 parts of poly (oxytetramethylene) glycol (molecular weight 2000) become 0 , 1 part of Irganox (antioxidant) and 0.1 part of tetrabutyl titanate (catalyst) a copolyester with 43.7 to 47.0 percent crystallizable blocks and 53.0 to 56.3 percent amorphous blocks.

The polymer solidifies to a tough, flexible, colorless, opaque material with an inherent viscosity of 0.85 dl / g, a Tm of about 79 ° C, a Tg of - 72 ° C and an acid number of 5. The product has a open time of 6 minutes, a tensile strength at room temperature of 105 kg / cm2 and an elongation at break of 600 percent. The T-peel strength is 4.3 kg / cm width.

The copolyesters of the other examples are produced essentially by the same method, unless special information is given.

Examples 3 to 7

From adipic acid, 1,4-cyclohexanedimethanol and poly (oxytetramethylene) glycol with a molecular weight of around 2000, copolyesters with a proportion of amorphous components and control products varying from 30 to 70 percent are produced. The composition is as follows:

7

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Example of an amorphous percentage by weight

Molar ratio of short-chain diol to long-chain diol product produced. The products of the individual examples have the following composition:

-

polymeric amorphous

Molar ratio of

3rd

0

100/0

5 game

Glycol

Proportion of,

short chain diol

4th

30.3

95/5

% By weight

to long chain diol

5

40.0

92.5 / 7.5

6

48.0

90/10

13

-

0

100/0

7

67.6

80/20

14

PTMEGÖ0

11.9

95/5

io 15

PEG | 000

16.4

95/5

16

PTMEGg9 {|

16.3

95/5

Examples 8 to 12

17th

PCLD, 250

19.3

95/5

From adipic acid, 1,4-cyclohexyndimethanol and various

18th

ptmeg990

29.3

90/10

Different polyglycols with molecular weights of about 1000 are copolyesters with an amorphous content which varies from about 25 to about 65 percent. The products of the individual examples have the following composition:

With polymeric amorphous

Molar ratio of play

Glycol

Proportion of,

short chain diol

% By weight

to long chain diol

3rd

-

0

100/0

8th

pecg750

27.3

90/10

9

ptmeg990

32.5

90/10

10th

pbdiooo (l)

32.6

90/10

11

ptmeg990

52.2

80/20

12

ptmeg990

65.1

70/30

15

Examples 19 to 21 From adipic acid, cyclohexanedimethanol and hydrogenated dilinoleic acid, copolyesters with an amorphous content varying from 20 to 65 percent and a control product are produced. The products of the individual examples have the following composition:

example

3rd

19th

20 30 21

(1) a polybutadiene with terminal hydroxyl groups and a molecular weight of about 1000, which is sold under the name "Hystl G-1000" by the company Hystl Development Co.

EXAMPLES 13 to 18 Copolyesters with an amorphous content varying from about 10 to 30 percent and a comparative process are

amorphous fraction,% by weight

0

22.9 39.9 64.0

Molar ratio of adipic acid to hydrogenated dilinoleic acid

100/0 90/10 80/20 60/40

Examples 22 to 25 From adipic acid, 1,4-cyclohexanedimethanol, poly (oxy-35 tetramethylene) glycol with a molecular weight of about 2000 and hydrogenated dilinoleic acid, copolyesters with an amorphous content varying from 30 to 65 percent are produced. The products of the individual examples have the following composition:

40

example

22

23

24th

25th

amorphous fraction, molar ratio of% by weight of short-chain diol to long-chain diol

34.3-38.0 41.0-44.5 53.0-56.3 (1) 61.8-64.8

95/5 95/5 95/5 95/5

Molar ratio of adipic acid to hydrogenated dilinoleic acid

05/5 90/10 80/20 70/30

(1) corresponds to example 2.

