DE1926949A1 - Process for the production of heat-stabilized halogen-containing polymers - Google Patents

Description

PATENT LAWYERS DR.-INQ. H. FINCKE βΜΟΝΟΗΕΝ «. DIPL.-ING. H. BOHR MMnmt · »Y 7. MM 1969 DIPL.-ING. S. STAEGER Farnrufi · 2ίί0 40

Folder 21982 - Br, K. Case 713

Billiton-MkT Chemieehe Industrie M.V., The Hague, Netherlands

"Process for the production of heat-atabilized halogen-containing polymers"

The invention relates to a method of stabilization of halogenated. Polymers such as s.B. Polyvinyl chloride, and on new stabilized halogen-containing Folyner accessory sets.

It is well known that various halogen-containing organic polymers, particularly vinyl halide polymers such as e.g. Homopolymers of vinyl chloride and copolymers of vinyl chloride with other monomers are degraded if they are one exposed to heat for a longer period of time, which manifests itself in a darkening of the resin and an increase in brittleness ο These disadvantages can make the resin unsuitable for many

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High appearance results and the increased brittleness can result in mechanical failure. A large number of τοη materials was previously used to stabilize halogen-containing polymers. Many of these additives have some degree of τοη Success in stabilizing τοη halogen-containing resins against brought the degrading influence τοη heat, but there are still many applications in which a greater degree of τοη heat stability is desired than was previously possible,

A special characteristic of the known stabilizer systems is that they do not completely prevent the degradation of resins or polymers such as polyvinyl chloride during the periods of time during which the composition of resin and stabilizer is kept on the hot mill on which it is mixed. During this period of time, which can be 5 to 50 minutes or longer, the various ingredients, such as pigment, plasticizer, stabilizer, lubricant, etc. _, can be mixed with the resin. The mixture is exposed to the influence of heat and pressure in order to produce an essentially homogeneous mixture. During this period of intense heating, typically 175 ° C or above, the resin can degrade much more quickly than under normal processing conditions. This means that the product coming out of the Banbury mixer or extruder can be darker than desired »

The experts have been trying this caused by heat degradation of various by adding materials such as _o auxiliary heat stabilizers to eliminate ,, Ss showing features unsufriedenstellender, it has been found, however, that the presence of these additional materials undesirable side effects can result, the Can change resin or polymer »Accordingly, it has not previously been possible to produce resin compositions that are completely satisfied in a»

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are stabilized against the degrading influence of heat “. _4th

Ba is an object of the present invention to provide a method for Stabilization clay containing organic polymer or halogen Resin compositions, especially vinyl halide polymers, to create against heat-induced degradation ο Bb is a Another object of the invention to provide new stabilized halogen-containing To create polymers. Further goals emerge from the following description.

Thus, according to the present invention, there is first a method proposed for the production of a new halogen-containing polymer, which is stabilized against the degrading influence of heat, characterized in that a halogen-containing one Hare adds a stabilizing amount of the following ingredients: a first stabilizer of the formula R ^ SnX ^, wherein R is selected from the group consisting of alkyl having 1 to 20 carbon atoms, Aryl, alkaryl, aralkyl and cycloalkyl,

where an R is -SR or -OR when X is «0Sn ^ 2 or" -OSn ^ _P

^ SR ^s 0R

^s 0R and wherein X is selected from the group consisting of R ¹ , -OR, -SR, -OCQR, a residue of a meroaptooarboxylic acid ester

-SR "-OCOR and -OSnC are selected _f where e is the same

^ (OH) (SE)

0 or 1) and R * differs from R and is selected from the group from which R is also selected and b is 1-3} X is different from R and from R ** and R ^{1 is} different from H is? and a second stabilizer R * Sn (R **) _ _, where R *

a g ~ * a

represents a hydrocarbon radical selected from the group which consists of alkyl, cycloalkyl, aralkyl, alkaryl and aryl »and is an R * -SR when R **

