DK146927B - BISMUTH- AND ANTIMON-FREE HEAT-STABILIZED SUBSTANCES BASED ON A VINYL CHLORIDE POLYMER - Google Patents

Description

(19) DENMARK

oz) SUBMISSION WRITING (, d 146927 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Patent Application No .: 0082/76 (51) Intl. CI.3: C 08 K 5/09 (22) Date of filing: 09 Jan 1976 (41) Alm. available: 11 Jul 1976 (44) Submitted: 13 Feb 1984 (86) International Application No: - (30) Priority: 10 Jan 1975 FR 7500765 22 Sep1975 FR 7529466 (71) Applicant: 'RHONE-POULENC SPECIALITES CHIMIQUES; F-92400 Courbevoie, FR.

(72) Inventor: Michel * Crochemore; FR, Michel * Gay; FR.

(74) Plenipotentiary: The engineering firm Budde, Schou & Co_ (54) Bismuth- and antimony-free heat-stabilized resin based on a vinyl chloride polymer

The present invention relates to a bismuth and anti-monophonic heat stabilized resin based on a vinyl chloride polymer.

It is known to use polymers and copolymers of vinyl chloride to prepare finished articles at various

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processes, such as molding, pressing, spraying and molding, which N requires high temperatures to allow the polymers to have a sufficient degree of softening. At these temperatures, which can be in the range of J to 180-200 ° C, significant degradation of polymers on the basis of vinyl chloride occurs, which leads to a change in color D and mechanical properties. To avoid this change, it is proposed to add heat stabilizers such as metal chelates of dicarbonyl compounds either alone or in combination with carboxylic acid salts of such metals as calcium, lead and cadmium (U.S. Patent Nos. 2,307,075 and 2,669,548 ). Salts of heavy metals and higher fatty acids have also been used in combination with organic phosphites (U.S. Patent No. 2,564,646) or in combination with polyols (U.S. Patent No. 2,711,401). However, these various agents are not sufficient when the polymers are exposed to high temperatures and are used in the manufacture of light or transparent products, since even a short, vigorous heating produces a more or less vigorous yellowing of the polymer, making it unusable for certain applications. Thus, in the manufacture of transparent films or barriers or the manufacture of bottles and vials, a change in the color of the polymer cannot be tolerated as this will impair the transparency of the products.

U.S. Patent No. 3,493,536 states that bismuth cells antimony compounds, sometimes used as heat stabilizers for polyvinyl chloride, have a light sensitizing effect on this polymer, thus reducing the light resistance. According to the patent, the addition of dibenzoyl-methane to such mixtures, which may contain barium-cadmium laurate, reduces this light sensitization, while the addition of benzoylacetone does not provide this same improvement.

According to the present invention, good stabilization of polymers based on vinyl chloride is possible without the use of bismuth or antimony compounds.

The present invention thus relates to a bismuth and antimony-free heat-stabilized resin based on a vinyl chloride polymer, which resin is characterized in that it, based on the weight of the polymers, contains a heat-stabilizing addition of (a) 0.1-5% of one or more of the carboxylic acid salts of divalent metals usually used to stabilize these polymers, and (b) 0.05-5% of a β-diketo or β-ketoaldehyde compound of the general formula R1 - CO - CHR2 - CO - R3 (I) 3 wherein R and R, which may be the same or different, each means a straight or branched alkyl or alkenyl group having up to 30 carbon atoms, an aralkyl group having 7-36 carbon atoms, or an aryl group or cycloalkyl or alkenyl group having less than 14 3 carbon atoms, the above-mentioned aryl groups being optionally substituted by a methoxy group or a 1,3-dioxobutyl group, and the groups being modified by the presence of one or more e chain link -CO-O- 1 3 or -CO-, or wherein the groups R and R together form a di-2-alkylene group of 2-5 carbon atoms, at the same time that R is / C \ CH- CH-CHO-I 2 I 2

CH0 CO

In addition, for both groups R and R, the carbon atom attached to the carbonyl group is not ethylenic or carbonyl unsaturated, and for one of groups R and R the carbon atom bonded to the carbonyl group is not aromatic unsaturation, and one of the groups R and R may also mean a hydrogen atom when the other is methyl or phenyl and wherein R is otherwise a hydrogen atom, an alkyl or alkenyl group containing up to 30 carbon atoms, or a group of the formula -CO-R wherein R represents an alkyl group of 1-30 1 3 carbon atoms or an aryl group if R and R are not aromatic groups.

Resins based on vinyl chloride polymers are defined as resins containing a homopolymer or a copolymer of vinyl chloride as well as various additives usually used to facilitate the use of the resins or to give special properties to the finished products.