Examples 26 to 30 Copolyesters with an amorphous content varying from 10 to 45 percent and a comparison product are prepared from azelaic acid, 1,5-pentanediol and poly (oxytetramethylene) glycol with a molecular weight of about 630. The products of the individual examples have the following composition:

Example amorphous fraction, wt .-%

26 0

27 13.8

28 35.0

Molar ratio of short chain diol to long chain diol

100/0 95/5 85/15

29 55 30

39.3

43.4

82.5 / 17.5 80/20

Examples 31 to 32 Two copolyesters with an amorphous content in the range 60 of 30 to 34 percent have the following composition:

example

Feed (parts by weight) adipic acid sebacic acid cyclohexanedimethanol poly (oxytetramethylene) glycol,

31

32

32, 4 34, 5 7, 8 5, 3

33, 9 34, 2 25, 9 26, 0

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8th

(Continuation)

example

31

32

Molecular weight 990

Irganox 1010 (antioxidant)

0.1

0.1

Molar ratio of adipic acid to

85/15

90/10

Sebacic acid

Molar ratio of cyclohexane dimethanol

90/10

90/10

to poly (oxytetramethylene) glycol

amorphous fraction, percent by weight

31, 5

31, 8

The molar ratios of adipic acid to sebacic acid are about 80/20 to 95/5 and of 1,4-cyclohexanedimethanol to poly (oxytetramethylene) glycol about 85/15 to 95/5.

Examples 33 to 38 From dimethyl terephthalate, various linear (unbranched) aliphatic diols with 6 to 12 carbon atoms and poly (oxytetramethylene) glycol with a molecular weight of about 2000, copolyesters with an amorphous content varying from about 50 to 75 percent by weight are produced. The products of the individual examples have the following composition:

At aliphatic diol amorphous molar ratio game

Proportion of,

of short chain

% By weight

Diol to langketti

according to diol

33

1,6-hexanediol

60

85/15

34

do.

68

80/20

35

do.

74

75/25

36

1,8-octanediol

58

85/15

37

1,10-decanediol

55

85/15

38

1,12-dodecanediol

53

85/15

Examples 39 to 40 From dimethyl sebacate, dimethyl terephthalate, 1,4-cyclo-hexanedimethanol and poly (oxytetramethylene) glycol with a molecular weight of about 990, copolyesters with 20 amorphous units from 16 to 17 percent are produced. The products of the individual examples have the following composition:

Example Molar ratio of dimethyl sebacate to dimethyl terephthalate

39 95/5

40 97.5 / 2.5

Molar ratio of short chain diol to long chain diol

95/5 95/5

amorphous fraction,% by weight

16.3 16.5

The properties of the copolyesters of Examples 3 to 40 are summarized in Table I.

The copolyesters of Examples 3 to 7, which have an amorphous content of approximately 30 to 33 percent, 46 to 50 percent and 66 to 70 percent, represent preferred classes for hotmelt adhesives, primers (in particular for use on polyethylene terephthalate films) or binders for certain film products. The copolyesters of Example 10 adhere particularly well to acrylonitrile-butadiene-styrene terpolymers (in particular ABS-Royalite 20 from the Uniroyal Plastic Products Division of Uniroyal, Inc. Warsaw, Indiana). The copolyesters of Examples 22 to 25

containing 40 to 65 percent amorphous ester units form a preferred class. The copolyester of Example 24, which contains about 53 to 57 percent amorphous units and in which the ratio of glycol portion to dicarboxylic acid portion is about 3: 7, is particularly preferred as an adhesive in heat-activated transfer tapes, due to the combination of a relatively long open time and high liability. The copolyester of Example 34 is particularly preferred as an adhesive in heat-activatable transfer ribbons, which is due to the combination of open time, T-peel strength, adhesion and high-temperature warping adhesion.

Table I

At

Enamel

Glass

train

Break open

Tab-

inherent

Acid play tempera changeable

firm stretch,

Time,

peel

Worth viscous

tur, ° C

tempera-

speed,

%

min liability,

act

tur, ° C

kg / cm2

kg / cm

3rd

100

-28

~ 250

400

0.5

0

1.01

<5.0

4th

93

-76

210

500

2.0

0.9

0.84

0.7

5

90

-79

220

700

3.0

3.2

0.95

2.2

6

90

-82

135

650

4.0

2.9

0.80

2.0

7

72

-84

123

600

6.0

2.5

0.81

2.4

8th

82

-44

175

500

2.5

1.8

1.00

2.9

9

92

-70

174

500

2.5

1.8

0.95

3.6

10th

92

-26

175

500

3.5

2.3

0.70

1.5

11

70

-78

100-150

500-600

6.0

> 1.8

0.81

3.1

12

58

-82

100-150

500-600

7.0

2.1

0.85

0.7

13

50

-45

254

700

5.0

0.4

1.00

1.0

14

49

-57

188

600

5.5

1.8

0.85

1.8

15

44

-65

174

700

6.5

3.9

1.00

1.0

16

47

-64

181

750

6.5

4.1

1.00

1.0

17th

38

-54

134

600

6.5

2.9

0.80

2.0

18th

45

-70

145

850

9.0

6.8

1.10

1.5

19th

90

-33

100-200

400-500

1.5

0.9

0.75

0.5

9

641819

Table I (continued)

