DE1923820A1 - Vinyl chloride polymer molding compositions and process for their production - Google Patents

Description

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS, DIPL-ING. GERHARD COLDEWEY

Patent Attorney « ·""'.":.""."■" ■ "■

MÖNCHEN 2 5 ^ J ^ JJJ ^^^^^^ TELEPHONE 34 5067- TELEQRAM ADDRESSER · INVENT / MDNCHEN ■ TELEX 5-29686

1923820 ! T MAY 1955

UoZcI B 328 (Pi / Vo / kä) POS - 18118

SlTHITOHO CHBMICAL GOHPANY ₀ LTD ", Osaka" Japan

"Vinylohlorid-Polymerisat-Formiiiaesen and process for their Manufacture "

Priority! 10 »May 1968, Japan, No. ₈ 51 468/68

November 30, 1968, Japan, No. 87 956/68

Hart set Vlnylohlorid polymers have good weather resistance, öhenieohe Bee tändigke it, ο © adhere tensile strength and self-extinguishing own They are therefore used in large scope for _o Bo as materials in the chemical industry or as building materials "Its scope is nevertheless limited ₉ Oa 8IE have poor impact strength and heat resistance.

Processes for improving the impact strength of polyvinyl chloride are known in which an acrylonitrile-butadiene copolymer or an aorylnitrile-butadiene-styrene terpolymer is used Vinyl chloride polymer is added; be in the first EaIl however, the heat resistance and tensile strength are strong, im in the latter case the chemical resistance and the weather

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persistence noticeably reduced, 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 however been found that these methods entail a reduction in the impact strength of the vinyl chloride polymer mit.sich ₀

A process in which both the fawn resistance and the Impact strength of the polymers can be greatly improved, is hitherto unknown. If one can nevertheless improve both Can observe properties, one of them will be only slightly improves, in other words, it only becomes one of the properties improved without significantly worsening the other.

The object of the invention is to provide new vinyl chloride polymer compositions which have a significant improvement both in terms of impact strength and heat resistance.

The invention relates to vinyl chloride polymer thus-Pormmaasen from 99 BIB 10 Qew ₀ parts by a vinyl chloride Polymerisatsund 1 to 90 parts by weight of an aromatic polysulfones containing sulfone-ffruppen in the main chain, and benzene rings "

Surprisingly, the molding compositions of the invention do not have only a greatly improved impact strength, but also a greatly improved heat resistance and also a superior chemical resistance and superior self-piercing properties

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Properties.

The yinyl chloride polymer materials used according to the invention are Vinyl chloride co-polymer and random, blook or graft copolymers consisting of at least 75% by weight of vinyl chloride and from consist of one or more other unsaturated comonomers, vie vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, Ethyl acrylate, methyl methacrylate, allyl acetate, allyl chloride, '· Ällyläthyläther, vinylidene chloride, ethylene or propylene. An example of the graft copolymers of vinyl chloride old unsaturated comonomers is that obtained by grafting vinyl chloride Graft copolymer obtained on an ethylene-vinyl acetate copolymer ·. ·

The degree of polymerization that is suitable according to the invention Vinyl chloride polyesters are Torsugevftie · 400 to 4000 · Der Polymerization ingredient is determined according to JIS I.-6727.

The aromatic polyulfones used in the invention contain in the high molecular weight chain.Bensol rings and sulfone groups and preferably have one of the general principles

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809847 / 1U2

so, -f V ο -V V so.

SO ₂ -O- O "Ο" ^S ° 2 "Ο" ^CH 2

CH,

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CH

_(g) -j-

CH ₃

O -V V CH ₉ -O- O -O- ^S0

t °

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Il c

o "X_y- c - \ _ y- ο -v_y- so ₂ - \ _,

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ο -e> -ο- ^ JVSC ₂ -O

9098Α7 / 1 U2

Dl. EUSABETH JUNG D «. VOLKER VOSSIUS OIPl-ING. G.COlDeWEY

PATENT LAWYERS ■ '. ·

β Munich J3 Or · * · _; ·:. ·

TeUfon: 34 5047

(n)

in which η indicates the degree of polymerization. The aromatic polysulfones of the general formulas a wad f are used with particular preference · ■ ··: "*.. -

Molding compositions which contain less than 1 part by weight of the aromatic polysulfones do not have superior impact strength and Heat resistance; at a content over 90 parts by weight the terabellability of the molding compounds deteriorates -