All types of homopolymers of vinyl chloride can be used, regardless of their preparation, which can be carried out by mass polymerization, suspension polymerization, emulsion polymerization or by any other means.

Many different types of copolymers of vinyl chloride can be made heat resistant in the same way as the homopolymers. The copolymers can e.g. may be prepared by copolymerizing vinyl chloride with other monomers containing a polymerizable, ethylenic bond / such as ethylene, acrylic esters, styrene, vinyl esters, maleic acid, maleic anhydride and maleic esters.

The copolymers usually contain at least 50% by weight of vinyl chloride. Preferably copolymers containing at least 80% by weight vinyl chloride are used and the other monomer is vinyl acetate or vinylidene chloride. These copolymers can be used alone or in admixture with other polymers, especially with polyvinyl chlorides.

The resin according to the invention may also be based on over-chlorinated polyvinyl chlorides, the chlorine content of which may be up to 65-70% and which are very sensitive to thermal decomposition when subjected to high temperatures.

The carboxylic acid salts of divalent metals are preferably salts of calcium, barium, zinc, lead or cadmium with saturated or unsaturated aliphatic acids or with aromatic acids.

These salts include acetates, diacetates, ethylhexanoates, octoates, stearates, oleates, laurates, palmitate, myristates, castorolates, benzoates and phthalates. The salts are usually used in the form of mixtures of two of these, e.g. calcium salts plus zinc salts. For the preparation of food packaging or bottles, it is especially appropriate to use salts of alkaline earth metals and fatty acids with long chains, as such salts are non-toxic and have a lubricating effect. In particular, mention may be made of calcium and zinc stearates, laurates and 2-ethylhexanoates. As mentioned, these salts are used in an amount of 0.1-5%, based on the weight of the polymer.

The dicarbonyl compounds of formula I used in the invention in conjunction with said metal salts may be β-diketones. The dicarbonyl compounds can also be β-keto aldehydes when one of the symbols R and R in the formula I represents a hydrogen atom.

β-diketones are known compounds prepared according to known synthetic methods. For example, refer to the work "Organic Reactions" by R. Adams, 1954, VIII, pages 59 et seq. Certain more specific syntheses are described in "Rec. Trav. Chem. Pays-Bas" by M.J. Kramers, 16 (1897) p. 116, in "J. Chem. Soc." by G.T. Morgan and E. Holmes, 127 (1925), p. 2891, in "J. Chem. Soc." by R. Robinson and E. Seijo (1941) p. 582, and in "Chemische Berichte" by Claisen, 20 (1887) p. 2188.

Β-Keto aldehydes are prepared according to classical synthetic methods, e.g. can be found in the above-mentioned work "Organic Reactions" by R. Adams, pages 59 et seq.

The dicarbonyl compounds are used in an amount of between 0.05 and 5%, preferably 0.1-1%, based on the weight of the polymer.

As examples of such compounds, mention may be made of aliphatic β-diketones such as heptane-2,4-dione, decane-2,4-dione, ethyl nonan (2,4-dione) carboxylate, 8-methyl 7-nonen-2,4-dione, acyloxyacetones such as acetylacetone, 1,1-diacetylacetone or triacetylmethane, stearoylacetone or other stearoylalkanones.

Also mentioned are aromatic or arylaliphatic β-diketones such as benzoylacetone, diacetylacetobenzenes, stearoylacetophenone and palmitoylacetophenone. To obtain a long-lasting stabilizing effect, it is particularly convenient to use diketones containing a long alkyl chain such as stearoylacetone, palmitoylacetone, lauroylacetone, stearoylacetophenone, palmitoylacetophenone and lauroylacetophenone.

Among the β-keto aldehydes there are mentioned 2-acyloxy-acetaldehydes and 2-acyloxypropionaldehydes, such as benzoylacet aldehyde and 2-acetyl-2-methylacetaldehyde.

The homopolymers or copolymers used may be rigid or flexible. When rigid polymers are used, agents can be added which modify the impact strength, e.g. copolymers of butadiene and styrene or terpolymers of butadiene, styrene and acrylonitrile, often used to improve the mechanical properties of polymers. Various additives, such as plasticizers, pigments, fillers, antioxidants, agents for providing light resistance, etc., can also be added to the inventive resins.

It is also possible to add other organic compounds known for their stabilizing effect, e.g. pentaerythritol or trihydroxyethyl isocyanurate, for the heat-stabilizing additives used in the inventive resins.