At

Enamel

Glass

train

Break open

Tab-

inherent

Acid play tempera changeable

firm stretch,

Time,

peel

Worth viscous

tur, ° C

tempera-

speed,

%

min liability,

act

tur, ° C

kg / cm2

kg / cm

20th

77

-39

100-200

400-500

4.5

0.9

0.52

0.5

21st

45

-42

100-200

400-500

5.5

0.9

0.70

0.5

22

96

-76

254

650

3.0

0.9

1.00

5.0

23

92

-74

152

550

4.0

1.8

0.80

5.0

24th

79

-72

105

600

6.0

4.3

0.85

5

25th

65

-68

100

400

10.0

2.1

0.70

2nd

26

45

-70

100-400

400-1000

6.5

> 0.9

0.50

4th

27th

44

-80

100-400

400-1000

10.0

> 0.9

0.50

5

28

38

-82

100-400

400-1000

17.0

> 0.9

0.90

5

29

38

-85

100-400

400-1000

30.0

> 0.9

0.50

4.1

30th

38

-82

100-400

400-1000

35.0

> 0.9

0.50

2.3

31

76

-69

120

650

4.0

> 0.9

0.90

32

79

-72

130

600

3.5

> 0.9

0.89

33

130

-84

100-400

400-1000

0.25-1

0.9

0.90

34

114

-86

100-400

400-1000

0.25-1

4.1

0.95

35

100

-82

100-400

400-1000

0.25-1

4.4

0.86

36

130

-84

100-400

400-1000

0.25-1

1.8

0.80

37

120

-84

100-400

400-1000

0.25-1

1.8

0.80

38

110

-84

100-400

400-1000

0.25-1

1.8

0.81

39

48

-62

100-400

400-1000

1-7

> 0.9

> 0.50

40

46

-64

100-400

400-1000

1-7

> 0.9

> 0.50

Examples 41 to 42 A copolyester of sebacic acid, 1,4-cyclohexanedimethanol and poly (oxytetramethylene) glycol with a molecular weight of about 630, which has 11 weight percent amorphous units and a molar ratio of short-chain diol to long-chain diol of 95/5 (same Components as in example 14) are expanded. The copolyester is prepared in the customary manner and then reacted with 1 percent by weight of an epoxysilane (β-3,4- (epoxycyclohexyl) ethyl trimethoxysilane (“AI 86”, Union Carbide and Carbon Corporation)). 1 g of epoxysilane is added dropwise to 100 g of the original copolyester at 180 ° C. with stirring and under nitrogen over the course of about 15 minutes. The mixture is reacted for 2 hours under these conditions. The properties of the original copolyester (Example 41) and the modified copolyester (Example 42) are summarized in Table II.

Tables

example

41

42

A \ y (l)

1610

2150

On (D

473

880

AW / AN ratio

3.40

2.44

Inherent viscosity (dl / gm)

A) 0.5% in tetrahydrofuran

0.59

0.61

B) 0.3% in chloroform

0.71

0.74

Glass transition temperature, ° C

-58

-56

Melting temperature, ° C

+ 42

+42

example

41

42

Overlap train

9.05

15.42

strength (2), kg / cm2

Acid value

4.20

3.50

(1) Aw is the weight average of the length of the polymer chain in Angstrom units. AN is the number average of the length of the polymer chain in Angstrom units. These values will be

30 by gel permeation chromatography according to “Preparative Methods of Polymer Chemistry”, 2nd edition, Sorenson and

Campbell, Interscience Publishers, New York.

(2) This tensile strength is determined at room temperature in accordance with ASTM D-1344-72 using overlapped aluminum 35 mm strips which are bonded to a 1.8 mm thick polymer sample in an area of 2.5 cm × 2.5 cm .

