CS211665B1 - Stabilizing composition based on antimony/iii/ and organo-tin/iv/compounds - Google Patents

Description

The present invention relates to stabilizing compositions whose main active ingredient are organic sulfur containing antimony compounds and organotin compounds which achieve a high thermal stabilizing effect in chlorine-containing polymers.

Organotin compounds are potent metal stabilizers and are commonly used in the processing of vinyl chloride polymers. The patent literature on organotin stabilizers is very extensive and includes the field of preparation and application of organotin compounds with additives of various chemical composition (US Pat. 2,267,777, 2,307,157,

731,482, 2,832,750).

Mixed stabilizers are known in a variety of variations and have been used in the plastics processing industry (Germany Pat. 2,538,409, US Pat. 3,919,165, 3,803,083, 3,845,017, British Patent 1,060,067).

they often utilize the synergistic effect of a suitable combination of the individual components of the stabilization system, or the cheaper stabilizer will partially replace the economically expensive active component without substantially affecting the overall activity of the system.

In addition to mutual combinations of simile and sulfur-free organotin stabilizers, there are synergistic mixtures based on mono-, di- and less often trialkyltin stabilizers

Mixtures of mono- and dialkyl tin sulphides with conventional organotin stabilizers in various proportions are described. Combinations with phenolic antioxidants, thio compounds, organic phosphites, epoxy plasticizers have proven to work well. Combinations with terpenes, polyols, mineral oils, etc. also appear.

In addition to previously published mixtures of organotin compounds with inorganic compounds, such as tribasic lead sulfate, magnesium carbonate, mixtures of organotin compounds with organic alkaline earth metal salts (Ba,

(Cd, Mg, Zn).

While organotin mercaptides have gained a dominant position in the field of PVC stabilization, the importance of antimony compounds was rather theoretical. The industrial use of antimony stabilizers has only recently occurred.

Similar to organotin stabilizers, multi-component systems containing antimony mercaptides and additives of different chemical compositions are known. In Germany Pat. No. 2,602,726 discloses a stabilizer composition for vinyl chloride polymers comprising antimony mercaptide and dialkyl tin oxide in a solution of organic acid esters.

In Germany Pat. No. 2,454,986 discloses a synergistic mixture of antimony mercaptides with alkaline earth or alkali metal salts and carboxylic or thiocarboxylic acids. The synergistic effect also applies to the organoantimonite compounds of the general formulas R @ ¹ SbX @ ¹ , where X is S, SR @ ¹ , SR @ ² COOr @ 1 is 1 to 2.

Germany Pat. No. 2,704,487 discloses a three-component composition composed of antimony-trisdzooctyl mercaptoacetate), a hydrogen chloride acceptor, and an organic compound with chelating properties.

Examples of hydrogen chloride acceptors include oxides, hydroxides and salts of divalent metals with carboxylic or mercaptocarboxylic acids, amines, especially alpha-phenylindole.

Compounds of the group of polyols, polyolamines, organic phosphites and hydroxycarboxylic acids are proposed as chelators.

Belg. U.S. Pat. 866 428 also contains a tri-component composition. The first component is based on alkali metal or alkaline earth metal salts, e.g., BaíCH ^COOCgHg ^. The second component is a sulfur-containing organotin or antimony compound having a -C-Sn-S-, Sb-S- bond. The third component is the basic metal forming the organic complex or the alkaline earth metal carbonates.

Both antimony and organotin stabilizers have a number of disadvantageous application properties. Antimony mercaptide-based stabilizers are poorly effective in vinyl chloride polymers at higher concentrations. Antimony mercaptides are characterized by lower storage stability, are highly sensitive to light, air and moisture. Organotin stabilizers, unlike antimony stabilizers, achieve a high protective effect in vinyl chloride polymers at higher dosages.

At lower concentrations they are less effective than antimony stabilizers and also the transparency of the products is lower. The invention solves the deficiencies in the action of antimony mercaptides and extends the possibility of their application even in applications requiring a higher stabilizer dosage. At the same time, the application properties of the organotin stabilizers are improved and their economic disadvantage is eliminated.

