DE2151802C3 - Thermoplastic molding compounds - Google Patents

Description

! i ii The following description is as follows:

HC = CCOR ₂ built:

(a) Production of typical tetrapolymers,

consists in which R _{1 is} hydrogen or a methyl 20 _(b) production of vinyl chloride polymer tetrarest and R _{a is} an alkyl radical with 1 to 8 carbon polymer mixtures,

atoms mean. _{(c) Description of the} typical mixing processes,

2. Molding composition according to claim 1, characterized in _{that (d)} production of various mixtures for unterkennze.chnet that the tetrapolymer (B) from different applications and

64 parts by weight of 1,3-butadiene, 29 _{parts by weight of 25 (e) values of} physical comparative tests for ver-acrylonitrile 2 to 5 parts by weight of »-chloroacrylic different compounds,

nitnl and 2 to 5 parts by weight of ethyl acrylate. In all examples, approaches, etc., the quantities are

3. Molding composition according to claim 1, containing given for each component in parts by weight, 30 percent by weight polyvinyl chloride and 70 percent unless otherwise stated.

weight percent tetrapolymer. _R. · 1 1

4. Molding composition according to claim 1, containing B e 1 s ρ 1 e

50 percent by weight of polyvinyl chloride and 50 percent by weight of an improved tetrapolymer

weight percent tetrapolymer. Several examples are given in DT-OS 20 40 220

5. Process for further processing the thermo- 35 given, according to which butadiene, acrylonitrile, Λ-chloroplastic Molding compositions according to one of the anacrylonitrile and alkyl acrylates to give elastomers with versprüche 1 to 4 to vulcanizates. improved properties are copolymerized.

The alkyl acrylates have the formula

40 HR ₁ O

The invention relates generally to form I I i!

masses of a vinyl chloride polymer, in particular H - C = C - C - O - R ₂

polyvinyl chloride, and a butadiene-acrylic

nitrile copolymer, wherein the molding compounds in which R _{1 is} hydrogen or a methyl radical and R ₂

are characterized in that in them polyvinyl 45 bechlorid an alkyl radical with 1 to 8 carbon atoms (PVC) in amounts of 10 to 90 percent by weight. In these examples are compositions with 90 to 10 percent by weight of an improved tetrahedral tetrapolymer, practically all of them polymer is mixed, the from 30 to 90 Ge also for the tetrapolymer-PVC mixtures according to parts by weight of a butadiene, 10 to 50 parts by weight of the invention are suitable. Below is a

an acrylonitrile, 1 to 9 parts by weight of an alkyl 50 refinement only a preferred method for heracrylate and 1 to 9 parts by weight of a halogenated position of such tetrapolymers are given.
Acrylonitrile, such as α-chloroacrylonitrile, composed of an emulsion according to the following approach

is. manufactured:

From U.S. Patent 23 30 353 are masses

known, in which a nitrile rubber mechanically 55 Demineralized water 142

is mixed with a polyvinyl halide. In this potassium hydroxide 0.132

Patent is stated that these masses in all-potassium chloride 0.5

generally have good high-temperature properties, sodium formaldehyde hydrosulphite 0.2

whereby the scope of application for both the ethylenediaminetetraacetic acid

Polyvinyl chloride, as well as for the nitrile rubber 60 disodium salt 0.15

types is expanded. These masses also have the sodium salt of lauryl alcohol sulfate .. 4,5

good physical properties that are not only ferrous sulfate 0.0024

from the high-temperature and low-temperature natural ammonium persulfate 0.2

to derive the shafts of each individual component. Mixture of tertiary mercaptans 0.4

The invention is particularly directed to masses, 65-1,3-butadiene (BD) 65.0

the improved nitrile rubbers in combination with acrylonitrile (VCN) 30.0

with a vinyl chloride polymer and the «-chloroacrylonitrile (\ -CLAN) 2.0

pinp excellent abrasion and aging resistance - ethyl acrylate (ÄAC) 5.0

- τ

The unit from the above monomers are the tetrapolymers corresponding to

The emulsion produced was designated in a pressure vessel in Table 1 below with A, B, etc., brought, whereupon the persulfate catalyst added

would. The contents of the container were shown in a table 1

a thermostatically controlled bath 16 hours at 5 ■ '