The invention further relates to a method of producing mis-Vlnylchlorid Polymerieat-Formmaasenj d @@ Sadurch is characterized in that a Gemisoh of @ in @ ia aromatic polysulfone und.eines Vinylohlorid'-Poljcä ^ is incorporated isat a niedermolekulare'Verbindung, the resulting mixture through melting

mixes and finally removes the low molecular weight compound »

For the preparation of the molding compositions of the invention may be used any conventional mixing process, melted in the di © ground and is mixed, S ₀ B ₀ using a Vialzen-Btuhlea, Banbury mixer or extruder "S ₀ Bo mixing the, one of the The aromatic polysulfone containing stabilizers described below is used alone with the aid of a two-wheel chair at a temperature of 240 to 25O ⁰ C to soften the polymer, then the vinyl chloride polymer containing one of the stabilizers described below is gradually added and mixed through »

Since the melting point of the aromatic polysulfones about 250 ⁰ C and 80 ⁰ C above that of the vinyl chloride polymer is, in usual mixing temperature is needed, but higher than the melting point of the aromatic polysulfones "Sine such high Miachtemperatur is unfavorable since the decomposition point of the vinyl chloride polymers is from about 200 ⁰ C and was carried on mixing at such a high temperature, a violent thermal Zersetsung of the vinyl chloride-Poljmerisats

In the process of the invention for producing the molding compounds, there is no discoloration of the vinyl chloride polymer due to thermal decomposition _{o A molding compound of excellent quality without discoloration is obtained if Z 0} B * the aromatic folysulfon * and a vinyl chloride polymer impregnated with a low molecular weight compound a uniform mixture resounds and mixed and then the low molecular weight compound is removed. ν

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All compounds that cause the aromatic polyulfone to swell and which can be removed after mixing with the vinyl chloride polyperissate, such as aromatic hydrocarbons, chlorocarbons _for ketones, ethers or EBter, are suitable as low molecular weight compounds.

For reasons of ease of removal it ναοβ

are ethylene dichloride _e trichlorethylene, carbon tetrachloride, chloroform _p Methylenchlortd, benzene, methyl ethyl ketone, tetrahydrofuran or ethyl acetate, preferably used ale IbprägnierungsiaAttel

For impregnation of the aromatic polysulfone with the low molecular weight Compound gives a variety of methods other than those illustrated in the examples., The molding compositions of the invention ZoB “can be produced by making a powdery aromatic polysulfone and powdery vinyl chloride polymer mixed in a mixer at room temperature and then the low molecular weight compound into the mixture dripped in

An extruder of the ventilable type is suitable for the recovery of the low molecular weight compounds «

In another mixing method, the vinyl chloride Polyaeri "can sate and the aromatic polysulfone dissolved in a suitable solvent for both mixes" and are then precipitated in a solvent in which both are soluble. One solves Zr. Bo Vinylchloriu the polymer and oaa aromatic Polyeulfon in any proportion in the solution is stirred vigorously _f tetrahydrofuran and pours it in anschliessond Excess BADORlGlNAt 909847/11 * 2

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 and dimethyl sulfone or ρ, ρ-dichlorodiphenyl sulfone, aliphatic and aromatic Chlorides such as methylene chloride, tetrachloroethane, 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 using a Solution of the aromatic polysulfone with a solution of a vinyl chloride polymer in the same solvent or in tetrahydrofuran, the entire solution is stirred in methanol or water poured, filtered and the residue washes and dries

However, a large amount may be required when dissolving and mixing the common solvent for the vinyl chloride polymer and the polysulfone, as well as the precipitant, which is why the Melting and mixing process is more advantageous from a technical point of view.