The disadvantages of the stabilizing effect of the antimony and / or organotin stabilizers themselves are overcome by the composition according to the invention, composed of up to 5% by weight, preferably 80 to 20% by weight, of antimony sulphide. organic compounds of general formula (1) (SR ¹ COOR ² ) _{3 x}

Sb '(I) ^(SR-2) x

up to 95% by weight, and preferably 20 to 80% by weight, of an organotin compound of the general formula (XI) ^R n ^S n ^(X) 4-n (II)

2 wherein X is a mercaptocarboxylic acid ester residue -SR COOR, a thiol -SR, a carboxylic acid residue -OCOR \ a maleic ester -OCOCH = CHOCCO ² , a stannous salt of a dicarboxylic acid, or mixtures thereof, R is C 1 -C 8 alkyl , C 1 -C 6 alkylene, R ² C 1 -C 18 alkyl, C 5 -C 7 cycloalkyl, C 4 -C 18 alkyl, x 0 to 3, n 1 to 3, and typically containing up to 40 wt. of a mixed tris (1-phenylethylphenyl) foaphite of formula (III) (III) wherein R 1, R ² , R ⁴ , 1-phenylethyl, optionally one or two of Z 1 to R 4 are 1-phenylethyl and the remaining are hydrogen .

R in formula II is most often n-butyl-n-octyl and methyl. Of the alkylene radicals R1, most often those having 1 or 2 carbon atoms, methylene, ethylene.

O

R can be methyl, isopropyl, butyl, isooctyl, dodecyl, cyclohexyl, 2-alkoxyethyl or 2-alkylthioethyl.

Typical examples of sulfur-containing antimony stabilizers are antimony-tris (isooctylmercaptoacetate), antimony-tris (dodecylmercaptide), antimony-tris (butyl 3-mercaptopropionate), antimony-tris (dodecylmercaptoacetate), antimony-tris (cyclohexylmercaptoacetate) bis (2-ethylhexyl mercaptoacetate) and mixtures thereof.

The compounds of formula II are commonly known as organotin stabilizers. They include compounds such as di-butyl-tin-bis (iso-octyl mercaptoacetate), dioctyl-tin-bis-isooctyl mercaptoao-acetate, mono-butyl-tin-tris (iso-octyl mercaptoacetate), dibutyl-tin-bis- (dodecyl mercaptide), dimethyl (iso-octyl-3-mercaptopropionate), dimethyl tin-bis (dodecyl mercaptoacetate), dibutyl-en.bis (butyl-3-mercaptopropionate), dibutyl-tin-bis (isooctyl maleate), dibutyl-tin-bis (isopropyl maleate), tin-bis (isooctyl maleate), polymeric dibutyltin maleate, dibutyl-tin bis (cyclohexyl maleate), dioctyl tin bis (isooctyl maleate) dibutyl-o-isopropyl-cyclohexyl maleate, dibutyl-tin-dilaurate and the like and mixtures thereof. compounds.

The proposed composition may contain further additives which favorably influence the homogeneity of the composition, contribute to improved dispersion of the stabilizing system in the polymer, participating in the stabilization reactions during the degradation processes, by antioxidant action or the ability to deactivate the resulting products, accelerate dehydrochlorination reactions. products.

For this purpose, up to 40 wt. epoxy plasticizers of the epoxidized type of soy or sunflower oil fatty acid esters, phenolic antioxidants up to 30% by weight, in particular 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-alkylphenol alkyl having 30 to 50 carbon atoms.

Addition of up to 40 wt. organic phosphites such as mixed iris (1-phenylethylphenyl) phosphite, triphenyl phosphite, pentaerythritol-based phosphites and the like.

The dispersion improvement of the stabilizing system according to the invention is achieved by adding up to 40% by weight to the composition. polyhydric acid esters such as dioctyl phthalate, dibutyl phthalate, alkyl esters of adipic acid, sebacic acid, phosphoric acid esters, polymers of polyethylene glycol or polyesters formed by condensation of dibasic acids and polyhydric alcohols, optionally alkylaryl ether, higher glycidyl ether, e.g. polyolamines and the like.

The proposed compositions have a number of advantageous application properties which are achieved within a certain range of system component ratios. The action of the individual components in the polymer is suitably complementary to one another. Accordingly, the stabilizing composition of the present invention is highly effective at both low and high concentrations in vinyl chloride polymers and solves stabilization problems in a wide range of applications.

In addition to its high thermal stabilizing effect, its use also has other advantages. The composition is characterized by a higher storage and handling stability compared to the antimony compounds themselves, since the addition of the organotin compound positively affects the stability of the liquid mixture and prevents the formation of a solid fraction.

Due to the high heat resistance of the components used, no volatile products are formed during processing which would lead to a deterioration of the working environment. The individual components are well miscible and do not form a phase interface.

The stabilizing composition is preferably prepared by vigorously mixing all components at elevated temperatures of 40 to 100 ° C for 30 to 120 minutes. Direct dosing of the individual components into the polymer base without prior homogenization is also possible.

The composition of the invention is economically advantageous and the individual components are readily available technically.

