LU82526A1 - ORGANOSTANNIC STABILIZER COMPOSITIONS FOR HALOGENOVINYLIC RESINS - Google Patents

Description

S5 A - BL-2896 / vd —y- Rsrand-duchy of Luxembourg ..... mr .......................

from .3.3, .. June, 1980 ..................... ^ Ipy ^ Minister ¢ 5¾¾¾ of the National Economy and the Middle Classes

Title issued: ..................................... jr »Vjî. .

Industrial Property Service

S & y LUXEMBOURG

Patent Application I. Application

The so-called soc.anonyme: SOCIETE NATIONALE ELF AQUITAINE. Aquitaine Tower,

F ~ ^^ g24Ô0 '^ 0UF; Ë-EV0Î' £ '”/" "'" FrëSce51 ................ ~ HprIsint € e''pâF

, 46 rue du Ci ^ stiêre, LuWbourgit '(2) acting as agents 00 deposit ...... this thirteenth June mil r <euf hundred ouctre-twenty ............. ................................................. ( 3) at ....... 1Ü ................. hours, at the Ministry of National Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a breie: invention relating to: 11 Compositions es orga-sstâr stabilizers; r.icuss ps ^ r nalogsno- (4) vinyl resins "_ ôéi-Tsre. assuming the resooasabüité.de of this cerlarEiiisu. to the inventor (s) is (are): hicîïôI ftförrrTCKts î.êti & r. & ie Π /, r - cAî / l k-.üa 2. 1ε delegation of power, dated ....... Nr . “.:!" ....................... the —1 „ti— XslÎT ™ —............ ....

2. description in language ..... !! ... s: 'r12L ".r ........................... ........... of the invention in two copies; 4. ................ / ............ drawing board, in duplicate; 5. the receipt of the fees paid to the Luxembourg Registration Office, the [trpïE jâi] nauf r: rcvenâlotie for the above patent application the priority of an ideas) asked) from -; --- / (6i ...................................... L ................................................. .... filed !?) in i7. ”...................................... .i ___________________________________________________________________________________________ îe -........... ............................. -..... .................................................. .................................................. .................................................. ............................................ (8) i (at name of ................................................ ..... L ........................................ .................................................. .................................................. .................................. (9) elect domicile for the saddle and, if appointed, their representative , έ Luxembourg .......................................

_ 46, ΓΙξί __ C; û_ .......................................... .................................................. .................................................. ......................... n 0: requests the delivery of ur. invention patent for the subject described and represented in the abovementioned appendices. - with adjournment of this issue έ ....................................... month.

dt.Ifl? £ 6 £ '' •• in.ctâ '· .-' ·:!: I IL Statement of Deposit

The aforementioned patent application has been filed with the Ministry of National Economy and the Middle Classes. Industrial Property Service in Luxembourg, dated:

1Z June 1SSC

Pr. The Minister at ............................. hours National Economy / Studies Middle Classes, f - A (SSfifff ' '' - • - • ts & feÿ JÈJ ~ t —ί * · “* '* · *' ·

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BL-2896 DPI 3803 i! ί

PATENT

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So-called anonymous company; : i Soc i ët.ê Nati ona i e lît nouinaine il Tour Aquitaine

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'' O-ganostannic stabilizer compositions for resins' i ha 1 ûoén; - vi ny 11 eues h \: i - ί ί fr I?:

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The present invention relates to compositions of new stabilizers: organotins for halo-vinyl resins, as well as to their process | preparation.

j The new organotin stabilizers are of the form i 5 H »1Sn (S (CH2) n0CR6) 30 j in which R’ ^ is the residue of an olefinic compound containing a carbonyl group adjacent to the carbon-carbon double bond. Such olefinic compounds are of the form I .10 * 2 Λ 1 R, -CC = C (1) 1 ut \ ° \ R5 in which R ^, R ^, R ^ represent this hydrogenated or a residue alkylated hydrocarbon containing from 1 to 3 carbon atoms; R ^ represents an alkyl group, a hydroxyl, an oxygen-containing hydrocarbon group.