Examples 43 to 44 40 An expanded copolyester, the composition of which corresponds to the product of Example 28, except that PTMEG2ooo is used instead of PTMEG630, is added dropwise at 180 ° C. in the course of 15 minutes with stirring and under nitrogen at 1.0 Weight percent 45 percent isophorone diisocyanate. The mixture is reacted for a further 2 hours under the conditions mentioned. The original copolyester has the values Aw 1200 and An 200. The expanded copolyester has the values Aw 2300 and AN 320.

50 The binders for the magnetic recording media contain segmented copolyesters which consist essentially of about 25-75% by weight of amorphous units and about 75-25% by weight of crystallizable units as defined above, with the exception that R] preferably means 55 tetramethylene, phenylene and / or naphthalene and the DTA melting temperature of the copolyesters mentioned is about 65-150 ° C., the inherent viscosities measured at least 0.5 dl / g, as described above and Tg less than 0 ° C. The open time of these binders can be 60 more or less than 1/4 minute at 20 ° C. Therefore, certain copolyesters produced according to the invention can advantageously be used in binders of the magnetic medium, although the copolyesters used in the magnetic recording media are not restricted to the copolyesters produced according to the invention. Magnetic tapes were made with these binders using a 40 µm polyethylene terephthalate film as the base which was biaxially oriented about 3 times in each direction

641 819

had been manufactured. Usual needle-shaped y-Fe203 particles were used with a 75% by weight loading, which resulted in a Hc in the longitudinal direction of 300 to 320 Oe. The following investigations are particularly important for those applications in which the tape moves over the magnetic heads at high speed.

Square ratio: The ratio of 0r0max or the square ratio of the hysteresis loop with an applied field of 3000 Oe using an M-H meter with 60 cycles should generally be greater than 0.75.

Distribution value (G "): Gn is determined by differentiating the above-mentioned hysteresis loop and is defined by the ratio HC / AH, where AH is the width of the differentiated hysteresis loop at half the height of its maximum. Gn should generally be greater than 2.0.

Abrasion: A 1.27 cm wide tape is glued into a 91.5 cm loop. This loop is moved at a tension of 482 g at a speed of 36.6 m / sec over four magnetic recording heads. The tape is weighed before the test and after a 10 minute test period. A weight loss of less than 5 mg means sufficient abrasion resistance. This experiment is generally compared to a conventional tape, such as No. 888 from Minnesota Mining and Manufacturing Co. or another commercially available tape, which is known to have a weight loss of less than 5 mg.

Blocking: A 1.27 cm wide and 91.5 cm long tape is wound under a tension of 2 kg on a spindle made of corrosion-resistant steel with a diameter of 1.27 cm. After 18 hours of storage in an air circulation oven at 65 ° C. and 80 percent relative humidity, the tape is unwound and examined. If there has been no layer splitting, the tape is described as good. If there are only traces of layer splitting, the tape receives that Satisfactory rating.

In general, the recording tapes have excellent blocking resistance. However, if a tape, which otherwise has the desired properties, only shows a satisfactory resistance to blocking, this can be improved by the magnetizable layer with a very thin coating of a highly fluorinated alkyl polyether, such as "Krytox" 143 from the company EGG du Pont de Nemours & Co., is provided from a 1 percent solution.

Module: The dynamic module of the strip coating is measured on a Rheovibron test device in the temperature range from 0 to 70 ° C. This value should have good constancy over the entire temperature range and should preferably be below 5 x 1010 dynes / cm2. Above this value, there is too much abrasion for the magnetizable layer in a high-speed abrasion test.

Copolyester A is prepared in the usual way and corresponds in composition to the copolyester of Example 32, i.e. the molar ratio of adipic acid to sebacic acid is 90/10 and the molar ratio of 1,4-cyclo-hexanedimethanol to poly (oxytetramethylene) glycol with an average molecular weight of 990 is 90/10. This product has an inherent viscosity of 0.8 dl / g, a melting temperature (Tm) of approximately 79 ° C, a glass transition temperature (Tg) of - 72 ° C and an acid number of 2.0.

