DE1719330C3 - Impact-resistant molding compounds made from chlorinated polyvinyl chloride - Google Patents

Description

In order to produce moldings from chlorinated polyvinyl chloride, especially those with chlorine values over 62% to achieve an effective impact resistance, that of a medium to high impact resistance Equipment corresponds to polyvinyl chloride, up to 25% and more are additions of elasticizing agents, based on chlorinated polyvinyl chloride, required. Affect such amounts of foreign substance however, the properties characteristic of chlorinated polyvinyl chloride are sometimes considerable. Nice with an added amount of 20% of elasticizing agent, the heat resistance in most Cases so low that the corresponding moldings are no longer resistant to hot water is. The addition of an elasticizing agent that goes beyond 20 ° ο is also economical Reasons hardly justifiable, although in view of the achievable impact resistance, this is often a requirement consists.

There were now impact-resistant molding compounds based on chlorinated polyvinyl chloride, if necessary with the admixture of small amounts of other polymers, found that meet increased requirements. The molding compositions are characterized in that they contain 5 to 25 percent by weight of butadiene-styrene copolymers, which are modified with acrylonitrile or methacrylic acid ester, and low-pressure polyethylene with an average molecular weight between 20,000 to 200,000 in amounts from 0.1 to 5.0 percent by weight, preferably 0.5 to 3.0 percent by weight, based on the total mixture.

By adding low-pressure polyethylene and a butadiene-styrene copolymer, the copolymers Modified either with acrylonitrile or with methacrylic acid ester are molding compounds obtained that have almost double the notched impact strength and therefore, for example, for the Manufacture of hot water resistant pipes or fittings or plates for chemical apparatus engineering be used.

The high heat resistance of the chlorinated polyvinyl chloride is made possible by the additives in the in most cases hardly affected, in fact sometimes even improved. This surprising result was not to be expected, because low-pressure polyethylene

ίο completely unsuitable as an impact-resistant component alone is.

The chlorinated polyvinyl chloride used is produced in the usual way. Possibly are also mixtures of different levels

chlorinated polyvinyl chloride types are suitable. As acrylonitrile-butadiene-styrene copolymers is for example the commercially available copolymer of 55 percent by weight Butadiene, 30 percent by weight styrene and 15 percent by weight acrylonitrile can be used. With

A butadiene-styrene copolymer grafted with methyl methacrylate can also achieve the same success from 27 percent by weight butadiene, 40 percent by weight styrene and 33 percent by weight methyl methacrylate can be used.

The customary stabilizers can be added to the mixtures according to the invention individually or as a mixture be added, such as polybasic lead sulfate, lead sufficiency phosphite, basic lead carbonate, lead oxide, dibutyltin dilaurate, dibutyltin maleate, alkaline earth silicates, Hydroquinones, lead phenolate, and aromatic compounds that contain phenolic and amine groups be able. Mixtures of higher unsaturated fatty alcohols, waxes, oils and metal salts of stearic acid in question. However, other processing agents can also be used will.

The parts given in the examples are parts by weight.

example 1

Trials 1 to 21

In each case 90 and 80 parts of chlorinated polyvinyl chloride with a chlorine content of 66.7% and a K value of 47.1 are with 10 or 20 parts of an acrylonitrile-butadiene-styrene copolymer (55 percent by weight butadiene, 30 percent by weight styrene and 15 percent by weight Acrylonitrile), together with 4 parts polybasic lead sulfate, 2 parts liquid lead stabilizer and 2 parts of lubricant (mixture of more highly saturated fatty alcohols) mixed. To 100 parts 1, 3 or 5 parts of low pressure polyethylene are added to this mixture and the entire mixture processed into a rolled sheet at 175 ^ C on the mixing mill. The still warm rolled head is in the Then pressed at 175 ° C. and 20 atm within 10 minutes to form a 4 mm thick pad.

For determining the notched impact strength according to DIN 53 453 and the Vicat temperature according to VDE 0302 the corresponding test specimens are cut out of this press plate. In Table 1 are the Measured values for the various mixtures in which the molecular weight of the low-pressure polyethylene between 50,000, 80 to 90,000 and 110,000 is varied, compiled. Experiments 1, 2 and 12 serve as comparative experiments.