Stirred 2O ⁰ C. The polymerization was then carried out by tetrapolymer ABCD

Addition of a common breaker, such as sodium ~

dimethyldithiocarbamate, with a conversion of BD 65 65 65 65

about 80% interrupted. The latex was made under VCN 30 30 30 30

Twist of Al ₂ (SOj) ₃ coagulated and in a hot io, .- CLAN 2 2 2 2

air oven at 100 ⁰ C dried. - _ _ _

The procedure of Example 1 was repeated with others

Alkyl acrylates in the same proportions again - methyl methacrylate - 5 - -

fetches, i.e. in the ratio BC / VCN / ^ - CLAN / AlUyl butyl acrylate - - 5 -

acrylate of 65: 30: 2: 5. For reasons of simplicity is 2-ethylhexyl acrylate - - - 5

Example 2
Manufacture of PVC tetrapolymer mixtures

Mixtures of the high-temperature tetrapolymer prepared according to Example 1 (dried Coagulate) with polyvinyl chloride according to the following table 2:

Table 2

- - - 70 70 - - , 75 - 30th 30th 30th 30th 30th 50 75 90 1.0 1.0 1.0 1.0 1.0 1.0 0 0.90

Mixture I U III IV V VI VII VIII

Tetrapolymer A 70 50 25 10

Tetrapolymer B - 70

Tetrapolymer C-70

Tetrapolymer D
Polyvinyl chloride

Organotin PVC stabilizer

Calcium stearate - - - ] q

Antimony Oxide - - - - 5 ₅ O

Epoxy PVC stabilizer - 0.5 0.5 0.5 - - - -

Example 3 of the procedure described in Example 3 as follows

Mixing process produced:

The mixtures according to Example 2 (and other commercially available 45 Table 3

common PVC-nitrile rubber mixtures) are based on r -

a two-wheel chair or according to the Banbury-Ver Composition I Π ΙΠ

drive as indicated below, worked through. Mixture I (table 2) 100.0 - -

Jcü "Method of operation ₅₀ Mixture V (Table 2) - 100.0 -

(Minutes) Commercially available - - 100.0

0 to 2 filling the mixture into the mixer mixture M *)

2 to 4 addition of a quarter to half zinc oxide

the dry powder ₅₅ stearic acid

4 to 6 Addition of plasticizers and waxes. Hard clay

6 to 8 adding the rest of the powder,. ,,,.,, -. ~ _M

8 and more interrupting at about 127 to 132 ° C D. octyl phthalate (DOP)

Chlorinated Polyphenyls (CP)

The accelerators are cooled to the, from 6 °

brought the web coming to the roller. bcnwetel

Mercaptobenzothiazyl

Example 4 disulfide (MBTD)

Elaborated mixture approaches for different - tetramethylthiuram-

Applications ⁵ disulfide (TMD)

Masses specially made for the manufacture of wire- ²¹⁵ O ²¹⁵ - ° ²¹⁵ <°

and cable insulation are suitable, according to *) A nitrile rubber-PVC mixture (70/30).

3.0 3.0 3.0 1.0 1.0 1.0 80.0 80.0 80.0 25.0 25.0 25.0 3.0 3.0 3.0 1.5 1.5 1.5 1.0 1.0 1.0 0.5 0.5 0.5

After removing the web (rolled skin) from the Roll the masses were vulcanized in an ASTM mold at about 177 ° C for 5 minutes.

Masses that are suitable for particularly heavily stressed electrical insulation were as follows manufactured:

Table 4

were worked through according to the following table 5 as follows:

Table 5

Dimensions IV V VI Mixture I (table 2) 100.0 Mixture V (table 2) - 100.0 - Commercially available - - 100.0 Mixture N *) Zinc oxide 3.0 3.0 3.0 Stearic acid 1.0 1.0 1.0 Hydrated silica 40.0 40.0 40.0 DOP 15.0 15.0 14.0 CP 3.0 3.0 3.0 sulfur 1.0 1.0 1.0 MBTD 1.0 1.0 1.0 TMD 0.5 0.4 0.5

Dimensions VII VIII Mixture Vl 100.0 Mixture O *) - 100.0 Zinc oxide 3.0 3.0 Wax (sunlight resistant) 3.0 3.0 Stearic acid 1.0 1.0 Hard tone 100.0 100.0 DOP 30.0 30.0 MBTD 2.0 2.0 Tetra methylthiuram monosulfide 0.5 0.5 sulfur 1.5 1.5 Diphenylguanidine 0.5 0.5 4,4'-thiobis- (6-tert-butyl- 2.0 2.0 meta-cresol)

164.5 164.5 ·) A nitrile rubber-PVC mixture (70/30).