The proposed stabilizing composition is universally applicable to a variety of applications of softened, unplasticized, tough polyvinyl chloride and plastisols.

Further advantages resulting from the use of the stabilizing composition according to the invention are given in the examples.

He did

The DC stabilizer composition is preferably prepared by vigorously mixing all components at a certain ratio to each other and at an elevated temperature in the range of 40 to 100 ° C for 30 to 120 minutes. Stabilization systems based on antimony and organo-zinc compounds and systems containing other ingredients in addition to the mentioned main components have been prepared. The composition of the compositions is shown in Tables 1 and 2.

Designation of compounds used:

Antimony tris (isooctylmercaptoacetate)

B Dibutyltin bis (isooctyl mercaptoacetate)

C dibutyl tin bis (isooctyl maleate)

D dibutylein bis (cyclohexyl maleate)

E Dibutyl tin bis (isopropyl maleate)

F dioctyl tin bis (isooctyl mercaptoacetate)

Q dimethyl tin bis (isooctyl mercaptoacetate)

H dibutyl-tin-dilauryl mercaptide

J Dibutyl tin dilaurate

K polymeric dibutyltin maleate

L antimony-tris (laurylmercaptide)

2H665

M laurylmercapto-antimony-blsdzooktylmercaptoacetate j

N mixed tri3 (1-phenylethylphenyl) phosphite

2,6 di-tert-butyl-4-methylphenol

P isooctanol

Q dioktyladipdt

R is phenylglycidyl ether

With epoxidized butyl ester of soya and sunflower oil

Table

Composition of stabilizing compositions based on antimony and organotin compounds

designation composition AND. Component ratio (% by weight) TO 'B C D E P G H J AND 80 20 May II 50 50 III • 20 80 IV 80 20 May in 80 20 May VI 80 20 May VII 50 50 VIII 50 ___ 50 _r . IX ⁸⁰ 20 May X 50 - 50 XI 80 __ 20 May XII 50 50 XIII 50 50 XIV 50 50 XV 30 __ - 70 XVI 30 70 XVII 60 40 XVIII 60 40 XIX 70 - 30

Table 2

Designation of the composition

Composition of compositions based on antimony and organotin compounds and other additives

Component ratio (% by weight)

AND (B) E N 0 P Q R WITH XX 45 45 10 XXI 45 45 10 XXII 20 May - 64 8 8 XXIII. 45 40 5 10 XXIV 45 45 5 5 Example 2 Powder mixtures, containing 100 ALIGN! % by weight parts of suspension PVC with K = 62.1 . 1 mass-

The lubricant and stabilizer composition I to III in the concentration range 0.5 to 2.5 parts by weight were mixed in a mixer and foils were prepared by rolling at a temperature of 180 to 190 ° C for 5 minutes.

The obtained films were thermally stressed at 180 [deg.] C. under static conditions and the heat-stabilizing efficiency of TS at the minimum thermal stress and transparency of the films was evaluated from the development of PVC color.

2t 1665.

Table 3 shows the achieved values and compares them with the organotin and antimony stabilizers.

Compositions I to III are highly effective over the entire concentration range and are characterized by a synergistic effect at the component ratio used and a certain dosage in PVC, e.g. at a component ratio of A: B = 50:50 and a concentration of 1-2 parts by weight.

At concentrations above 1.5 parts by weight, they are more effective by 5 to 18 minutes than the organotin compound. The prepared films are highly transparent with a light solubility of 80 to 89 56.

Due to the high transparency of the polymer blends, stabilization systems I to III are suitable for stabilizing transparent products and products in pastel color tones.

Table 3 Thermal stability (TS) and transparency (T) of non-soft mixtures. suspension PVC depending on the content and composition of the stabilization system

Designation Contents (parts by weight)

0.5 1.0 • 1,5 2,0 2 , 5 TS T TS T TS T TS T TS T (min) <%) (less) (56) (min) (56) (min) (56) (min) (56) AND 35 85.0 55 87.4 67 88.0 80 87.0 75 84.7 (B) 25 77.9 50 81.1 72 84.0 100 ALIGN! 85.7 130 86.9 AND 38 85.4 58 87.8 80 89.0 100 ALIGN! 87.7 120 89.1 II 35 83.0 60 87.6 90 88.5 125 87.7 130 87.2 III 30 80.1 58 83.4 85 86.1 125 86.5 165 85.5 Ex íkl · ad 3 They were prepared mixtures emulsion PVC, containing 100 parts by weight polymer 50

parts by weight of dioctyl phthalate, 0.5 parts by weight of lubricant and composition in a concentration range of 0.4 to 1.2 parts by weight, homogenization on a twin-roll at 155 ° C, 5 minutes.