Among these olefinic compounds, mention may be made of: methyl aerylate, ethyl, hexyl, acrylic acid, vinyl nethyl ketone, this methyl crotonates. The group

SiCKJ OCR, ît n „c

20 O

j is the residue of an msrcapto alkyl ester in which the mercapto group is [I found in the alcohol residue of the ester, R, is an alkyl containing from 1 to 16

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carbon atoms; it can belong to any mono or di-aliphatic acid; however, the preferred esters are derived from fatty acids, especially caprylic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic ‘isostearic, or mixtures of such acids.

”N" can be 2, 3 or L; ur. Of CrL. Can be substituted by a hydroxyl group.

These new organostanr.iq-.es stabilizers 30 R ’.Sn (S '; CHJ OCR')> * r. „T - w are obtained by the action of organotin trihalides R ', Sa Kal on mercaptoalkyl esters I μς / ru \ noo ί ^ ^ π ^ i 35 0 that is to say esters in which the group mercapto is found in the alcohol residue of the ester and not in the acid residue as is the case with certain products described in the prior art. It is surprising to see that thanks! ! with this difference this position of -SH. the activity of new esters oreann- '2 9. fc, advantages of the ease of preparation and purification of these bodies.

The stannic trihalides themselves can be obtained either according to the process described in French patent 2,285,392, or and preferably according to the process described in the French patent application filed on the same day by Société Nationale Elf Aquitaine ( Production), by the action of a stannous compound. On an excess of an olefinic compound of formula (1), in the presence of a hydracid, the medium being free of solvent.

These new organotin compounds have excellent properties for the stabilization of halo-vinyl resins and particularly for that of polyvinyl chloride; they make it possible to reduce the coloration of the halo-vinyl resins during the heating without harming the control of the viscosity.

They can be used either alone or in combination with other very stannic stabilizers known from the prior art; in particular, they give excellent results in combination with dialkyl tin such as I, for example bis (isooctylmercaptoacefcate) of di n-butyl tin l Bu2 Sn (SCHgCOgi.CgH ^) ^ in proportions varying between 5 and 95 % of monoalkyl tin for 95 to 5% of dialkyl tin.

The halogen-containing resins to which the invention applies can be homopolymers, such as, for example, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, polytetrafluoroethylene, polychloroether, polydichloro-styrene, etc. ., eopolymers such as polyvinyl acetochloride or the like, or else various combinations or mixtures, for example pc-lyvinyl chlorides modified with this ethylene or / and propylene, with acrylonitrile- butadiene-styrene, ethylene-acetate, this vinyl and the like.

The new stabilizers can be incorporated into the resin after the polymerization, but before the polymer has dried, or else at the time of setting. implementation of it; their proportion can vary between wide limits, in particular from 0.1 to 5% of the weight of the resin, and especially between 0.5 and 2%.

[i- - The invention is illustrated nor. 1 imitatively by the following examples: EXAMPLE 1 i {Preparation of stabilizers: H, Sc: (S (CH „) OCR, · | 's 2 n„ b 3 | 35 0 f! Preparation of (Metboxy-carbonyl-3 propyl) -tris (palir.itoyloxy-2-ethyl-thio) tin.

A 50C ml flask fitted with a stirrer and a thermometer is placed I in a heating bath: 7.8 c (G.025 mole) of 3 f ί *! Are introduced into the flask; p 300 ml of dry hexane. It is heated until the products are completely dissolved, then j. the temperature is allowed to return to 40 ° C. 7.6 g (0.075 mole) of triethylamine are then added dropwise, then the mixture is heated for three hours at 40 ° C. the precipitate of triethylamine hydrochloride; in the cooled filtrate, 18.5 g! 5 of a white solid crystallizes; it is analyzed and it is characterized as being I CP3 OCO CH2 CH2 Sn (S CH2 CH2 0C0 I * Analysis: C ^ g H112'0g Sn: 1151

Calculated: C: 60.47% H: 9.73%; S: 8.34%; Cl: 0

Found: C: 60.89%; H: 9.91%; S: 8.32%; Cl: O

From the mother liquors, an additional quantity (5.1 g) of recovered product is recovered.

