DE1923820C - Compositions containing aryl sulfones and their use for the production of molds - Google Patents

Description

Have hard adjusted vinyl chloride polymerisals good weather resistance, chemical resistance, tensile strength and self-releasing properties. You are therefore on a large scale z. B. as materials in the chemical industry or as building materials used. However, their field of application is limited because they have a low impact strength and Possess heat resistance.

Processes for improving the impact strength of polyvinyl chloride are known in which an acrylonitrile-butadiene copolymer or an acrylonitrile-butadiene-styrene terpolymer is added to the vinyl chloride polymer; in the first case , however, the heat resistance and the tensile strength are great, in the latter case the chemical resistance and the weather resistance are markedly lowered, although an improvement in the impact strength is achieved in both cases. On the other hand, several processes have been developed to improve the heat resistance of vinyl chloride polymers in which either the vinyl chloride polymer is post-chlorinated or post-chlorinated vinyl chloride polymer is incorporated into the vinyl chloride polymer or the molecules are crosslinked. It has been found, however, that these processes reduce the impact strength of the vinyl chloride polymer.

A process in which both the heat resistance and the impact strength of the polymers To be greatly improved is not yet known. If one can nevertheless observe an improvement in both properties, then only one of them will be slightly improved, in other words, only one of the properties is improved without the other is significantly worsened. There are z. B. Epoxy resins containing compositions based on known from polyvinyl chloride. The addition of epoxy resins improves the heat resistance of the polyvinyl chloride, while at the same time softening it.

From the USA patents 2,643,954 and 2,728,738 the use of monomeric alkoxyalkyl esters of Bis (4 - carboxyphenyl) sulfone is known as a plasticizer in cellulose esters and vinyl chloride polymers. The products are characterized by a improved surface hardness.

The object of the invention was to provide new vinyl chloride polymer molding compositions to make available, both in terms of impact strength and Heat resistance show a significant improvement. This object is achieved by the invention solved.

The invention thus relates to compositions containing aryl sulfones, consisting of

(A) 10 to 90 parts by weight of a vinyl chloride polymer,

(B) 1 to 90 parts by weight of an aromatic polysulfone. which contains Donzol rings and sulfonic groups in the high molecular chain, and

(C) customary additives, if any.

Surprisingly, molded articles produced from the compositions of the invention do not have just one greatly improved impact resistance, but also greatly improved heat resistance and moreover superior chemical resistance as well as superior self-extinguishing properties.

The vinyl chloride polymers used according to the invention are vinyl chloride homopolymers and random, block or graft copolymers, that of at least 75 percent by weight vinyl chloride and one or more other unsaturated ones Comonomers exist, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, ethyl acrylate, Methyl methacrylate, allyl acetate, allyl chloride, allyl ethyl ether. Vinylidene chloride, ethylene or propylene. This is an example of the graft copolymers made from vinyl chloride with unsaturated comonomers graft copolymer obtained by grafting vinyl chloride onto an ethylene-vinyl acetate copolymer.

The degree of polymerization of the vinyl chloride polymers suitable according to the invention is preferably from 400 to 4000. The degree of polymerization is determined in accordance with JIS 1-6727.

The aromatic polysulfones used in the present invention are described in Japanese Patent Publication Nos. 12 919/1966 and 7799/196 " ^7. They contain benzene ring c and sulfone groups in the high molecular chain and preferably have one of the general formulas (a) to (o):

ο-

SO ₂

_r -C) ■■ 'f --SC) ₂

SO,

SO,

. '■ r

SO ₂

SO ₂

- Ο

CH ₃

-Ο — ν V- <

Vo- /

in which η indicates the degree of polymerization. The superior impact resistance and heat resistance;

aromatic polysulfones of the general formula (a) 65 at a content above 90 parts by weight is the

and (O are particularly preferably used. Processability of the molding compositions is impaired.

Molding compositions which are less than 1% by weight

fc-omatic polysulfones contain, have no manufactured that one e: inem mixture of an aromatic

(ical polysulfone and a vinyl chloride polymer a low molecular weight compound confers, mixed dus trhultene mixture with melting and Eventually the low molecular weight compound is removed.