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ORIGINAL INSPECTED

/ ^R 2 Λ

-OSn ^ 1st, R ** S, -SR or OSn "^ a remainder of a Mei-capfco-

^ -SR ^ SR

carboxylic acid ~ S-R "-OOO ~ or a residue of a mercaptocarboxylic acid ester -S-R'-OCOR is, R "is a divalent hydrocarbon radical is obtained by removing a second hydrogen from a radical belonging to the same group is selected, from which R is selected and a is an integer from 1-5, and when R ** is a residue of a mercaptoearboxylic acid is, a is 2 and g is 3 and in all other cases g is 4 -,

The polymers or resins which can be stabilized by the process according to the invention bind halogen-containing organic polymers, specifically typically those which contain chlorine atoms bound to a polymer chain. These polymers can be homopolymers, such as, for example, polymers of the vinyl chloride type , for example polyvinyl chloride, polyvinylidene chloride; etc _o , be * They can also be copolymers obtained by polymerizing vinyl chloride or vinylidene chloride with other ethylenically unsaturated monomers. Ethylenically unsaturated monomers are compounds that contain polymerizable carbon-carbon double bonds and include acrylates , such as ζ-B, acrylic acid, ethyl acrylate, acrylonitrile, etc. _, vinyl monomers, such as, B, styrene, vinyl acetate, etc.; Maleates, such as • e.g. maleic acid, maleic anhydride, maleate ester, etc., for the sake of convenience, the following is simply on Vinyl chloride polymers

These polymers can be either hard or soft. When tough Polymers are used, then they can be impact modifiers, Pigments and / or fillers, lubricants, etc. in addition other

to contain resin / stabilizers. When using wiche polymers

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then they can contain plasticizers (primary and secondary), pigments and / or fillers _f , lubricants etc. in addition to the resin stabilizer *

The vinyl chloride polymers may also contained plasticizers such as dioctyl _o, lubricants such as stearic acid z.Bo, fillers

The first stabilizer which is used according to the invention has the formula R ^ SaX, * .. ^ ¹ ^ of this compound, R is a hydrocarbon radical which is preferably selected from the group? selected from alkyl, cycloalkyl, aralkyl, aryl, alkaryl and such inertly substituted radicals. When R is alkyl, it can typically be straight chain alkyl or branched chain alkyl, such as Z ₀ B ₀ methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl , Neopentyl, isoamyl, n-hexyl, isohexyl, heptyl, octyl, decyl, dodecyl, tetradecyl »octadecyl etc. Preferred alkyls are the lower alkyls, i.e. those? which contain 8 carbon atoms or less, such as Z ₀ B ₀ the octyls and lower groups ο If R is cycloalkyl, then it can typically be cyolopentyl, cyclohexyl, cycloheptyl, cyclooctyl etc. _{o be} , if R is aralkyl then it can be in typically, benzyl, beta-phenylethyl, t-phenylpropyl, ß-phenylpropyl, etc. _o "If R is aryl, it may typically be phenyl, naphthyl, etc to be _{o o} If. R is alkaryl, it may typically be tolyl, xylyl, p-ethylphenyl, p-nonylphenyl, etc _e be "R may be inertly substituted, for example it may bear a non-reactive substituents such as Z ₀ B ₀ alkyl, aryl, Cycloalkyl, aralkyl, alkaryl, ether etc. Typical substituted aryls are, for example, _o anisyl, biphenyl etc. _o Inert substituted aralkyls include chlorobenzyl, p-phenylbenzyl, p-methylbenzyl etc. An inertly substituted alkaryl is e.g. 2j, 6-di-tert-butyl -4-methyl-phenylo You don't have to

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all groups R be the same.

In the compound R ^ SnX. ^ can be XR ³ , -OR, --SR, -OCOR or JSi ₂

-OSn 'be; b can be 1-3 if X equals R ^s ,

^ (OR) (SR)

R ¹ differs from R, but is selected from the same group from which R is selected o Typical first stabilizers for the Pail that X equals Ii 'are:

Allyl triphenyltin
Dibutyl-diphenylζinn

fc triphenylbutyltin

Diallyl diphenyltin
Dimethyl diphenyl tin
Dicyclohexyl-diphenyltin =

The preferred of these compounds are allyl briphenylsense and dibutyl ~ diphenyltin

If X equals -OR, then typical arsta stabilizers are:

Dibutyltin dimethoxide
Octyltin-tris (propozyd)
Tricyclohexyltin ethoxide

The preferred of these compounds is octyltin ~ tris (propoxide)

If X equals -SR then typical first stabilizers are:

Butyltin tris (lauryl mercaptide) Dibutyltin-dilauryl-mercapt id Dibutyltin-stearyl-mercaptidr.