FXEMPLE_2

Preparation of (methoxy-carbonyl-3-propyl) -tris (myristol-oxy-2ethyl | ^ thio) -tin.

j Bans a 1 liter flask placed in a heating bath and fitted with a | stirrer, a thermometer and a dropping funnel, 21.8 g (0.07 mole) of (trichloro) - (3-methoxy-carbonyl-propyl) -tin, 61 g (0.21 mole) are introduced • ethyl mercapto rayristate and 450 ml of dry hexane. The mixture is heated until complete dissolution, and the temperature is allowed to return to 40 ° C., and 21.3 g (0.21 mol) of this triethylamine dissolved in 50 ml of hexane are added dropwise; I heat 3 hours at 40 ° C. 25 g are filtered (ie 100% of the theoretical quantity) | of tris-ethylamine hydrochloride formed. The filtrate is cooled to 0 ° C. It is filtered and 63.2 g of white solid is obtained which crystallizes. This product is characterized by | 2 ^ p j as having the formula j. CK3 OCQ CK2 CH2 Sn (SCCH ^ 0C0 I Analysis: K, 00 Og S, Sn: 1067

Calculates: C: 58.48%; H: 9.37%; S: o, qo% 30: c: 58 »M6 * î K: 9.55%; S: S, Qb%! EXAMPLE 3 repair of ^ nstncxy — canocr-yl-t prcovi) —cris (scs £ royi-cxy — 2! Éfchylthio) -tin.

! Iß procedure is identical to that described in Example I 2. 15.6 g (C, Q5 mole) of CU Sh CH, CH, C0 „CH, and! '$ d c £ 5! 51.6 g (0.15 mole) of mercapto ethyl stearate. At the end of the treatment, 47.5 g are obtained, ie with a yield of 77% a white solid whose melting point is 57 ° C. This product is characterized by horn spectrosoopie being the desired product: 5 nu ηηη. r * · - r · »* o / - I '* * \ 4 • J EXAMPLE 4 I Stabilizing effect of compounds of type R' Sn (S (CH0) 0 C Rc) - 1 2 n„ o 3 (stabilizer B ) 0 j In this example, samples of polyvinyl chloride stabilized with the compound prepared in Example 1 are subjected to color tests.

Ition to heating. To do this, knead at 185 ° C. on a roller mixer a composition comprising: - 100 parts by weight of polyvinyl chloride known under the name! commercial LACOVYL S 071 S with viscosity coefficient K = 56 ï · I 10-0.5 part of wax "E” which constitutes the external lubricant | ’- 0.5 part of stabilizer prepared in Example 1.

i dd f | Under these conditions, a resin is obtained having an excellent initial color I. The coloring of the resin is observed and the time at the end of the duel occurred the beginning of the coloring is 9 to 10 minutes and that 115 after which the browning of the sample appears is 14 minutes. This result is close to that which is observed with the butyl tin compound corresponding to day corresponding to Sn Sn (S CfL, CK2 0C0 H ^) ü EXAMPLE 5

Stabilizing effect of a formulation consisting of a stabilizer of j 20 type R "Sn (SCCKJ 0 C E,) s (stabilizer B); 1 2 n „63 d 0 | associated with a tin dialkyl (stabilizer C) j Stabilizers of the above fcyoe with P '= C "- ,, C„ _, are I' 1 i'- 'O 1f μ tested jointly with bisCisooctylme rea ^ -oacetate , es gî n-butyl - - * r 25 The formulation comprises: - Polyvinyl chloride 100 parts by weight - Stabilizer B 0.1 parts, r; - Stabilizer C 0.2 part - Wax ”E” C, P part i 30 The results depending on the nature of the radical P are given! the following table 1- oempares with an icrnu_3T-xor. they don't correspond i - \ νί {the stabilizing C.