Copolyesters B to D are produced in the same way from equivalent amounts of dicarboxylic acids and diolic acids:

10th

Polyester B: adipic acid and 1,4-cyclohexanedimethanol and poly (oxytetramethylene) glycol with an average molecular weight of 990 in a molar ratio of 90/10.

s Polyester C: adipic acid and 1,4-cyclohexanedimethanol and poly (oxytetramethylene) glycol with an average molecular weight of 2000 in a molar ratio of 90/10.

Polyester D: adipic acid and sebacic acid in a mol ratio of 85/15 and 1,4-cyclohexanedimethanol and poly (oxytetramethylene) glycol with an average molecular weight of 990 in a molar ratio of 90/10 (same composition as the copolyester from Example 31 ).

A 25 n thick, heat-cured polyethylene terephthalate film biaxially oriented approximately 3 times in each direction is used as a base for a typical magnetic recording tape. To improve the adhesion of the magnetizable coating, the base is first primed with a solution of an aminated reaction product of an epoxidized 2o polybutadiene (cf. US Pat. No. 3,661,874). A 33.7 percent solid dispersion in cyclohexanone composed as follows is applied over the primer:

25th

acicular y-Fe203 particles anionic phosphate dispersant

Aluminum oxide conductive carbon black A 35 lubricant based on fatty acid derivatives

Parts by weight

70.73 3.54

Parts by weight

1.13 4.24 19.30 1.06

The dispersion is produced as follows: The y-40 Fe203 particles, the dispersant and the aluminum oxide are mixed with 64 g of cyclohexanone (54 percent solids) on a Red Devil shaker in a 0.95 liter «Quickie Mill», the 1800 g contains 0.3 cm grinding medium (steel balls), ground for 45 minutes. 45 soot and 55 g of cyclohexanone (total solids content 40 percent) are then added. The mixture is then ground for a further 15 minutes. Finally, 96.5 g of a 20 percent solution of the copolyester in cyclohexanone and the lubricant are added. The grinding process is then continued for a further 15 minutes 50.

The dispersion is applied to the primer using an engraving roller with corrugation of 127 lines per cm. The coating is dried in an air circulation oven for about 1/2 minute at 82 ° C and then for 1 minute at 55 104 ° C. Within about 1 hour, the surface is polished to an average peak-to-peak roughness of about 0.12 to 0.20 µm (using a Bendix Professional Corder Model No. 5.2.5 (in the pen).

Magnetic recording tapes containing 60 copolyesters B, C and D instead of copolyester A are then produced and subjected to the aforementioned tests. At the same time, commercially available tapes with the same general structure are examined, with the exception that they contain a crosslinked phenoxy-65 urethane system as a binder. The results are summarized in Table III.

11

641 819

Table III

Copolyester in

square

Gn

Abrasion

To block

module

Binder ratio

(dyn / cm2)

A

0.78

2.5

1.8 mg good

4.5 x 10 '°

B

0.75

2.3

*

Good

1.7 x 1010

C.

0.75

2.4

*

Good

1.9 x 10 '°

D

0.79

2.1

3.0 mg satisfied

3.2 1010

posed

control

0.76

2.1

3.2 mg satisfied

6.1 x 1010

posed

* not examined

The following subclasses of magnetic recording media (from the general class indicated at the beginning of the magnetic tape explanatory section) are particularly noteworthy: only one of R3 and R4 is R5 or R6; Rj is predominantly the divalent residue of adipic acid; R2 is a cycloaliphatic radical and contains up to 8 carbon atoms; R3 is a divalent radical of a C36 dimeric acid; R4 denotes poly- (oxyethylene) glycol, poly- (oxypropylene) -glycol, poly- (oyte-tramethylene!) -Glycol and / or copolymers thereof; and R!

20 is essentially completely aromatic and the copolyester contains at least 50 percent by weight of amorphous units.

C.

