DE2036305A1 - Stabilized molding compounds made from polymers containing vinyl chloride - Google Patents

Description

Stabilized molding compounds ^:

from polymers containing vinyl chloride

Known to suffer halogen-containing polymers _not like ζ.Β "polyvinyl chloride, a drastic reduction under the influence of light and heat, among other things, au an unwanted discoloration of the moldings leads" are "already a colander of stabilizers" known before therm. Load are added to the vinyl chloride polymers. Of these, organotin mercaptides are the most effective thermostabilizers. They are organotin derivatives of. Mereaptanes, mercapto acids and mereapto acid esters »

Alkyl tin sulfides have also been proposed for stabilization, e.g. in the American patent specification 2,746 »946 the French patent specification 1,111,320, the German Patent specification 1 160 177 and the German Offenlegungsschrift 1,544,902. These alkyl tin sulfides are economically superior to the alkyl tin mercaptides and can therefore be used there where the latter are too expensive. Because of the poor initial color of the vinyl chloride polymer stabilized with it In comparison with those containing organotin mercaptides, however, they could practically not be used on their own. An improvement of the initial color through the additional use of

109885/1 $ 72

Sheet for writing from

at

wist ia ier English ίο- Si "© @ © loaliaati 'the 2 ³ IiWS ³ Ue for this

ti

It was snffi g® £ iaaiea _s dal the A & fangsfartee- "of

19169 _s 770 learn tail section ₉ jireriea Hiiss © a ₂ f iaiea "and

/ above all ".manufactured-

are ρ simiaiast small Zmsäts sini

pre s eiilag © a © a

the Aiisgaa ,; sulfides.

The H © rst © llmag d © 3? lllsflsiaasmlfii®. takes place; in the manner of diarek ¥ ®satg tos Alteylsinacliloriäeii or -broaidea with aqueous lisiaagsa w © & Aüteali- or AaaoaiuasBlfiä @ a. or BXL & h. ins ¹ © !, UBsati T © a A13qflsis®. © 2SÜ © ait sulfur =

hydrogen ia @iaao g @ © iga © t @ a

The © rfiaiiuigsgesäl © Ιθέ ^ θ ss © Eiuag i © r Wirltaaag voa Alkjl trbareneiL Znsats to the ■ special one fttr tie

or.

utr.oaas as amsfe ias ~

ait

sulfides,

1OiSiS / 167

, j. - -German-.

"■" 2— Advance

Production Ltd. Sheet for writing from · to

In combination with alkyl tin sulfides have proven to be ■ particularly effective the mono- and di-alkyltin chloride and -bromide proven. This was surprising and not predictable, since these compounds are halogen-containing polymers; As is known, they do not impart a stabilizing effect against the effects of heat, but rather accelerate the elimination of hydrogen chloride and thus catalytically accelerate the degradation. See e.g. J. Voigt, The Stabilization of Plastics Against Light and Warmth, 1966, page 370. So it occurs when using a mixture of alkyl tin sulfides with alkyl tin chlorides or bromides evidently have a real synergistic effect one that turns these mixtures into extremely effective thermostabilizers for halogen-containing.polymers. ·.

Small amounts of alkyltin chlorides are already sufficient -bromides in the stabilizer mixture in order to improve the thermal stability of vinyl chloride polymers in the initial phase to improve. Due to the small amounts of alkyltin halides added on the other hand, the good long-term stability of the polymers stabilized with alkyltin sulfides is not disadvantageous influenced.

The alkyltin sulfites and halides that can be used correspond to the gross formula

where R is an alkyl group, preferably with 1-8 carbon atoms, X is S., - or chlorine or bromine

o, 0 ■■ - ■ ' ■ - ■

and η is 1, 2 or 3.

The alkyl tin compounds can also be used as a mixture of different Degrees of alkylation are present.

10 9 8 8 5 / 1B 7 2

GmbH

Sheet for writing from to

Di® stabilizers are 'useful ia.! Narrow from 0 _? 1 to 5 $, preferably vosa O ₉ 5 Ms 2 $ _r on ias su stabi-. line Rende polymers sucked verw @ alet "In". Desa 'S-tabili-' satorengeiaiscfe -can the ratio sulfide halide jbu 100 s 1 to 2 s 1 amount is preferred.... "means a ratio of 20 ι 1 to 3: 1" . '. : '. . '·

Di © aynergistiseh. wirJceaaea © eaissfee τοη Allqrlzinnsulfiden. and AlkylsiianclilorideEL oi © r -teomidea can, also au-saiimen " with other known stabilizers, - "especially with organo--" ainnmereaptiden or OrgaaogiBaearfeozylaten, used will.

The following examples are intended to illustrate the invention. without them on the named. YsrMaiiÄgen to restrict.