Chlorinated
Polyvinyl
chloride
KW 47.1
Cl 66.7 · /. 3 17 1 9 330 J <1.9 _ 4th -40 ° C Vicat
tempe-
rature 100 - 2.2 2.2 110 90 Buladicn-
Styrene
Acrylonitrile
Mixed
polymer - 5.3 3.2 -20 ° C - 109 9C Low pressure polyethylene
(Molecular weight)
50,000 80 to 90,000 - Notched impact strength
(kp cm / cm ^! )
Π0ΟΟΟ 22 ° C 0 ⁰ C 10.0 5.8 2.3 Ul Table 1 90 10 - 8.8 5.0 <1.9 2.7 110 Ver
search 90 10 - ι 4.3 35 3.2 3.0 108 1 90 10 I. 3 8.7 5.6 4.1 2.1 108 2 90 10 3 5 - 8.4 5.3 3.8 3.1 108 3 90 10 5 - 6.6 4.3 2.6 3.2 108 4th 90 10 - - 7.8 4.6 3.4 3.1 UI 5 90 10 - - 8.9 5.4 3.8 2.8 111 6th 90 10 - - 8.0 5.9 3.6 3.2 109 7th 80 10 - - 1 13.0 10.5 4.2 2.9 108 8th 80 10 - - 3 n.g. 13.0 5.0 5.2 108 9 80 20th - - 5 16.5 9.3 4.5 7.3 106 10 80 20th - 1 - 15.0 11.5 6.4 6.2 107 11th 80 20th 1 3 - n.g. 11.1 9.5 4.8 106 12th 80 20th 3 5 - n.g. 11.0 7.2 5.9 106 13th 80 20th 5 - - 17.0 11.1 7.2 5.7 107 14th 80 20th - - - n.g. - 8.8 5.3 108 15th 80 20th - - - n.g. 9.8 8.4 5.7 107 16 80 20th - - 8.0 4.1 109 17th 20th - 1 8.2 18th 20th - 3 5.3 grafted with methyl methacrylate (27 Ge
weight percent styrene and 33 weight percent methyl 19th = not broken). - 5 20th 21 Example 2
Attempts 22 to 36 (η. g. =

In analogy to Experiments 2 to 21, instead of the acrylonitrile-butadiene-styrene copolymer a graft copolymer based on butadiene-styrene,

Table 2

y) g

Try 1 through 21. The measurement results are compiled in Table 2. The trials 1, 22 and 31 serve as comparative tests.

attempt Chlorinated
Polyvinyl
chloride
LTU / Al 1 Plug
mix
polymer Low pressure polyethylene
(Molecular weight) I 80- to 90,000 110000 Notched impact strength
(kp cm / cm ⁴ ) o ° c -20 ° C -40-C Vicat
tempe-
rature Cl 66.7 · / « 5000C 22 ¹ C C-C) 1 100 - - <1.9 2.2 <1.9 <1.9 110 22nd 90 10 - - - 3 ', 6 5.8 3.5 2.7 108 23 90 10 1 - - 8.0 6.1 4.2 2.8 112 24 90 10 3 - - 11.4 6.0 3.5 2.9 110 25th 90 10 5 1 - 9.5 6.8 3.8 3.2 111 26th 90 10 - 3 - 9.6 7.7 3.5 3.1 108 27 90 10 - 5 - 11.1 4.3 3.0 2.8 108 28 90 10 - - 3 11.4 9.0 3.9 3.5 108 29 90 10 - - 5 11.4 5.6 3.8 2.7 111 30th 90 10 - - - 8.0 6.8 3.4 2.2 112 31 80 20th - - - 15.0 28.5 13.2 9.3 108 32 80 20th 1 - - 52.0 11.9 8.0 6.0 110 33 80 20th 3 - - 26.5 12.7 7.8 5.4 107 34 80 20th 5 - 3 28.5 11.4 6.9 4.8 107 35 80 20th - - 5 28.0 10.9 6.4 3.5 107 36 80 20th - 22.0 110