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If X equals -OGOR, then bind typical first stabilizers:

Butyl tin tris (octanoate) diphenyl tin dilaurate
Dibutyltin bisi iso-octyl maleate) "

If X is equal to -S-R "-OOOR, then typical first stabilizers are:

Dibutyltin bis (iso-octyl-mercaptoacetate) tributyltin-iso ^ octyl-mercaptoacetate butyltin ~ tris (iso-octyl-mercaptoacetate) dioctyltin-bis (iso-octyl-mercaptoacetate) _e

If X is -OSnCT, then e can be 0 or 1 leg.

If e equals 1, then X can be -OSrf ^ ² _o In this case-

Ie is an R equal to -OR, and then the general formula is , and are the typical first stabilizers

QR OR
then z «B _o :

Bis (dibutyl-lauryloxy tin) oxide Bie (dibutyl-decylocytin) oxide.

If e equals 0 »then one R equals -SR, and the general formula is then R ₂ -Sn-O-Sn-R ₂ * Examples of first stabilizers

SR SR
liBators are then:

Bis (dibutyl-lauryl-mercaptotin) oxide Bis (dibutyl-octyl-mercaptotin) oxide.

This formula can also be (dibutyl-lauryloxytin-dibutyl-lauryl-

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mercaptotin) oxide: Bog-Sn-O-Sn-Bug embracing _e

OLa SLa

Preferred :: erate. Stabilizers are: dibutyl-diphenyltin; Monobutyltin ~ trls (ootanoate); and bis (dibutyl-lauryloaytin) oxide

The second stabilizer that can be used in the process according to the invention is a compound of the formula ί R * Sn (R **), where a is an integer of 1 _f 2 or 3 .. If

^ae ~ ^a below

R ** is a residue of a Meroap.tocarboxylic acid (as / indicated), then a is 2 and g is 3 p giving the formula the following form receives: R * pSnR **. If R ** is one of the other substituents (such as given below), then g equals 4ο in this formula can R * be a hydrocarbon radical selected from the group which consists of alkyl, cycloalkyl, aralkyl, alkaryl and aryl, and an R * is -SR or -OR when R **

RR R

/ ² your -OSn ^ ² is »R ** can be S, -SR or -OSn ^ ²

a residue of a mercaptocarboxylic acid -S-R "-OGO or a residue of a Mercaptocarboxylic acid esters -S-R "-OCOR. In this formula is R "is a divalent hydrocarbon radical selected from the same group from which R is selected. If R ** is a residue of a meroaptocarboxylic acid, then the residue can cyclize (or polymerize-cyclize), like this for example for the compound dibutyltin-ß-mercapto-propionate Case is because of the presence of the correct number (5-8) atoms that can cydissize »

Typical second stabilizers are butyltin tris (iso-octyl mercaptoacetate) and tributyltin lauryl mercaptide, Bar preferred second stabilizer is R * ₂ Sn (R **) ₂ o

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! Typical preferred second stabilizers are:

Dibutyltin bis (lauryl mereaptide) Butyltin-tris (lauryl-mereaptide) Dibutyltin bis (octyl meroaptide) Tri-cyclohexyltin-iauryl-mercapt id Dibutyltin bis (benzyl- »mercaptM) Diphenyltin bis (oetyl-mercaptide) dibutyltin-bis (xylyl-mercaptide) Octyltin-tris (iso-octyl-mercaptoacetate) Dibutyltin bis (eyclohexyl mercaptide) . Octyltin trisidecyl mercaptide) Dibutyltin ^ bis (phenyl-mereaptide) bis (dibutyl-lauryl-mercaptotin) oxide Diootyltin ~ bis (lauryl-merqaptid) Dioctylzine tri-bis (octyl-mercaptid) Dioctyltin bis (ben2grl-meroaptid) Dioctyltin bis (xylyl mercaptide) Dioctyltin bis (cyclohesqyl-mereapt id) Dicyolohexyltin bis (lauryl mereaptide) Dimethyltin bis (lauryl mereaptide) Dimethyltin bis (benzyl mercaptide) Dimethyltin bis (cyclohexyl mercaptide) Dimethyltin bis (xylyl mercaptide)