The molding compositions of the invention can be conventional stabilizers for Yinylchlorld polymers, such as dibutylsine dilaurate and dibutyltin maleate. Mercaptotin compounds, basic lead hydroxide, lead oxide, tribasic8 lead sulfate, dibasic lead ipboephite, dibasic lead stearate, cadmium stearate, barium etearate, alkaline earth metal silicates, hydroquinone or epoxies, or stabilizers for the aromatic polysulfones * 'such as thionaphthol, Benzimidazoles organic sulfides, imides, phosphates or organic

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Tin compounds, contain "The molding compounds can also contain lubricants, pigments and fillers"

The uniformly mixed molding compositions of the invention can be used in be deformed at a temperature which is close to the deformation temperature of the vinyl chloride polymer itself. You can do it Use extrusion, injection molding or calendering processes and thereby obtain objects with high impact strength and impact resistance, e.g. pipes, corrugated sheets, paneling or a wide variety of building materials ο

The examples illustrate the invention. example 1

6 kg βine8 commercially available polyvinyl chlorides (SUMIRIT SX-II) and 3 kg of a commercially available aromatic polysulfone are mixed with 500 g three-base lead sulfate, 50 g lead stearate and 50 g potassium stearate, and the mixture is at about 130 ⁰ C in one

Henschel mixer dry mixed. The Heneehel mixer is then cooled to room temperature and the aforementioned mixture with 1 kg of polyvinyl chloride, the old 4.5 kg Xtnylendiohlorid is impregnated, treated, Sa · resulting mixture is on at a maximum polymer temperature? 190 ⁰ C ait Ernest extruder with a diameter τοη 50 au * extruded. You can use a foamed molding compound. Bann, the Xthylendlchlorid at 100 ⁰ C in a vacuum dryer removes "There is obtained a molding material having. high quality, without the polyvinyl chloride decomposing and discoloring «

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- ίο -

Γ.- ».« Cutting and mixing is carried out according to Example 1 with the aid a beltiftbareii, an extruder equipped with two screws

carried out. If one works under the following conditions, one obtains pellets from molding compounds of high quality without that when the polyvinyl chloride decomposes and discolors

The working conditions are as follows:

1 · Maximum polymer temperature ι 190 ⁰ C *

2. Pressure on the polymer ι 70 kg / cm ·

3. Reduced pressure on the venting looh ■ t 60 Torr ·

£ s is used a conventional cold trap, di · is provided with a Ausläseöffnung and is cooled to -78 ⁰ C, üb the "ethylene

regain diohlorid.

■ ■ ». ■■ ■

Example 3. ·;

100 g of the Geaieche »from dtn in fabeile Σ specified proportions a commercially available polyvinylchloride (SUMIBIf SX-II) bit Average - Poiyaerlaationtgrad of UOO unct of a commercial aromatic polysulfone $ «r aligeinen formula £

in which a indicates the degree of Polyeerieatioaagrad that

from a. Nozzle old «inea diameter of 1 mm. «Nd a Sassge of

i-0 BB at 300 0 and., at a pressure of 1 kg / cm g @ mdas @ n &

. 90984 W <Ä2 · ^ßAD

- ii -

sity of 2 _f 2 χ IO has poise be gelöstο in 1 .Liter tetrahydrofuran under stirring, the solution obtained is dissolved in methanol gegosseiu The resulting precipitate is filtered off and dried at 100 ⁰ C under reduced pressure

The molding compound obtained is treated with a stabilizer for polyvinyl chloride added and mixed at 170 ° C with the help of a roller mill ο The molding compound is then pressed at 180 C «The softening point according to Vicat and the tensile impact strength of the compact are determined.

The Vicat softening point is indicated by the temperature with a needle at a heating rate of 0.8 ° C / min. with a load of 2 kg a depth of 1 mm is reached » The test body and the test device have a thickness of 3 turns corresponds to ASTM PrOfnorw D 1525ο The tensile impact strength is at 20 ° C and at a pulling speed of 330 cra / sec. using the tensile strength testing device from Yasuda Seiki definitely «

Table I shows the. Results »If tin is specified as the stabilizer, this means that the polymer molding compound contains 5% by weight of a kercaptotin compound, based on the molding compound; Lead is "specified as the molding material contains from 3 percent by _o - # tribasic lead sulfate and 0.5 wt _o - # stearate, based on the molding composition.

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Table I.

co ο co oo

Test specimen
No. ₀ Polymer »Molding Compound» Gewo -teile aromatic
Polysulfone Softening
point after
Vicat, ⁰ C. Train blow
ä6ÄM.gkelt,
kg cm / cm * Stabilizer,
link
from 1 Polyvinyl chloride 10 87 120 tin 2 90 50 103 100 tin 2a 70 30th 113.4 120 lead 3 70 50 119 120 tin 4th 50 70 128 100 tin control 30th 0 75.5 50 tin 100

ro co oo ro

From Tatelle I it can be seen that the polymer molding compositions of the Invention both have higher heat resistance and higher impact strength than polyvinyl chloride alone «

Example 4

The thermal resistance of the in Table I with number 2a bezeichnetenpormmasse of Example 3 is by means of a heated to 19O ⁰ C Gear Alterungsbestähdigkeits Tester examined the polymer-molding material 2a is after 180 minutes only brown, only the same stabilizer polyvinyl chloride containing However, black after 120 minutes as a result of strong decomposition

Example 5.