To produce the molding compositions of the invention, any conventional mixing process can be used in which the composition is melted and mixed, for example with the aid of a roll jig, Banbury mixer or extruder. For example, mixing the one of the described _{below) Q} surrounded stabilizers containing aromatic poly-sulfone alone with the help of a Zweiwalzcnstuhls Piner at temperature 240-250 "C for softening of the polymer before, then sets the vinyl chloride an animal stabilizers described hereinafter containing Polymerisal gradually adds and mixes.

Since the melting temperature of the aromatic polysulfones is higher than that of the vinyl chloride polymerizate, For normal mixing, a temperature is required that is above the melting temperature of the aromatic Polysulfone lies. Such a high mixing temperature is unfavorable, however, since the decomposition point of the vinyl chloride polymers is around 200.degree and when mixing at such a high temperature violent thermal decomposition of the vinyl chloride polymers takes place.

In the aforementioned process for producing the molding compositions, there is no discoloration of the vinyl chloride polymer as a result of thermal decomposition. A molding composition of excellent quality without discoloration is obtained if, for. B. the aromatic polysulfone and a vinyl chloride polymer impregnated with a low molecular weight compound melts and mixed into a uniform mixture and then the low molecular weight compound is removed.

All compounds that use the aromatic polysulfone are suitable as low molecular weight compounds Bring sources and which can be removed after mixing with the vinyl chloride polymer, 'vic aromatic hydrocarbons, chlorinated hydrocarbons, Ketones, ethers or esters.

For reasons of ease of removal and recovery, ethylene dichloride becomes. Trichlorethylene. Carbon tetrachloride, chloroform. Methylene chloride, benzene, methyl ethyl ketone, tetrahydrofuran or ethyl acetate is preferably used as the impregnating agent.

There is one for impregnating the aromatic polysulfone with the low molecular weight compound Variety of procedures other than those illustrated in the examples. The molding compositions of the invention can z. B. be prepared by adding a powdery aromatic polysulfone and powdery vinyl chloride polymer mixed in a mixer at room temperature and then the low molecular weight compound is added dropwise to the mixture.

An extruder from the ventilator is suitable for recovering the low molecular weight compounds Type.

. In another mixing process, the vinyl chloride polymers and the aromatic polysulfone can be used dissolved in a solvent suitable for both, then mixed in a solution medium in which both are insoluble. One solves z. B. the vinyl chloride polymer and the aromatic polysulfone in any proportions in tetrahydrofuran, stir the solution vigorously and pour out they then in excess methanol, whereby both polymers are precipitated together. The precipitate obtained is washed with methanol and dried.

Examples of inert organic solvents for vinyl chloride polymers and for polysulfones are aliphatic and aromatic sulfoxides and sulfones, such as dimethyl sulfoxide, dimethyl sulfone or ρ, ρ-Πί-chlorodiphenyl sulfone, aliphatic and aromatic chlorides, such as methylene chloride, tetrachloride. Monochlorobenzene or dichlorobenzene, as well as aliphatic and aromatic nitro compounds such as Nitropropane or nitrobenzene. Uniformly blended molding compositions of the invention can be obtained by a solution of the aromatic polysulfone with a solution of a vinyl chloride polymer added in the same solvent oa.T in tetrahydrofuran, the total solution rests, poured into methanol or water, filtered and the residue washes and dries.

However, in dissolving and mixing, a large amount of the common solvent is required for the vinyl chloride polymer and the polysulfone and the precipitant, which is why the melting and Mixing process more advantageous from a technical point of view is.

The molding compositions of the invention can be conventional stabilizers for vinyl chloride polymers, such as dibutyltin dilaurate, Dibutyl tin maleate. Mercaptotin compounds. basic lead carbonate, lead oxide, tribasic bisulfate, dibasic lead phosphite. dibasic lead stearate, cadniium stearate. Barium stearate, Alkaline earth metal silicates, hydroquinone or epoxies, or stabilizers for you. · Aromatic Polysulfones, such as thionaphthol, benzimidazole, organic sulfides, imides. Phosphates or organic tinplate Bindings included. The molding compositions can also contain lubricants, pigments and fillers.

The uniformly mixed molding compositions of the invention can be molded at any temperature, which is close to the deformation temperature of the vinyl chloride polymer itself. You can do it Use extrusion, injection molding or calender processes and thereby obtaining articles with high impact strength and heat resistance, e.g. B. Pipes. Corrugated sheets, paneling or all kinds of building materials.