164.5

After removal of the rolled sheet from the roller, these compositions were vulcanized in an ASTM mold 5 minutes at about 177 ⁰ C.

A commercial mixture (50/50) and the 50/50 mixture identified in Table 2 as mixture VI

Table 6

242.0 242.0

*) A PVC-nitrile rubber mixture (50/50).

The samples indicated above were molded 10 minutes at about 16O ⁰ C in a compression mold.

The masses marked I to VIII were tested under different conditions to get their determine the original properties as well as the properties after aging; the results are given in Table 6 below.

II III

IV

VI

VII

VIII

Mixture (Table 2) I.

Elastomer (rubber / PVC) 70/30

Flame retardant no

Original properties

Tensile strength ¹ ) 115

Elongation ² ) 605

Hardness ³ ) 72

Tear resistance ⁴ ) 40

Module (100%) ⁵ ) 590

Module (300%) ⁵ ) 985

Charring 34 according to Mooney ⁸ )

Hot air aging

(a) 168 hours at 212 ° F (00 ° C) tensile strength 150 elongation 240 Module (100%) 1450 Hardness 82 Tear strength 52.0

(b) 168 hours @ 121 ° C (250 ° F) tensile strength 193 elongation 155 Module (100%) 2200 Hardness 82 Tear resistance -

70/30

Yes

135

600

72

44.3

635

1080

38

70/30

no

104

620

69

34.3

495

760

46

⁷ 0/30

no

215

720

80

69.0

460

1080

V
70/30

217

665

78

70.5

580

1405

70/30

no

183

675

62.3

445

1100

VI O

50/50 50/50

no ·; · ηη

125 116

450 375

74 74

51.8 39.4

164 130 224 262 165 169 128 240 102 400 375 283 170 140 1625 1825 850 1183 850 85 86 85 85 81 82 79 - - 48.5 37.9 52.2 48.5 37.9 44.6 37 ,! 207 81 178 186 91 _ 110 15th 122 100 40 - - 2750 - 2066 2458 - - - 88 93 92 92 95 - - - - 35.7 32.5 35.2

table 6 (continued)

. ■
■ let ^ ^ ι. -
I. -
II III IV V VI VII VIII . - ■ * ■ ~~
(c) hours ( ^{aged at 121 0} C, until specimen when bending around 180 ° broke) 500 410 81 410 400 84 - - Aging in oil ASTM No. 2 oil at 121 ° C, 18 hours tensile strenght 279 141 109 241 222 177 134 107 strain 410 375 400 637 600 620 - - Module (100%) 995 1145 750 725 915 550 - - Module (300%) 1685 1875 1300 1825 2010 1287 - - hardness 78 76 73 78 75 75 88 86 Moisture absorption ⁸ ) Distilled water at 100 ^° C. for 70 hours tensile strenght 108 109 97 141 148 120 147 114 strain 680 680 690 650 690 740 - - Module (300%) 530 480 340 680 620 500 - - hardness 57 62 56 67 68 63 67 63 Volume change (%) 7.2 5.7 4.6 12.6 10.9 16.0 3.5 5.3

Electrical Properties

Dielectric strength ⁹ ) 330 316 375 -

Specific resistance

(Vol.) ¹⁰ )

XlO ¹⁰ ) 6.21 6.49 4.55 -

Color retention

(a) Aged for 70 hours at 100 ⁿ C (% residual reflection

480 Ä) 70 74 43 66

(b) Aged for 70 hours at 121 ^° C. (% residual reflection

at 480 Ä) 35 38 14 32

Low temperature break point ^{1 J} )

71

35

42

Passed (° C)
Failed ( ⁰ C) -46
-49 -46
-49 -51
-54 - - - Abrasion resistance ¹² ) (Taber)
Weight loss (mg) 38 22nd 170 6th 3 8 9 Flame retardancy ¹³ )
UL test, vertical burns passed
UL 94
Group I. burns burns passed burns
UX. 94
Group I. -

Notes to Table 6:

) Mooney conspiracy_

') Hot air aging ~ ^ Immersion test-ASTM D 471. ·) Moisture release em ^ chts «/ o _

«) Dielectric * & ^l & ^at r ^ h isTM D 257 - Ohm · cm. ") Specific resistance (VoD - ^ ™ ₇ ^ _ * C.«) T ^ emperature breaking point ~. ^ F ™ £ '_ Weight loss in mg - H ») Abrasion-resistant a * ber] I- · ^ ™ ^ _p £ . 94 vertical 1 ") flame retardancy - U. U-iesigruw =" gatat 24 hours at 121 ° C and aged) for 24 hours at 100 ⁰ C..