Example 3 Trials 37 bis

In contrast to experiments 22 to 36, a chlorinated polyvinyl chloride with a chlorine content of 65.1% and a K value of 58.5 is now used, which is modified as in experiments 22 to 36. The corresponding measured values are given in Table 3. Experiments 37, 38 and 44 are comparative experiments.

table

attempt

Chlorinated polyvinyl chloride KW 58.5 Cl 65.1%

Pfrcpf- low pressure polyethylene

mixed (molecular weight)

Kerbsch polymerizate resistance
(kpcm cm ^; )

50,000 80 to 90,000 110,000 22 ^C C 0 "C Vicat temperature

-2O ⁰ C -40 "C (" C)

37 38 39 40 41 42 43 44 45 46 47 48 49

100 90 90 90 90 90 90 80 80 80 80 80 80

10 10 10 10 10 10 20 20 20 20 20 20

3 -

5 -

- 12.7
40.0
20.5
13.6
20.0
19.0
30.0
58.0
50.0
27.0
44.5
43.0

5.5
17.5
11.7

8.0
10.2
11.1
12.9
31.0
20.4
18.5
18.5
13.8

2.8

6.8

5.9

7.0

6.8

6.7

6.3

15.0

12.4

10.2

11.3

10.6

2.1

7.4
4.9
3.7
5.3
4.8
3.7
10.0
9.8
4.5
5.9
5.9

109 109 112 112 112 110 112 108 110 109 109 109 110

Example 4 Try 50 to

There were 90 and 80 parts of chlorinated polyvinyl chloride with a chlorine content of 66.7 ⁰ Zn and a K value of 47.1 or with a chlorine content of 65.1 ″ and a K value of 58.5 with 10 and 20, respectively Parts of a vinyl acetate-ethylene copolymer and 4 parts of polybasic lead sulfate, 2 parts of liquid lead stabilizer and 2 parts of lubricant are mixed and compared in each case with a mixture to which 1 part of low-pressure polyethylene with a molecular weight of 110,000 was also added The measured values of the impact strength and the Vicatt permeability are given in Table 4.

The impact strength-increasing plastic pressure polyethylene flow only results from 80:20 mismatches. However, there is a sharp drop in the Vicatt temperature. It turns out that the addition of Low-pressure polyethylene not with every Elastitlzierungsmiltel together with the inventive. benefits results, but to the use of Butadicn-St) rol Copolymcrisate with acrylonitrile or methacrylic acid ester are modified, is bound.

table 4th _ Vinyl acetate
Ethylene
Mixed
polyrr> erisat Nicdcr-
push
polyethylene
Molecular
Weight
110,000 Impact strength
(kp cm cm'-)
22 ¹ C 0 ⁰ C --- -20 ⁰ C _ - 2.6 Vicat
tcmpcrauir
Γ C) Ver
search 100 _ <1.9 _ <1.9 110 1 Chlorinated
Polyvinyl chloride
KW 47.1 KW 58.5
Cl 6CiJn ₁₁ CUiSJ ⁰ O -. - - <1.9 2.1 - 3.1 109 37 100 - 10 <1.9 2.1 <1.9 89 50 - 90 10 I. 2.5 2.7 2.1 2.0 R6 51 90 90 10 - 2.2 - 2.1 2.4 91 52 90 - 10 1 3.5 2.7 2.5 91 53 - - 20th - <1.9 1.9 65 54 - 80 20th 1 3.2 3.7 2.5 67 55 80 80 20th - 2.5 2.0 65 56 80 20th 1 11.1 3.4 69 57 - -

Claims (2)

«Γ Claims: 1. Impact-resistant molding compounds, consisting of A. chlorinated polyvinyl chloride, B. 5 to 25 percent by weight of bmadiene-styrene copolymers, which are modified with acrylonitrile or methacrylic acid esters, characterized in that the molding compounds additionally C. 0.1 to 5 percent by weight of low-density polyethylene with an average molecular weight between 20,000 and 200,000, based on the total mixture, contain. 2. Molding compositions according to claim 1, characterized in that they are 0.5 to 3% low-pressure polyethylene contain.