The heat stabilizing additives used in the inventive plastics can be added at the same time as the other additives. They can also be mixed together, either alone or with certain additives. Thereby a stabilizing mixture is obtained, which is subsequently mixed with polyvinyl chloride. All conventional known methods can be used to mix the various components. However, it is conveniently homogenized in a blending mill.

The compositions of the invention can be processed and formed by the methods usually used for compositions based on polymers or copolymers of vinyl chloride, e.g. injection molding, extrusion, blow extrusion, calendering, rotational molding, etc.

By means of the combination of an organic stabilizer and two metallic stabilizers, it is possible to delay the yellowing of the plastics and to produce final products which are transparent and homogeneous and do not exhibit any perspiration. The invention is illustrated by the following examples.

Examples 1-5,

A mixture A, which can be used especially for the preparation of bottles by blow extrusion, is prepared by mixing in a cylindrical ball mill the following substances: 1000 g of a PVC powder (sold under the name "Lucovyl RS 8000") having a viscosity index of 80 (according to NF T 51 013) and is prepared by suspension polymerization, 100 g of an agent for increasing the impact strength which is a copolymer of butadiene, styrene and methyl methacrylate, 10 g of a lubricant which is a wax based on a carbonate ester and are marketed under the name "Cire E", 10 g of calcium stearate, 7 g of zinc stearate, 30 g of epoxidized soybean oil, 3 g of a trinonylphenyl phosphite.

The resulting mixture is homogenized in a mixing rolling mill for 15 hours.

In 5 mortars with a volume of 250 cm containing some porcelain balls, 56 g of this mixture A and (B), respectively, are placed 0.12 g of heptane-2,4-dione with a boiling point of 180 ° C at a pressure of 760 mm Hg, (C) 0.16 g of decane-2,4-dione, (D) 0.2 g of ethyl-nonane-2,4-dione carboxylate having a boiling point of 130 ° C at a pressure. of 0.5 Nun of Hg, (E) 0.21 g of 1-benzoyl-2-octanone and (F) 0.15 g of 2-methyl-decane-6,8-dione with a boiling point of 234 ° C at a pressure of 760 mm Hg.

The prepared mixtures are homogenized in a mixing rolling mill for 15 hours to obtain homogeneous mixtures B, C, D, E and F.

Of these mixtures, sheets with a thick "look" of 2.5 mm are prepared by means of a calender heated to 175 ° C.

Of the sheets produced, rectangular specimens with dimensions of 10 x 20 mm are cut, after which the specimens are placed in a ventilated oven (180 ° C) for various periods.

Then, the color of the samples is determined according to Gardner's scale using a Lovibond comparison chart. The results obtained are summarized in the following table.

Time, minutes 0 7 14 21

Grades Gardner for:

Mixture A 8 9 10 11

Mixture B 2 3 3.5 5

Mixture C 1123

Mixture D 2456

Mixture E 1245

Mixture F 1 1 1 2.5

It is evident from the test results that the specimens containing organic stabilizer are stained much less during manufacture and have a much greater heat resistance than the specimen A containing no ketone compound.

Examples 6-10.

Mixtures Η, I, K, L and M are prepared by proceeding in the same manner as in Example 1 and mixing 56 g of Mixture A prepared in the same manner as in Example 1 but with another vinyl resin, respectively ( H) 0.18 g of 2,2'-methylene bis - (cyclohexane-1,3-dione) having a melting point of 134 ° C, (I) 0.15 g of benzoylacetone having a melting point of 56 ° C (K) 0.15 g of triacetyl methane having a boiling point of 95 ° C at a pressure of 0.1 mm Hg, (L) 0.2 g of 1,4-diacetylacetobenzene having a melting point of 184 ° C and (M 0.2 g, 4-diphenylbutane ~ 1,3-dione. The prepared mixtures are homogenized in a mixing rolling mill for 15 hours.

Of the mixtures prepared, plates having a thickness of 2.5 mm are prepared by means of a calender heated to 180 ° C.

Of the sheets produced, rectangular specimens with dimensions of 10 x 20 mm are cut, after which the specimens are placed in a ventilated oven (180 ° C) for various periods.

The color of the samples is then measured in the same way as in Example 1. The results obtained are summarized in the following table.

Time, minutes 0 7 14 21

Grades Gardner for:

Mixture A '8889

Mixture H 1223

Mixture I 1 1 1 1.5

Mixture K 1.52.53 4

Mixture L 3344

Mixture Μ 1 1 1.5 3

Example 11.