The examples illustrate the invention.

example 1

6 kg of a commercially available polyvinyl chloride and 3 kg of a commercially available aromatic polysulfone 500 g tribasic lead sulfate, 50 g lead stearate and 50 g calcium stearate are added, and that Mixture is dry blended in a Henschel mixer at about 130 ° C. The Fienschel mixer is then cooled to Raumtcmpcratui, and the aforementioned Mixture is with 1 kg of polyvinyl chloride, which is impregnated with 4.5 kg of ethylene dichloride. offset. The mixture obtained is at a maximum polymer temperature of 190 C with an extruder extruded with a diameter of 30 mm. A foamed molding compound is obtained. Then it will be the ethylene dichloride is removed at 100 "C. in a vacuum dryer. A molding compound is obtained with high quality without the polyvinyl chloride decomposing and discoloring.

H e i s ρ i c I 2

Melting and mixing is carried out according to Hebeispiel I mil I ulfe one ventilated, with two snails equipped l-.xtrudcrs carried out. If you are at Working under the following conditions, you get Pellets made from high quality molding compounds without the polyvinyl chloride decomposing or discoloring.

The working conditions are as follows:

1. Maximum polymer temperature: 190 C.

2. Pressure on the polymer: 70 kg / cm ² .

3. Reduced pressure at the vent hole: 60 Torr.

i:

a common cold trap is used, which is provided with an outlet opening and cooled to -78 C. is used to recover the ethylene dichloride.

1) c i s ρ i e I 3

100 g of the mixture of the proportions given in Table I of a commercially available polyvinyl chloride with an average degree of polymerization of I KK) and a commercially available aromatic Polysulphone of the general formula (f)

CII,

-so,

in which η indicates the degree of polymerization that has a viscosity of 2.2 χ 10 * poise measured when flowing out of a nozzle with a diameter of 1 mm and a length of 10 mm at 300 ° C. and at a pressure of 1 kg / cm ² dissolved in 1 l of tetrahydrofuran with stirring. The resulting solution is poured into methanol. The resulting precipitate is filtered off and dried at 100 ° C. under reduced pressure.

A stabilizer for polyvinyl chloride is added to the molding compound obtained and at 170.degree Mixed with the help of a roller mill. The molding compound is then pressed at 180.degree. The softening point according to V i c a t and the tensile impact strength of the compact are determined.

The softening point according to V i c a t is indicated by the temperature at which a needle is at a heating rate of 0.8'X / min. at a load of 2 kg reaches a depth of 1 mm. The test specimen has a thickness of 3 mm, and the test device corresponds to ASTM test standard D 1525. The tensile impact strength is at 20 C " and at a pulling speed of 330 cm / sec. using the tensile strength testing device from Yasuda S e i k i determined.

The table shows the results. When a tin compound is specified as a stabilizer. this means, that the polymer molding compound contains 5 Uewichlsprozenl of a mercaplocin compound, based on aul the molding compound; if a lead compound is specified, the molding compound contains 3 percent by weight three basic lead sulfate and 0.5 percent by weight lead stearate. based on the molding compound.

Test specimen no.

control

Polymer molding compound (icwichtsicile aromatic Erttcichunespunk Polysulfone to Vic'at. C. Polyvinyl chloride 10 ._. . . -
90 30th 87 70 30th 103 70 50 113.4 50 70 Π9 30th 0 128 KK) 75.5

Tensile impact strength
kg cm cm ²

120
KK)
120
120
100
50

Stabilizer compound yon

tin

tin

lead

tin

tin

tin

The table shows that the polymer molding compositions According to the invention, both a higher softening point and a higher impact strength own as polyvinyl chloride alone.

Example 4

The thermal resistance of the molding composition of example identified by the number 2a in the table 3 is made using a gear aging resistance tester heated to 190 ° C checked. The polymer molding compound 2a becomes after 180 minutes lcdiulich brown, the one containing only the same stabilizer However, polyvinyl chloride turns black after 120 minutes due to severe decomposition.

60

Example 5

30 Ciewichtsteile of the Example 3 was used "aromatic polysulfone are using a mixing roll, on whose surface a Temperat ¹ of 240 prevails to 250 C, softened and rr 70 Gewichtsicilen polyvinyl chloride having a Pieter sectional degree of polymerization of 1100. 5 g weight parts of a Mercaptozinnverbindung contained as a stabilizer, gradually added and vermiscl The mass is homogenized for 5 minutes.