Dibutyltin-ß-mercapto-propionate (including the Polymers thereof)

Dioctyltin-ß-mercapto-propionate (including the Polymers thereof)

Dibutyltin bis (iso-octyl-mercaptoacetate) Dioctyltin bis (iso ~ octyl mercaptoacetate) Dicyelohexyltin bis (iso-ootyl-mercaptoaoetat) Dimethyltin bis (iso-octyl-mercaptoacetate) Diphenyltin-bis (iso-octyl-mercaptoacetate) Dibutyltin bis (lauryl mereaptoacetate)

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Dibutyltin bis (benzyl-mercaptoacetate) Dibutyltin-bis (cyoloheagrl-mercaptoacetate) _Q

The preferred second stabilizer is dibutyltin bis (isooctylmeroaptoacetate). The first and the second stabilizer can Typically, the first stabilizer is in an amount of 0.1-10 parts by weight _e 100 parts by weight of halogen-containing resin, typically vinyl chloride resins are used to be "in stabilizing amounts present. Preferably, it can be used in an amount of 0.25-2 wt parts by _o, preferably 1.0 percent, -part, per 100 parts of halogen containing resin "

Typically, the second stabilizer can be used in the amount of 0.1-10 parts by weight per 100 parts by weight of halogen-containing resin. Preferably, the amount used can be about 0.2-2, for example 0.7, by weight _o parts per 100 parts by weight of halogen-containing resin

Thus, the preferred heat-stable Vinylchloridpolymerzusaimnensetzungen can according to the invention 100 parts by weight _o a vinyl chloride polymer, a stabilizing amount, typically 0.1-10 parts, a first stabilizer and a stabilizing amount, typically 0.1-10 parts eine3 second stabilizer contained

The novel heat and light stable compositions of the invention can be prepared by such techniques as milling, dry mixing, Banbury mixing, or any other commonly used mixing method. _E

A mixing process, which can be particularly useful, consists in the preparation of a stabilizer composition ', which the first stabilizer, the second stabilizer and

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Contains auxiliary accessories · You can set up stabilizers later added to the vinyl chloride polymer and carefully mixed with it “If this technique is used, then the stabilizer composition typically contain stabilizing amounts of the stabilizers, typically 0.1-10 parts by weight of the first stabilizer and 0.1-10 parts by weight of the second stabilizer ο It can preferably be about 0.25-2 Qew "parts, for example 1.0 part by weight of the first stabilizer and about 0.2-2 parts by weight, for example 0.7 parts by weight, of the second stabilizer included.

Whichever mixing method is used, the first stabilizer and the second stabilizer are desirable in each case essentially entirely through the vinyl chloride polymer composition to mix.

Eb is a feature of the new stabilizer systems of the present invention is that they allow the preparation of stabilized halogen-containing polymers and resins, in particular vinyl halide polymers such as _o vinyl chloride, which are distinguished from heat by its resistance to the decomposing effect ,. The degree of stabilization obtained in such systems can be considerably higher than that which has hitherto been achieved with the known stabilizer systems »

Because of the exceptional properties of this new stabilizer sy st ems it is possible to achieve a stabilization with a smaller amount and thereby a more effective system, in terms of cost.

The invention is explained in more detail with the aid of the following examples. In the examples, all parts are expressed by weight, unless otherwise stated ₀

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These examples used a hard vinyl chloride polymer which had a specific gravity of 1.40, a Shore Durometer "D" hardness of 80, and a final tensile strength of approximately 490 kg / cm and which is sold under the trademark Geon 103 BP ₀

Selected compositions were thoroughly mixed by the polyvinyl chloride was applied to a two-roll mill was heated differential "the oil to a temperature of 175 ⁰ C. At the same time, the specified amount of the first and the second stabilizer was added. The mixture was rolled for approximately 5 minutes. An endless band of the composition formed around one of the pods. This tape was cut and the composition was removed from the hot roll as a continuous sheet. Squares measuring 2.54 cm × 2.54 cm were cut out of this material for the heat stability tests.