Claims (9)

641819 PATENT CLAIMS 1. A process for the preparation of segmented copolyesters, characterized in that (1) dicarboxylic acid of the formula H02CRiC02H, in which Ri denotes a divalent saturated aliphatic radical having 2 to 8 carbon atoms or a divalent aromatic radical, as such or in the form of an ester with a volatile alcohol or in acid chloride or acid anhydride form, (2) Diol of the formula HOR2OH, in which R2 denotes a 1,4-cyclo-hexanedimethylene group or a divalent saturated aliphatic radical which has 2 to 12 carbon atoms, in the case where R] is a divalent aromatic radical, but 6 to 12 Has carbon atoms, and additionally (3) hydrogenated dilinoleic acid as a saturated dimeric acid, the molecules of which are ascribed the formula H02CR3C02H, and / or (4) converting long-chain aliphatic diol with a weight average molecular weight in the range from 200 to 4000, the molecules of which are attributed to the formula HOR4OH, to give a thermoplastic segmented copolyester which consists essentially of crystallizable ester units of the formula O O II II - * C R j C-0R20- and from amorphous ester units of the formula O O II II -CRaC-ORbO- (I) (H) where in formula II Ra stands for R3 or R, and Rb stands for R4 or R2 and the combination Ra = Rj and Rb = R2 is excluded, which are connected by ester bonds, in which copolyester of the total weight of the crystallizable and amorphous ester units of the formulas I and II 5 to 75%, in the case that Ri is a divalent aromatic radical, but 50 to 75%, are accounted for by the amorphous ester units of the formula II, and which copolyester has a DTA melting temperature of 25 to 150 ° C. an inherent viscosity of at least 0.5 dl / g in solution in chloroform at 25 ° C and at a concentration of 0.3 g copolyester per dl chloroform, an open time of at least 1/4 min. at 20 "C, an im essential complete solubility in toluene at 25 ° C in the ratio of 10 wt .-% copolyester and 90 wt .-% solvent, a tensile strength of 100-400 kg / cm2, an elongation at break of 400-1000 percent, a T-peel strength compared to polyvinyl chloride at least 0.9 kg / cm wide and has a DTA glass transition temperature, Tg, below -25 ° C. 2. The method according to claim 1, characterized in that the reaction takes place in the presence of a catalyst. 3. The method according to claim 1, characterized in that the divalent aromatic radical Rj is phenylene. 4. The method according to claim 1, characterized in that Ri the divalent residue of adipic acid, R2 the divalent residue of 1,4-cyclohexanedimethanol, Raden residue Rj and Rb the divalent residue of poly- (oxytetramethylene) -glycol with a weight average of the molecular weight of about 2000, the proportion of the amorphous ester units of the formula II in the copolyester being in the range from 30 to 70% by weight. 5. The method according to claim 1, characterized in that R] the divalent residue of adipic acid, R2 the divalent residue of 1,4-dyclohexanedimethanol, Ra the residue R! and Rb denotes the divalent radical of polyglycol with a weight average molecular weight of approximately 1000, the proportion of the amorphous ester units of the formula II in the copolyester being in the range from 25 to 65% by weight. 6. The method according to claim 1, characterized in that Ri is the divalent residue of adipic acid, R2 is the divalent 10-valent radical of 1,4-cyclohexanedimethanol, Ra is the divalent radical of hydrogenated dilinoleic acid and Rb is the divalent radical of poly (oxytetramethylene) glycol with a weight average molecular weight of about 2000, the proportion of the amorphous ester units of formula 15 in the copolyester is in the range from 30 to 65% by weight. 7. The method according to claim 1, characterized in that R] the divalent radical of terephthalic acid, R2 the divalent radical of a linear, saturated, aliphatic 20 diols having 6 to 12 carbon atoms, Ra the radical Rj and Rb the divalent radical of poly (oxytetramethylene) glycol with a weight average molecular weight of about 2000, the proportion of the amorphous ester units of the formula II in the copolyester being in the range of 50 up to 75 2s% by weight. 8. The method according to claim 1, characterized in that R] the divalent radical of terephthalic acid, R2 the divalent radical of 1,6-hexanediol, Ra the radical R, and Rb the divalent radical of poly (oxytetramethylene) glycol with a Weight average molecular weight of about 2000 means, the proportion of the amorphous ester units of the formula II in the copolyester being in the range from 60 to 75% by weight. 9. The method according to claim 8, characterized in that the proportion of the amorphous ester units of the formula II is 68% by weight. 10 Use of the segmented copolyesters produced according to claim 1 to form a strong, reliable bond on a substrate at a temperature below the melting temperature of the copolyester and without the inclusion of volatile constituents. 35 40 55 60 Process for the production of segmented copolyesters