Compositions I to III have a long-term thermal efficiency comparable to that of an organotin stabilizer and are more economical. In comparison with antimony stabili-. the source is a heat stabilization of the mixtures containing compositions I to III by 10 to 20 minutes. Said compositions are highly effective in emulsion PVC as shown by comparison with the effect of the Ba / Cd stabilizer.

Table 4

Systems efficiency in a softened emulsion PVC Designation Thermal stability (min) composition dosing of the composition (parts by weight) 0.4 0.8 1,2 AND 45 55 70 (B) 50 65 80 AND 50 62 75 II 50 65 80 III 55 70 85 Ba / Cd 8 10 10

Example á

From the blend containing 100 parts by weight of suspension PVC, 1 part by weight of lubricant and 1 part by weight of compositions IV to VII, highly transparent films with excellent surface quality and improved resistance to light and weathering were prepared. The thermal stability values are given in Table 5. These compositions comprise antimony tris isooctyl mercaptoacetate) and dibutyltin monoesters of maleic acid.

Table 5

Labeling Effectiveness of Compositions in Unplasticized Suspended PVC Compositions Thermal Stability at 180 ° C (min)

AND

IV

IN

VI

VII

Example 5

Highly transparent films were prepared from unplasticized suspension PVC blends containing 100 parts by weight of polymer, 1 part by weight of polymer, 1 part by weight of lubricant and 1 part by weight of Composition VIII, XII to XIV, which retained transparency after 30 minutes of heat treatment.

High thermal stability (60 min) and extraordinary transparency (90% light transmittance) were achieved by the stabilized composition XII (50 wt% antimony-tris / isooctyl mercaptoacetate and 50 wt% dimethyl-cin-bis / isooctyl mercaptoacetate).

Example 1 a d 6

To stabilize the unplasticized emulsion PVC blends, compositions containing 30 wt. % to 70 wt. antimony tris (isooctyl mercaptoacetate) and dimethyl tin-bis (isooctyl mercaptoacetate) (XV); and antimony tris (isooctyl mercaptoacetate) with dibutyltin dilau, rylmercaptide (XVI). The compositions used achieve higher thermal stability and transparency of the compositions than the individual components (Table 6).

Table Designation composition 6 System efficiency in unplasticized emulsion mixtures, Polymer suspension and modified PVC Pulse. stability at 180 ° C (min) Transparency% original after 30 min (B) PVC modifi- 70 80.2 63.6 VIII forged ko Po- 70 79.5 71.1 IX lymerem vi- 80 80.7 76.4 VII nylchlorid ' 70 80.2 73.0 X ethylen-vi- 90 80.3 72.6 XI nylacetate 85 80.8 74.5 AND 65 80.5 75.7 XII 60 90.3 79.2 XIII suspension 58 88.8 75.9 VIII PVC 52 84.8 75.6 XIV 60 83 2 74.5 AND 52 80.0 73.2

designation composition Polymer Pulse. stability at 180 ° C (min) Transparency ·% original after 30 min XV 50 67.5 66.2 XVI emulsion 50 69.4 44.3 H PVC 45 34 * 6 29.4

Example7

Films were prepared from blends containing 100 parts by weight of tough PVC modified with vinyl chloride (ethylene) vinyl acetate copolymer, 1 part by weight of lubricant and 1 part by weight of compositions VIII to XI (Table 6) prepared according to Example 1.

Compositions IX to XI contain antimony mercaptide and organo-zinc carboxylate in varying proportions. Composition II contains 50 wt. % antimony and 50 wt. sulfur containing organometallic compounds.

The films ae were characterized by high thermal stability and transparency (80% light transmittance). Compositions containing organo-zinc carboxylate were characterized by high color fastness without the formation of a pale yellow color during the thermal stress of the mixtures.

He does

The plasticized suspension polyvinyl chloride mixtures containing various types of plasticizers were stabilized with 0.5 parts by weight of composition XIV, XVII to XIX, composed of an antimony alkyl ester of mercaptoacetic acid and dibutyltin maleic acid ester or dibutyltin lauryl mercaptide, or dibutyltin dilaurate.

The compositions used with different proportions of antimony and organotin components ensured excellent transparency of the mixtures (light transmittance higher than 90%) and thermal stability ensuring safe processing (TS = 35-70 minutes at 180 ° C).

Table

Polymer

100 wt. parts

Heat-stabilizing effectiveness of the compositions in softened suspension polyvinyl chloride mixtures.