For the thermal stability test, the squares were placed in an air <oven which was controlled so that a temperature was maintained from 205 ⁰ C. Samples of each composition were removed from the oven at 15 minute intervals and visually rated for color change and degradation according to the following scale.

7 - clear, water-white

6 - just white

5 - slightest degree of yellowing 4 - moderate yellowing

3 - deep yellow-brown color

2 - deep brown color

1 - dark brown to black color.

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~ 13 -

The amount of time, in minutes, it took to pass a fourth of 3 or less was taken as the thermal stability value

Examples 1 - 4

In Example 1, 100 parts of vinyl chloride polymer were tested without the addition of a stabilizer and _o taken as comparison in Vergleiehsbeiepiel 2 was the first stabilizer Dibutyldiphenylzinn added in an amount of 3fo parts, and there was no further anweeend stabilizer. In Comparative Example 3, the second stabilizer was dibutyltin-bis-cisooctylf-mercaptoacetate) in an amount of 3.0 parts and no other stabilizer was present.

In Example 4, two stabilizers were present as follows:

Dibutyl-diphenyltin 2.0 parts

Dibutyltin bis (iso-octyl-mercapto- 1.0 part acetate)

Total amount of stabilizer 3.0 parts o

The results of the thermal stability tests are summarized in the following Table I:

Table I.

Example heat stability value in minutes. Color after grinding

1 no heat stability, 1 stuck to the IiUhIe after 1 minute

2 5 4

3 40 6

4 40 7

From Table I it can be seen that Example 4, which is an inventive Example is, best is = Bs has one

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Thermal stability value of 40 minutes and a color of 7 after grinding o Example 4 shows stabilization by a composition which is particularly characterized by low cost, low sulfur content and a low odor during grinding _o It is extremely unexpected to find a cheap one : Composition which, for example, dibutyl-diphenyltin (a component which is characterized by extremely poor heat stability properties) can be used to produce a stabilizer which can be compared with the best stabilizer according to the prior art of Example 3 »

In further examples, the heat stability values and the color after grinding were determined for other preferred systems, where stabilizers were used as follows:

Example 5

Vinyl chloride polymer * 100 parts

Octyl triphenyl tin 2.0

Dibutyltin-bisCiso-octyl-mercapto-

acetate) 1.0

♦ Diamond 40 vinyl chloride polymer

Example 6 (comparison)

Vinyl chloride polymer * 100 parts

Tetrabutyl tin 3.0

♦ Diamond 40 vinyl chloride polymer

The results of the thermal stability tests are given in Table II below

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BeJBPJel W ^ rmsStabilawert In minutes Color after grinding

5 40 7

6 5 3

From Table II it can be seen that the thermal stability value of the new stabilized system is eight times greater than when comparing Example 6. In addition, the color after milling was in comparison 3, which means a pronounced yellowing, while the color after grinding according to the invention was 7, what waeserhell means.

Further tests were carried out on another vinyl chloride polymer, a polymer having a specific gravity of 1.40, a Shore Durometer "D" hardness of 80, and a final tensile strength of approximately 490 kg / cm and under the trademark Diamond - 450 is sold. In the following examples, the resin compositions contained 0.1 part of 2,6-di-tert-butyl-oresol. The furnace temperature was maintained at 175 ⁰ C. The samples were prepared as follows, and the thermal etability value and the heat after milling were as given below.