A softened mixture Z is prepared by mixing the following substances in a ball mill: 1000 g of a PVC powder (sold under the name "Lucovyl GS 1200") having a viscosity index of 120 (according to NF T 51 013) and a K value of 69 and is prepared by suspension polymerization, 500 g of dioctyl phthalate, 5 g of a trinonylphenyl phosphite, 5.6 g of zinc stearate, 9 g of barium stearate.

9 146927

The prepared mixture is homogenized in a mixing rolling mill for 15 hours.

In a mortar with a volume of 250 cm containing some porcelain balls, 56 g of the prepared mixture Z and 0.15 g of benzoyl acetone are placed. The resulting mixture is homogenized in a mixture rolling mill for 15 hours to give a homogeneous mixture P. Of the mixtures P and Z, test pieces are prepared in the same manner as in Example 1, with the calendering temperature being 140 ° C.

The samples are placed in a ventilated oven (180 ° C) for various periods, after which the color of the samples is measured in the same way as in Example 1.

The results obtained are summarized in the following table.

Time, minutes 0 7 14 21

Grades Gardner fors

Mixture Z 0222

Mixture P 0001

It is evident from the test results that the specimens made from softened PVC mixtures are much less sensitive to yellowing than the specimens made from non-softened mixtures. In addition, by adding an organic stabilizer, the yellowing can be further greatly reduced during a heat treatment corresponding to the use of the resins.

Examples 12-13.

A mixture A is prepared in the same manner as in Example 1. In the same way as in Example 1, 56 g of the mixture A is mixed with (Q) 0.15 g of benzoylacetone and with (S) 0.15 g of benzoylacetone plus 0.15 g pentaerythritol.

A comparative mixture R is also prepared by mixing 56 g of mixture A with 0.60 g of pentaerythritol alone.

10 146927

The specimens of the prepared mixtures are heat treated in the same way as in Example 1, after which the color of the specimens is measured.

The results obtained are summarized in the following table. Time, minutes 0 7 14 21

Grades Gardner for:

Mixture A 6788

Mixture Q 1123

Mixture S 11 1.5 1.5

Mixture R 3.54.56 6.5

It is evident from the test results that not even a significant amount of pentaerythritol is sufficient to provide as good a heat resistance as that obtained with a diketone compound.

Examples 14-17.

In the same manner as in Example 1, the following substances are mixed: 800 g of polyvinyl chloride, 200 g of a copolymer of vinyl chloride and vinyl acetate containing 15% acetate, 100 g of a copolymer of butadiene, styrene and methyl methacrylate, 30 g of epoxidized soy oil, 5 g of wax ("Cire E"), 5 g of calcium stearate, 2.5 g of zinc stearate.

57 g of the prepared mixture is placed in a mortar, after which a certain amount of stabilizer is added (see the following table) and test pieces are prepared in the same way as in Example 1.

The heat resistance of the specimens is determined by keeping the specimens in an oven at 170 ° C for various periods of time.

The results obtained are summarized in the following table.

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Time, minutes O 7 14 21

Grades Gardner for:

Base mixture without ketone 1456

Base mixture + benzoylacetone (0.10 g) 0013

Base mixture + stearoylacetone (0.10 g) 0013

Base mixture tstearoylacetophenone (0.15 g) 0. 1.5

Base mixture + 8-methyl-7-nonen-2,4-dione (0.10 g) 0. 1.5

Examples 18-19.

These examples illustrate the heat resistance of an over-chlorinated polyvinyl chloride containing 65% chlorine.

A mixture of 1000 g of this polymer, 10 g of wax ("Cire E"), 15 g of calcium stearate and 1.5 g of zinc stearate is prepared.

To 57 g of the prepared mixture, a certain amount of a stabilizer is added (see the following table), after which plates of 2 mm thickness are prepared by means of a calender heated to 190 ° C.

An examination of the heat resistance in an oven at 180 ° C gives the following results.

Time, minutes 0 7 14

Grades Gardner for:

Base mixture 11 13 18

Base mixture tstearoylacetone (0.50 g) 6 10 11

Base mixture tbenzoylacetone (0.30 g) 5 9 11 146927 12

Examples 20-24.

Proceeding in the same manner as in Example 1, 56 g of mixture A is mixed with 0.2 g of stearoylacetophenone, 0.2 g of palmitoylacetophenone, 0.3 g of 1-stearoyl-2-octanone or 0.3 g of p-methoxystearoylacetophenone. By determining the heat resistance of the manufactured plastics, the following results are obtained.