Plasticizer 50 wt. parts

Composition 0.5 wt. parts

Tepel. staff. 180 ° C, min

Transparent st (%)

TKP XVII XIV 35 38 suspension PVC D0A XVIII 60 XIX 70

91.7

92.7

90.4

90.6

Example 9

Further increased thermal stability and resistance to light, oxygen and weathering effects and increased transparency of the suspension mixtures. % of polyvinyl chloride was achieved by adding 10 wt. mixed tris (1-phenylethylphenyl) phosphites (composition XX of Example 1).

At a dosage of 1 part by weight of composition XX per 100 parts by weight of PVC with 1 part by weight of lubricant, the mixture achieved 65 minutes of thermal stability at 180 ° C and high transparency (89% light transmittance).

The stabilizing composition is also very effective in the PVC modified with ethylene / vinyl acetate copolymer in which the thermal stability reaches 85 minutes β transparency of 80.3% (Table Θ).

The addition of organic phosphites to the polymer blend improves resistance to weathering and degradation caused by light and oxygen.

Example 10

High thermal stability is achieved in a mixture containing 100 parts by weight of unplasticized suspension PVC, 1 part by weight of lubricant and 1 part by weight of composition XXI prepared according to Example 1. The mixture is characterized by increased resistance to action, oxygen and weathering (Table 8).

T a bulka 8 Thermal stability and transparency and tough PVC containing 1 wt. them compositions of suspension part stabilizer Polymer Composition Thermal stability Transparency (%) 100 ALIGN! wt. parts 1 wt. part at 180 ° C (min) original after 30 min II 60 85.6 - XX 65 89.0 PVC suspension XXI 52 86.5 - XXIII 50 86.0 - XXIV 44 88.8 - II 85 80.5 69.5 VII 65 80.2 73.0 PVC tough XX 85 80.3 69.5 XXII 60 79.0 62.0 E 45 75.0 54.4 Ex example 11

The thermal stability and transparency of PVC modified with vinyl chloride (ethylene) vinyl acetate copolymer ae is increased by using 1 part by weight of composition XXXI compared to 1 part by weight of dibutyltin isopropyl maleate (E), tab. 8.

The composition XXII of Example 1 contains 8 wt. % 2,6-di-tert-butyl-4-methylphenol and 8 wt. 2-ethylhexanol, which contribute both to increased resistance to photooxidative degradation processes and to better dispersion of the stabilizing system in the polymer.

Example 12

Compositions containing an antimony and organotin compound and optionally other additives have proven to be well suited to stabilize polyvinyl chloride modified with 3.5% by weight. polypropylene.

From 100 parts by weight of modified PVC polypropylene, 1 part by weight of lubricant and 1 part by weight of compositions II, XX, XXII, quality films were prepared by rolling at 170 ° C. The obtained films achieved higher thermal stability by 5 to 10 min. (greater effect by 10 to 20%) and greater transparency by. 0 to 15% compared to films stabilized by components A (antimony compound), B (organotin) as shown in Table 9.

Table 9 Teaches Compositions In Polypropylene Modified PVC

Komposice Thermal stability (min) Transparency. (56) AND 40 67.5 (B) 45 65.0 II 50 79.5 XXII 44 80.5 XX 50 83.2

BACKGROUND OF THE INVENTION

Claims (1)

Stabilizing composition based on antimony and organotin compounds, characterized in that it contains 95 to 5% by weight, preferably 80 to 20% by weight, of antimony sulfur containing organic compounds of the general formula (I) WAS R ¹ COO R ² /, „z Sb '(I> s r \ 5 to 95% by weight, preferably 20 to 80% by weight, of an organotin compound of formula (XI) Sn ^ é-n <"> wherein X is a mercaptocarboxylic acid ester residue -Sr'c00R ^{2 of} thiol -SR ² , a carboxylic acid residue -OCGR ³ , a maleic ester -QCQCH = CHOCOR, a stannous dicarboxylic acid residue, or mixtures thereof, R 1 -C 8 alkyl C 1 -C 6 alkylene, C 1 -C 18 alkylene, C ² -C 18 alkyl, C 5 -C 7 cycloalkyl, C 3 -C 20 alkoxyalkyl or C 3 -C 20 alkylthioalkyl, R ³ alkyl and C 4 -C 18 alkyl %, x 0 to 3, η 1 to 3, and optionally up to 40 wt. a mixed tris (1-phenylethylphenyl) phosphite of formula (III) (III) wherein R ¹ , R ² , R ^{3 is} 1-phenylethyl, optionally one or two of R ¹ to R ³ 'are 1-phenylethyl and the remaining are hydrogen. 5wwfi »fi» β. ji zfrod 7. Mwi