Example 7 Vinyl chloride polymer 100 Di-n-butyltin bis (ieo-ootyl-

meroaptoacetate) 1.0

Bis (dibxrtyl-lauryloxytin) oxide 0.5 Thermal stability value 60 minutes Color after grinding 7

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~ 16

Example 8

Vinyl chloride polymer 100 100 Butyl tin tris (octonoate) 0.5 0.5 Di ~ n-butyltin bis (iso-octyl- mercaptoacetate) 1.0 1.0 Thermal stability value 60 minutes 75 minutes Color after grinding 7th 7th Example 9 Vinyl chloride polymer 100 Butyltin tris (laurate) 0.5 Dibutyltin bis (iso-octyl * 1.0 mercaptoaoetat} 60 minutes Thermal stability value 5 Color after grinding Example 10 100 Vinyl chloride polymer 0.5 Butyl tin tris (octanoate) Dibutyltin bis (lauryl-mer capt id) 1.0 Thermal stability value 90 minutes Color after grinding 7th Example 11 Vinyl chloride polymer Butyltin-trie (octanoate) Dibutyltin-S, O-ß-mercapt o- propionate. Thermal stability value Color after grinding

It can be seen from Examples 7-11 that the thermal stability value of the new products according to the invention is exceptional.

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Furthermore, the color is less after the new products have been milled high and typically 7, which is an exceptional value represents (when combined with the high thermal stability value is looked at),,

In further examples the extraordinary properties, these compositions can be seen.,

Example 12

Vinyl chloride polymer 100

Butyl tin tris (cydohexyl maleate) 0.5

Dibutyltin bis (iso-octyl-mercaptoacetate) * 1.0

Heat stability value 75 minutes

Color after grinding 7

Example 15

Vinyl chloride polymer 100 butyl tin tris (octanoate) 0.5

Dibutyltin suffid 1.0

Heat stability value 75 minutes. Color after grinding 5

It can be seen from Examples 12 and 15 that the heat stability value is exceptional _o

Examples 14-17

In Example H below, 100 parts of vinyl chloride polymer were tested without the addition of a stabilizer. This sample served as comparisons In Comparative Example 15, the first stabilizer was monobutyltin-tris (iso-octyl-mercaptoacetate) in one Amount of 2 ropes added, and no further stabilizer was present. In Comparative Example 16, the second sta-

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~ 18 ~

bilizer tributyltin-iso-octyl-mercaptoacetate, which is available in an amount of 2 parts with no other stabilizer present. "In Example 17, the following two were Stabilizers present:

Monobutyltin-tris (iso-octyl-mercaptoacetate) 1.3 parts Tributyltin-iso-octyl-mercaptoacetate 0.7 parts

Total stabilizers 2.0 parts

The results of the thermal stability tests are given in Table I as follows:

Table I a

Example heat stabilizer ι Value in minutes of color after grinding

14 no heat stability, 1 stuck to the mill after 1 minute

15 45 7

16 no heat stability, stuck

at the mill 4

17 75 7

From Table & can be seen that Example 17 of the present invention is significantly better _β than Comparative Examples 14-16 showed a thermal stability of 75 minutes, which is much longer than the Vergleichsb © ispielen _o The new composition is therefore longer by $ 60 effective as the best prior art comparison system. It should also be noted that the color after grinding is 7, which is an exceptional value

In further examples, the heat stability values and the color after grinding were determined for other preferred systems, where other stabilizers were used as follows:

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Example 18

Vinyl chloride polymer 100

n-Ootyl-tin-tris (iso-octyl-mercapto-

acetate) 1.3

Tributyltin iso-octyl-mercaptoaoetate 0.7

The results of the thermal stability tests are given in Table Ha below:

Table Ha

Example heat stability averted in minutes color after grinding 14 (comparison) no heat stability _t

stuck to the MUhIe 1 after 1 minute

18 75 7

From Table XIa it can be seen that the heat stability value of the new stabilized system is considerably greater than in the comparison of Example 1 and that the color after milling was 1 in the comparison, which means a definite black color , while in the test according to the invention a value of 7 was obtained became what water-clear means »

Further approaches result in the heat stability values given below and the given color after grinding »

Example 1Q

Vinyl chloride polymer 100 dibutyltin iso-octyl-mercaptoacetate 0.7

Butyl tin tris (lauryl mercaptide) 1,3

Shape stability value 75 minutes after grinding 7

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Example 20 100 »7 Vinyl chloride polymer 0 Sriphenyltin lauryl mercapt id , 3 n-octyltin-trisiiso-octyl-mercapto- 1 Minutes acetate) 60 Thermal stability value 7th Color after grinding

Example 21
Vinyl chloride polymer

Butyltin-trie (iso-octyl-mercaptoaeetat)