30 Gewo-parts of the aromatic poly used in Example 3 · "sulfone be by means of a mixing roll, a temperature of 240 prevails at the surface of up to 250 ⁰ C, softened and share Gewο-70 polyvinyl chloride having an average degree of polymerization of 1100 Contains 5 parts by weight of a mercaptotin compound as a stabilizer, gradually added and mixed _{o The Hasse is homogenized for 5 minutes.}

Subsequently, the mixture verpresstο The Erweichungepunkt NaOH Vicat and impact strength according to Charpy in accordance with ASTM test standard 2 ^ 6 determined the au a notched specimen at 20 ⁰ C certain impact strength is 5.1 kg / em orn ² and the Vicat softening point 104 ° C »

The impact strength of the polyvinyl chloride exclusively containing the aforementioned stabilizer is only 2 _P 2 cm / cm and the softening point is only 75 ^° Co

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Furthermore, the flammability test is carried out in accordance with the ASTM test standard 635-63 carried out ο The molding compound goes out 2 seconds after removal the flame of a bunsen burner.

Example 6

According to Japanese patent specification 7799/67, a dialkali salt of 2,2-bis = (4-hydroxyphenyl) propane is prepared from 2 _s 2-bis (4-hydroxyphenyl) propane and sodium hydroxide using anhydrous dimethyl sulfoxide as a solvent, and 5 Hours in a nitrogen atmosphere at 130 to 140 ⁰ C with Bi8- (4-chlorophenyl) -8ulfon condensed «The resulting solution of the aromatic polysulfone in dimethyl sulfoxide is a viscous liquid which contains 1.1 kg aromatic polysulfone in 45 liters of dimethyl sulfoxide reduced viscosity of the aromatic polysulfone obtained at 25 ^° C. in chloroform is 0.68 _o

The dimethyl sulfoxide solution of the aromatic polysul-

xxnü blow dryer mixed with 50 liters of monochlorobenzene / with a solution of 20 kg of polyvinyl chloride with an average degree of polymerization of 1100 in 400 liters (tetrahydrofuran is mixed with methanol for the joint! precipitation of the two polymers

M§ia @ ^ dried under reduced pressure at XlO ⁰ O maintains uniform polymerizate-> Fo7mmaese _e

3 lines of three-ply lead sulfate, 2 parts of a commercial, mainly octa & ecylss © @ i? At © mtl the lubricants are mixed with 100 ropes of the molding compound obtained above with the help of a Hensch @ l «Hischer @ Mixture is with the help of an extruder ₈ of a Schiisk-

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ke with a diameter of 30 MRA _P is a L / D Yerhältnis of 20 and a compression ratio of 3 _P 5 has _s at a mold »temperature of 200 ⁰ C to a Stat" a! diameter of 3 mm extruded * The bar is ⁰ at 190 C into a film verpresstc the softening temperature according to Vicat and the train-stroke toughness of the above film amount to 11O ^€ 'or C, 105 kg-cm / cm ο

Example 7

GemäsB to the method described in Japanese patent 37 876/64, 150 parts of a commercial ethylene-vinyl acetate copolymer, 3300 parts of water _p 3 parts Of _s Of * azo diisobuttersäuredinitril, 5 parts of polyvinyl alcohol and 1350 parts of vinyl chloride in an autoclave for 5 hours at Room temperature

vigorously stirred and then polymerized for 15 hours at 60 C ,, An ethylene-vinyl acetate copolymer grafted with vinyl chloride is obtained ο

80 parts by weight of the graft copolymer obtained and 20 wt ₀ parts of a commercial aromatic PoIysulfone be gemäsa Example 1 dissolved in tetrahydrofuran much methanol precipitated jointly _c dried, mixed with 5 wt ~ # _f based on the molding composition. ^ A Mercaptozinnverbindung added as a stabilizer, were mixed at 17O ⁰ C by means of a roll mill at 180 ⁰ C verpresstο the Vicat softening point or _0, the train ° impact toughness of the molding composition be 93 C bssWo 180 kg · cm / cm ₀ on the other hand be of the Vicat softening point and the tensile impact strength of the ethylene-vinyl acetate copolymer grafted with vinyl chloride 73 C or ₀ 165 kg cm / cm ₀