. Wheel - weight 250 g - 5000 revolutions.

Example 5
Thermoplastic molding compounds

Molding compositions in the range with more than 50% PVC can also be used. Mixtures VII and VIII (Table 2) were molded into specimens measuring 152 × 152 × 3.2 mm and together with a nitrile rubber / PVC mixture in a ratio of 25:75. The latter was done in the same way worked through like the mixture VII and consisted of a commercially available nitrile rubber of medium hardness and a medium molecular weight PVC. The physical properties are in the following Table 7 indicated:

Table 7

mixture Trade mixture VII more common VIII (from Nitrile (from Table 2) rubber Table 2) PVC

Rubber / PVC 25: 75
Limit tensile strength- 380
speed, kg / cm ²
Impact strength 26.8
after Izod
ft. lbs./in.

Elongation,% 315

Flexural modulus 1.9 ■ 10 ⁵

Thermal resistance 36
at 18.5 kg / cm ²

25:75
268

23.6

120

1.6 · 10 ⁵
35

10:90
500

1.5

100

3.9 ■ 10 ^s
50

merisate represent a well-known class of substances, those The essential feature is that the molecules are essentially based on the normal polymer chain structure the simple vinyl chloride polymers participate, but with the difference that the chains at intervals by the remnants of the other, externally unsaturated compounds involved in the polymerization were involved, are interrupted. Provided that (1.) the other unsaturated compounds in men

xo gen of no more than about 20% based on the Weight of the copolymer, and that (2.) the other compounds do not have a crosslinking effect, d. H. do not contain multiple, independently reactive unsaturated groups that split into different Being able to incorporate polymer chains becomes the fundamental character of the vinyl chloride polymer not changed by the addition of these foreign unsaturated compounds; rather, you get one certain advantageous plasticization and greater solubility and compatibility brought about by the discontinuity of the mixed polymer chain. In the copolymers of vinyl chloride can also contain up to about 2% crosslinking comonomers without affecting the properties of the one

fundamentally change multiple vinyl chloride polymer.

The acrylonitriles are compounds with the formula

30 CH, = C-CH

Under the designation »vinyl chloride polymers« used here one understands all polymers of vinyl chloride or copolymers with smaller ones Proportions of other unsaturated compounds that can be copolymerized with them. The mixed poly 40 be.

wherein R is a hydrogen atom or an alkyl radical means having 1 to 8 carbon atoms.

A halogenated acrylonitrile is understood to mean a compound of the type indicated above, wherein R represents a halogen atom.

When reference is made to a butadiene-1,3-hydrocarbon, isoprene, Understood chloroprene and similar compounds

Claims (1)

1 2 ... as well as an excellent resistance to ratent claims. permanent deformation, tear resistance and an 1. Thermoplastic molding compositions from (A) have a marked color retention capacity. Farther Vinyl chloride polymer and (B) a butadiene was found that the masses with the usual Acrylonitrile copolymer, as a result of which flame-retardant additives are compatible, so that k e η η ζ e i c h η e t that the too much of the normally flammable nitrile rubber itself 10 to 90 percent by weight based on the vinyl extinguishes. chloride polymer, present constituent (B) The molding compositions according to the invention can before represents a Tetrcpolymerisat, which are plasticized from a) 30 to their processing, so that the 90 parts by weight of a butadiene-l ^ -kohlenwas- io processor no special devices for the preparation hydrogen, b) 10 to 50 parts by weight of an acrylic heating and mixing required. Also are on none acid nitrile, c) 1 to 9 parts by weight of a halo stage of the mixing process higher than temperatures Generated acrylonitrile and d) 1 to 9 weight- they are normally applied, necessary, and it sharing of an alkyl acrylate with the formula, all common processes and devices can 15 applications for processing rubber H Rj O will be.