Tributyltin-iso-octyl-mercaptoacetate Heat stability worthy of color after grinding

100

1.5 0.5

75 minutes 7

A review of Examples 19-21 shows that the Thermal stability of the new products according to the invention The thermal stability value of the new compositions is exceptional is, for example, more than 75 minutes «

Furthermore, the color after grinding the new product is 7, which is an exceptional value (including the Thermal stability value of 75 minutes must be observed J)

Accordingly, it will be apparent to one skilled in the art that the novel process of the present invention can produce polymer resins, which are characterized by extremely high thermal stability,

More preferred stabilizer systems within the ranges of the invention _r properties similar to obtain the above-mentioned blank (if it 'file with 1OQ resin

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- 21 are mixed) are the following:

A ", 100 parts of vinyl chloride homopolymer 1.5 parts of dibutyl diphenyl tin 1.5 parts dibutyltin bisCiso-octyl-mercaptoaoetate)

Bo 100 parts of vinyl chloride / vinyl acetate-iiiBchpolymer 1.2 parts of dibutyl-diphenyltin 1.2 parts of di-n-octyltin-bis (iso-octyl-mercaptoacetate)

C. 100 parts vinylidene chloride homopolymer 1.5 parts of butyl triphenyltin 1.5 parts dimethyltin bis (iso-octyl-mercaptoacetate)

Do 100 parts of vinyl chloride homopolymer 1.5 parts of diallyl dibutyltin 0.12 part of 2,6-di-i8oan ^ yl-4-n-propyl-phenol 1.5 parts di-n-octyltin-biBfiso-octyl-mercaptoacetate)

Eo 100 parts vinyl chloride * ^ homopolymer

0.5 part of butyl tin tris (botanoate). 0.20 part of 2,4,6-tri-tert-butylphenol 1.0 part di-n-butyltin-bisCootyl-mercaptide)

P ₀ 100 parts of vinyl chloride homopolymer 1.5 parts of butyltin triacetate 1.5 parts of di-n-butyltin-bis (iso-octyl-meroaptoacetate).

Go 100 parts of vinyl chloride homopolymer 1.2 parts of methyltin trisdso-oc-byl-mercaptoacetate) 0.8 parts of tributyltin lauryl mercaptide

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Ho 100 parts vinyl chloride / vinyl acetate misoh polymer 1.2 parts butyltin-triB (laiiryl-mercaptide) 0.8 part of tri-butyltin-iso-octyl-raercaptoacetate

100 parts of vinylidene chloride homopolymer 1.2 parts phenyltin-tris (iso-octyl-mercaptoacetate) 0.8 part of triphenyltin iso-octyl-mercaptoacetate

J. 100 parts of vinyl chloride homopolymer, 1.2 parts of octyltin tris (isooctyl-mercaptoacetate) O ₁ 8 parts of tri-n-octyltin-iso-octyl-mercaptoacetato

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Claims (1)