The mixture is then compressed. Y) Softening point according to Vi cat and the susceptibility according to C'ha-py according to ASI M-1'rüfnoi 256 are determined. The notched Pr

909 MN /

body at 20 (certain impact strength is 3.1 kg tm!. 'tu ³ and the softening point according to V i cat 1 (14 C.

The impact strength of the polyvinyl chloride, which contains only the aforementioned stabilizer, is only 2.2 kg cm ² and the softening point is only 75 C.

the flammability test is also carried out in accordance with ASTM test standard 635-6.1. The shape mass goes out 2 seconds after removing the flame of a Bunsen burner.

H c i s ρ i e I. 6

According to Example I of Japanese Patent Publication No. 77 ¹ W67, a dialkali salt of 2.2-His- (4-hydroxyphenyl) propane is prepared from 2.2-bis (4-hydroxyphenyl) propane and sodium hydroxide using anhydrous dimethyl sulfoxide as a solvent and Condensed for 5 hours in a nitrogen atmosphere at 130 to 140 C with bis (4-chlorophenyl) sulfone. The resulting solution of the aromatic polysulfone in dimethyl sulfoxide is a viscous liquid which contains 1.1 kg of aromatic polysulfone in 45 liters of dimethyl sulfoxide. The reduced viscosity of the aromatic Pc 'ysulfone obtained at 25 ° C. in chloroform is 0.68.

Then the dimethyl sulfoxide solution becomes the aromatic Polysulfons mixed with 501 monochlorobenzene and with a solution of 20 kg polyvinyl chloride with an average degree of polymerization of 1100 in 400 l of tetrahydrofuran. The Methanol is added to the mixture for the joint precipitation of the two polymers. The precipitation is washed with methanol and dried under reduced pressure at 110 ° C. A uniform polymer molding compound.

3 parts tribasic lead sulfate. 2 parts of lead stearate and 1 part of a commercially available lubricant containing mainly octadecyl stearate are mixed with 100 parts of the molding composition obtained above using a Henschel mixer. The mixture obtained is made using an extruder which has a screw with a diameter of 30 mm. has an L / D ratio of 20 and a compression ratio of 3.5, extruded at a die temperature of 200 ° C. to give a rod with a diameter of 3 mm. The rod is pressed into a film at 190.degree. The softening temperature according to V icat and the ug impact strength of the aforementioned film are 110 and 105 kg cm.cm ^2, respectively.

Example 7

According to the method described in Japanese Patent Publication No. 37 876 64, 150 parts of a commercially available ethylene-vinyl acetate copolymer, 3300 "file water. 3 parts ii.a'-azodiisobiitterodinitrile, 5 file polyvinyl alcohol and 1350 parts of vinyl chloride were stirred vigorously in an autoclave for 5 hours at room temperature and then polymerized at 60 ° C. for 15 hours. An ethylene-vinyl acetate ('(! Polymerizat.

80 parts by weight of the graft copolymer obtained and 20 parts by weight of a commercially available aromatic polysulfone are dissolved in tetrahydrofuran according to Example 1, precipitated together with a lot of methanol, dried, with 5 percent by weight, based on the molding compound, of a mercaptotin compound as a stabilizer, at 170 ° C. with the aid a roller mill mixed and pressed at 180 C. The Frweichungspunkt according V icat train or the impact strength of the molding material be 93 C or lSOkgcm'cm. ² On the other hand, the V icat softening point and the tensile impact strength of the ethylene-vinyl acetate copolymer grafted with vinyl chloride are 73 ° C. and 165 kg cm / cm ^2, respectively.

It was made possible by mixing vinyl chloride polymers with an aromatic polysulfone at the same time an improvement in the softening point and the impact strength can be achieved.

Claims (2)

Patent claims: 1. Aryl sulfones containing compositions consisting of (A) 10 to 90 parts by weight of a vinyl chloride polymer. (B) 1 to 90 parts by weight of an aromatic polysulfone contained in the high molecular weight Chain contains benzene rings and sulfonic groups and (C) if necessary, the usual additives. 2. Use of the compositions according to claim I for the production of moldings.