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TABLE I

Color appearance formulation (time in nude)

Very light yellow Yellow B-un (decomposition) 5 -i ---- C: 0.3p 23-4 12 (reference) · 1 B: 0.1p + C 0.2p γ_8 18 (B: R '= C17H35 ) 2 10 ----- B: 0.1p + C 0.2p 5.5 8-9 22 (B: R '= C15H31) 3 B: 0.1p + C 0.2p ^ 7_g 25 (B: R' = C., H) 4 15 _13 ___

It appears from this table that formulations 2-3-4 have a synergistic effect with respect to formulation 1, both from the point of view of the initial color and of the long-term stability.

EXAMPLE 6 2C This example shows the favorable effect of formulations 2-3-4 of Example 11 on the viscosity of this polyvinyl chloride. The reported determinations are carried out by means of the Bratender apparatus making it possible to record the evolution over time of the kneading torque of the resin at a given ter.oérs-ture.

25 The formulation used is as follows: - Polyninyl chloride 100 parts by weight - CaCCL 5 parts by weight ~ ^ part in pics - Wax Γ · P · · · ** w LL U jC. 'JcCT'Æ. * 0 Tje. "Ne 30 - Stabilizing system · 2 ^ 2 ~ Β; -1?' 2 -" - part in pci os

ChgOL-0 (oi.g) 2 ^> n (Ct.gj ^ _r.0 ^ -s; 2 part er. Weight Oî operates at 200 ° C with a speed this rotation of the rotor of the mixer this 60 rpm.

35 The curves obtained indicate a level 1: minut-c torque of 1.6 m.kg.

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Claims (2)

1. New monoorgano tris-thioalkyl tin compounds of general form R '(,) Sn [S (ffl2) nra6] 3 5 0 "in which R ^ is the residue of an olefin: R ^ CC-rC O) 1" »\ I 0 r3 R5! 10 in which R ^, R ^, R ^, R ^ represent hydrogen or a residue! alkylated hydrocarbon containing from 1 to 3 carbon atoms; represents an alkyl group, a hydroxyl, an oxygen-containing hydrocarbon group, characterized in that the three groups j-SC ^^ OCR ^ j ^ are the remainder of an alkyl mercapto ester in which 15 1 0 · * the mercapto group is found in the alcohol residue of the ester, Rg is an alkyl containing from 1 to 18 carbon atoms, n is equal to 2-3-¾; one of the CHg can be substituted by a hydroxyl group. 2, - Organostannic compounds according to claim 1, carac-20 terized in that the group Ev belongs to a mono or an aliphatic diacid. 3 * - organotin compounds according to one of these claims 1 to 2, characterized in that the mono or diacids are: caprylic, * pelargonic, capric, undeaneanic, lauric, myristic, palmitic, ,, * 25 stearic, isostearic or mixtures of such acids. } ** · - Process for the preparation of organotin compounds according to one of Claims 1 to 3, characterized in that it consists in reacting organotin trihalides R '"SnHal-, with esters of mercapto alkyl HS (CH ^ ) OCR ,. ^ Γ; n - 30 0 5. Composition of stabilizers for halogen-vinylic polymers, in particular for polyvinyl chloride, characterized in that the composition contains ur. or more of the compounds according to one of Claims 1 to j, alone or in combination with other stannic stabilizers known per se, such as dialkyl tin and perfeciculiè- i 'IL-, j £ * “ . ^ 4? "7 ry bis (isooetylmercaptoacetate) di-n butyl tin. Ii '1 6.- Application of the compounds and compositions according to one of I! Claims 1 to 3 and 5, to the stabilization of halogenated polymers vinyl, in particular polyvinyl chloride, characterized in that it is produced in accordance with 1 * u ^ to 5 "i 15 ί 20 iiii, i * o" t ^ 30 i- 35