Claims Process for the production of a new halogen-containing polymer, which is stabilized against the degrading influence of heat, characterized in that one on a halogen-containing resin, a stabilizing amount of adding the following ingredients: a first stabilizer of the formula R ^ SnX ^ v, wherein R is selected from the group which from alkyl having 1 to 20 carbon atoms, aryl, alkaryl, aralkyl and cycloalkyl, where one R is -SR or -OR, when X is -OSn ^ or -OSriv *, and where X is selected from the ^ SR ^N 0R Group is selected from R ¹ , -OR, -SR, -OCOR, a residue of a mercaptocarboxylic acid ester -SR "-OCOR and -OSn ^ ² _ is selected, where e is 0 or 1 and R ¹ is different from R and is selected from the group from which R is also selected and b is 1-3; X is different from R and from R ** and R ^{f is} different from R; and a second stabilizer R * Sn (R **), where R * is a hydrocarbon radical selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl and aryl, and when R * is -SR ** S ~ H ** S, -SR or -OSn ^ , a residue of a mercapto- oarboxylic acid -SR ⁿ -OCO ~ or a residue of a hercaptocarboxylic acid ester ~ S-R'-OCOR, R "is a divalent hydrocarbon radical which has been obtained by removing a second hydrogen from a radical which is derived from the 009816/16 70 ORIGINAL INSPECTED ~ 24 - same group is selected except the R is selected, and a is an integer from 1-3, and when R ** is a residue of a meroaptocarboxylic acid is, a is 2 and g is 3 and in all other cases g is 4 ^ 2. The method according to claim 1, characterized in that the following stabilizers are incorporated: a first stabilizer of the formula RSn (SR ¹ ) ~, wherein R is selected from the group consisting of alkyl with 1-20 carbon atoms, aryl, alkaryl, aralkyl and cycloalkyl, and R ^{1 represents} the residue of a carboxylic acid ester or a radical that is selected from the same group as R; and a second stabilizer R * ~ Sn (SR **), where R * is a hydrocarbon radical selected from the group consisting of alkyl, cycloalkyl, aralkyl, alkaryl and aryl, R ** is a residue of a carboxylic acid or a Is radical that is selected from the same group as R * » Jo method according to one of claims 1 or 2, characterized in that the first stabilizer is present in an amount of 0.1-10 parts per 100 parts of polymer _o 4. The method according to claim 1 or 2, characterized in that the second stabilizer in an amount 0.1-10 parts per 100 parts of polymer is present * 5. The method according to claim 1 or 2, characterized in that the first stabilizer in an amount from 0.25-2 parts per 100 parts of polymer is present o 6. The method according to claim 1 or 2, characterized in that the second stabilizer in an amount 0.2-2 parts per 100 parts of polymer is present « 00981 6/1 670 ο Method according to claim 1, characterized in that that the first stabilizer is dibutyl-diphenyltin «, 8 »Method according to claim 1, characterized in that that the second stabilizer is dibutyltin bis (isooctyl mercaptoacetate) isto 9ο method according to claim 1, characterized in that that the second stabilizer is dibutylainn-ß-mercaptopropionate or a polymer of it is » 10. The method according to claim 1, characterized in that that the first stabilizer is butyltin tris (octanoate) o Ii ο _r A method according to claim 1, characterized in that the first stabilizer Buigrl2inn-tris (cyclohexylmaleat) isto 12. The method according to claim 1, characterized in that that the first stabilizer is diallyl dibutyltin. is, ο Method according to claim 1, characterized in that that the second stabilizer is dibutyltin sulfide «, = Method according to claim 1, characterized in that the second. Stabilizer dioctyltin-bis (isooctyl-mercaptoacetate) is _o 15 ". Method according to Claim 2, characterized in e t that the first stabilizer butyltin tris (iso-octyl mercaptoacetate) isto _{o The} method according to claim 2, characterized in that the second stabilizer is tributyltin-iso-octylmereaptocetate » 009816/1670 »26 - Process but production of a new halogen-containing polymer which is stabilized against the at-building effect of heat, characterized in that a stabilizing amount of the following ingredients is added to a halogen-containing ^{resin : a first stabilizer of the formula a} _ac i ffir) y ^SnX 4 ^ ( _{x +} y) »where R is an alkyl or alkenyl radical with 1-20 carbon atoms or a cycloalkyl, aryl, alkaryl or aralkyl radical, which radicals can be inertly substituted, T is oxygen or sulfur, X is a radical from represents the same group as R, but is different from R, or a radical from the group -YR, -OCOR, -OCOCH »CHOCOR, -SR ¹ -OCOR (where R ^{1 is} a divalent hydrocarbon radical) or -03η <Γ" ΐ ? £ represents, χ is 1, 2 or 3 and y is 1 when X is the same but is otherwise zero; and a second stabilizer of the formula R (RS), SnZ /. W wherein Z is S, -SR, OSnt ^ ² »-SR ^f -OCO- or -S-R '- OCOR is, al, 2 or 3 is, b is 1 if Z is -OSn """" ^ but is otherwise zero, and c is 4 if ΖγβΏ-Ιί ^ -OCO- or S, in which case a is 2 and c is 3 is. PATENT LAWYERS DUNG. Κ FlNCKE. DIPL-ING. H. BOH6 DH> HNG.S.STA £ GER 009816/1670