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Thus £ 8 was prepared by mixing Vtnylehlorid polymers with an aromatic polysulfone at the same time an improvement in the heat resistance and the impact resistance can be obtained ₀

BATH

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Claims (1)

Claims Vinyl chloride polymer molding compounds, characterized by 99 to 10 wt _o parts of a vinyl chloride polymerisation -sats and 1 to 90 Gewo-parts of an aromatic polysulfone, the "contains uruppen" in the main chain, and benzene rings sulfone 2 ο molding compounds according to claim 1, characterized in that that the vinyl chloride polymer is polyvinyl chloride ο 5o molding compositions according to claim I _9, characterized in that the vinyl chloride polymer is a random, block or graft copolymer, which consists of at least 75 wt _o - # vinyl chloride and units that are derived from one or more other unsaturated polymerizable compounds derive. 4 ° molding compositions according to Claim 3 _S, that the compounds oopolymerisierbaren acetate, vinyl propionate, vinyl butyrate, vinyl laurate, ethyl acrylate, Hethylmethacrylat, allyl acetate, allyl chloride, Allyläthyläther, vinylidene _$ Ithylen or propylene. 5o molding compounds according to claim 4 »characterized in that that the Gopolymerieat a graft copolymer of vinyl chloride on ethylene-vinyl acetate copolymer isto 6 «Molding compositions according to claim 1 to 5», characterized in that that the degree of polymerization of the vinyl chloride polymer is 400 to 4000 » BATH ORIGINAL -IQ- 7o molding compositions according to claim 1 to 6 "characterized by a content of a stabilizer for vinyl chloride polymers and an aromatic polyr stabilizer sulfone. · 8. molding compositions according to 'claim 7 * characterized in that that the stabilizer for the vinyl chloride polymer Difcutylsin dilaurate * diutylsin maleate, mercaptotin compounds, basic lead carbonate, lead oxide, three baai- εehea lead sulfate, dibasic lead phosphite, dibasic 31ei3tearate, cadmium stearate, barium stoarate, an alkaline earth metal oxide, Hydroquinone or an epoxy and the stabilizer for the aromatic poly sulfone. iliionaphthol, Benzimidazole an organic Sulfide, an imide, a phosphate or an organic Tin compound is ·. · 9 * Molding compositions according to claim 1 to 8, characterized in that that they also contain a lubricant, a pigment and a filler. . 10 · Molding compositions according to claims 1 to 9 »dad urea characterized in that a is the aromatic poly sulfone of the general formulas a to ο (a) 909847 / (e) -j- SO ₂ - ^ - O r @ - SC ₂ - ^ - CH ■ ok CH, c-f Vo CH, CH, Sn chQ-o SO ₂ (k) -HO c-O-o-O-soa 90984 7 / 1U2 In which η has the PolTserleationcgrad. 11 «Fornuaaeeen according to claim 10, characterized by it is worthwhile for the aromatic polyulfon one of the all & o- «Has a formula a and f. . 12 · The process of creating a vinylchlorld polyeerate form, dad.uroh ^ kennselohnet _f that a mixture of an aromatic polyulfone and a Tinylohlorid-Folynerieat a low molecular weight compound is incorporated, the mixture obtained by cutting through the melt and the low molecular weight compound is removed. 909 <U7 / iU2 .'BAPOR ₁ QWAL- 13 ο Method according to claim 12, characterized in that g e k e η η - ■ ζ e i ο h η e t that a low molecular weight compound is used » which causes the polysulfone to swell and after mixing can be removed with the Vinylohlorid-PolymeVisat « 14 ο method according to claim 13, characterized in that; that the low molecular weight compound is ethylene dichloride, Trichlorethylene, carbon tetrachloride, chloroform, methylene chloride, benzene, methyl ethyl ketone, tetrahydrofuran or Ethyl acetate used » 15ο method according to claim 12, to 14 » daduroh ge« indicates that the mixture is extruded with the aid of a ventable extruder, whereby the low molecular weight compound is recovered, - ■ LOCAL BATHROOM 909847/1 U2