Beiapi®! 1 ,

100 parts of an after de "Bias peas ionsws-f & hr en Merges divided polyvinyl chloride of K value 60 has been" stabilized the -gemäfl Tables A and B were, Tb @ i. "Vermischt- 18O ⁰ C 5 .Minuten long on a two-roll mill and anschließend.1 minute thick at 180 ⁰ and 200 atm O mm to 1 ■. press plate "■ pressed. In addition to the recipe, Tables A and B show the discoloration of the press plates. ; . "

Example 2

100 parts of a stabilized according to Safeeil © C. Polymers.

with a K value of 60, that of 80 ^ from polyvinylchloride - and. au 20 $ consists of chlorinated polyethylene, - were a © i 18O ⁰ C mixed for 5 minutes on a two-roll mill and then b 1 minute <

1 mm thick sheet TerpreBt »

anschließemfl for 1 minute at 180 ⁰ C and 200 · atü-. to a

In Table C, there are discolourations in addition to the Si © recipe the press plate reproduced. .

109885/157

Tabslie

j Ό - '- ΙΌ ί I · Η > H -H

:> ϊ «Η -PH

Χι 3 PS Pi -ρ ta, ο to ω ö Oo

• r>. · Η C · Η

-C

• Η

S Γ

-α

• Η j

OiOj ι η "; ■■ ι ο] ο i -ri '-.

. I · Η ■ ' H, HÄ- irtk H 1 I h \

I «Η I H« Η; 14! > t)! > ;, Ο 1 IA ^ HO]

HH ■ -:>: Η HO! 4 ³¹ H ϊ +5 · Η | HO>: Η |

4 ^ GO. j3 Oj c * j tQ fin -fj * Jq -4-3 ^: 40 rQ ■ »^ p> ^ ir 1 Θ13 ^

β-H ^: cβ c ν ^; öd iod ϊ., ο ti ή | -. ■ ·· Dlatte

Color of

• Η · Η

.η

• Η · Η

O -H - O · Η ^: · Η -H

• Κ ISI

j-. ' yellow

, 0.051.

greenish swara

0.95

i- ° «05 r j

colorless ^, greenish black

green black colorless

2 1.9

, 0.1 y

light brown colorless

0.1 ν *

i 1.9

ί 0.1

.1.85

ί ί

black colorless

Brown black

¹ 0.15

colorless

j '"" 7T 0.5 -' [t " _f 5

) 0.4: 1.3

ί 0.2 11.6

0.4 ii,

0.2 1.6

! yellow

ϊ colorless

i 0.2

colorless

'.; ■ Iq, 3'

ί colorless

1.4

0.2

: - colorless

■ dark brown 0.6 ■. '■ colorless

10 9885 / 1S72

BAD ORiQfNAL

Monooctyl
tin sulfide Dioetyl-.
tin sulfide Moaooctyl ^
simtri »
chloride Dioctyl ^
tin-dl.- ■■
chloride '■ -ι "Faiibe. The
.- PreBrslattB 1-. ■ V. "-. : -ι . . 0.2 ■ ■ ■■ 0.8
■ ι __ _jipi _, ^. ,, .. U = '0.2. . colorless U. .. ι,. -. . . , _ - _. . .... · ■ '· · - .—
2 ■ ": -; ■ ■ • daa cel brown _{m a fcullll} _ \ ■ 0.4 *. black "_; ■ 1.6 0.4
! - - colorless i ".- ■■■ · - ■■ ": - ■ -_ ■
. 0.5 greenish black 1.5 O ₉ 5 colorless

Tabel

Dibutyl sense sulfide

1.9

1.7

1.9

1.7

Monobutyl «tin-tri-

cfalorid

0.1 0.1

0.3

tyl ζ inn · = ^ color of - ■; Press plate

dark brown • brown-black

; very light j

• OeIb. "".

■ 0.1

black

■ colorless

^; Brown

■ light yellow ί swarm

= colorless

Claims (4)

Deutsche Advance Produktion GmbH sheet for writing to patent claims 1. Stabilized molding compounds made from vinyl chloride polymers or copolymers or from polymer mixtures with predominant content of vinyl chloride polymers, which as Stabilizer Allcyljsirinsulfide contain ^ characterized by that it is additionally stabilized with alkyl tin chlorides or bromides to improve the initial color are. ^Λ::: -: ". ■■■■■■." ■ ■■■■■■■■. ' i 2. Molding compositions according to claim 1, characterized in that they contain 0.1 - 5 # alkyl tin sulfides and the ratio of the alkyl tin sulfides to the halides 100: 1 to 2 s 1 amounts to. 3. Molding compositions according to claim 1, characterized in that they contain 0.5 - 2? 6 alkyl tin sulfides and the ratio of the alkyl tin sulfides to the halides 20: 1 to 3 s 1 amounts to. 4. Molding compositions according to claims 1 to 3, characterized in that the alkyl groups of the alkyltin bonds Contains 1 to 8 carbon atoms. A. 109885/1572