Time, minutes 1 7 14 21

Grades Gardner for:

Mixture A 8 9 10 11

Mixture A + stearoyl acetophenone 1 1 1 1.5

Mixture A + palmitoylacetophenone 1 1 1 1.5

Mixture A + stearoyloctanone 1 1 1.5 2

Mixture A + p-methoxystearoylacetophenone. 1 1 1 1.5

Example 25

In the same manner as in Example 1, a mixture of 1000 g of polyvinyl chloride, 100 g of a copolymer of butadiene, styrene and methyl methacrylate, 10 g of wax ("Cire E"), 2.5 g of zinc stearate, 5 g of calcium stearate is prepared. 30 g of epoxidized soybean oil and 3 g of trinonylphenylphite.

To three samples of 56 g of the mixture prepared, stearoyl acetone was added in an amount of 0.08 g (sample 1), 0.15 g (sample 2) and 0.25 g (sample 3). The heat resistance is determined in the same way as in the previous examples, which gives the following results.

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Time, minutes O 7 14 21 28 35

Grades Gardner for:

Base mixture 79 9 9 10 10

Sample 1 011,5235

Sample 2 000,5224

Sample 3 000124

Example 26

A mixture (a) is prepared by mixing 100 g polyvinyl chloride, 10 g ABS copolymer, 1 g wax ("Cire E"), 3 g epoxidized soybean oil, 0.7 g zinc stearate, 1.1 g calcium stearate and 0.64 g of decane-2,4-dione.

In addition, a mixture (b) which differs from mixture (a) is prepared in that the latter two components (the calcium salt and the dione) are replaced by 0.71 g of chelate of calcium and decane-2,4-dione. Of these mixtures, specimens are prepared in the same way as in the previous examples and the heat resistance of the specimens is examined. The results obtained are summarized in the following table.

Time, minutes 0 7 14 21

Grades Gardner for:

Base mixture 8888

Mixture (a) 0 0 0 2.5

Mixture (b) 1.5 2 '8 brown In mixtures (a) and (b), the molar amounts of β-di-ketone and calcium are about equal, but the heat resistance is much poorer when these substances are used in the form of chelates.

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Results of the same magnitude are obtained if zinc stearate and decan-2,4-dione are replaced with the corresponding zinc che-lat.

Examples 27-28.

In the same way as in Example 1, 56 g of mixture A is mixed with 0.15 g benzoyl acetaldehyde or with 0.15 g 2-methyl-2-acetyl acetaldehyde. Of the mixtures prepared, test pieces are prepared, the heat resistance of which is determined in a ventilated oven. The results obtained are summarized in the following table.

Time, minutes 0 7 14 21

Grades Gardner for:

Base mixture 6888

Base mixture + benzoyl acetaldehyde 2 3 3.5 4

Base mixture + 2-methyl-2-acetylacetaldehyde 3555

It is evident from the test results that the specimens containing organic stabilizer are stained much less during manufacture and have a much higher heat resistance.

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Examples 29-31

Proceed in the same manner as in Example 1, but use the organic stabilizers listed below.

29) C6H5-CO-CH2-CO-C21H43, m.p. 78 ° C.

This compound is added in an amount of 0.6 g / ml. 100 g PVC.

30) c17h35-co-ch2-co-c15h31.

This compound is added in an amount of 0.7 g / ml. 100 g PVC.

31) ch3-co-ch-co-ch3

CO

C15H31

This compound is added in an amount of 0.4 g / ml. 100 g PVC.

The color of the prepared specimens after heat treatment for various periods is given in the table below.

Time, minutes 0 7 14 21

Grades Gardner for mixing according to Example 29 111 1.5 30 1 1 1.5 1.5 31 11 1.5 2 16 146927

Example 32

The following basic mixture is used: PVC powder "Lucovyl RS8000" 100g (same as used in Example 1) butadiene-styrene-methylmethacrylate copolymer 10 g of "Cire E" 1 g of epoxidized soybean oil 3 g of calcium stearate 0.5 g of zinc 2-ethyl hexanoate 0.12 g

With this mixture partly alone and partly containing 0.3 g of the β-diketone allyl-benzoyl-acetone of the formula

CcHc-CO-CH-CO-CH_ 6 5 j 3 ch2-ch = ch2 pr. 100 g of PVC are prepared in the manner described in Example 1, plates having a thickness of 1 mm by calendering for 3 minutes at 180 ° C. Rectangular specimens of 10 x 20 mm are cut and placed in a ventilated oven at 180 ° C.

The color of the specimens is determined by different aging times and the results given in the following table are obtained: | Grades Gardner by Time in Minutes β-Diketon --- 1 -------- 0 5 10 15 20 25 30 40 50 60 70 .No 567 78 8 9 9 10 Black

Allyl Benzoyl Acetone 1 1.5 1.5 2.5 3 4 6 8 10 11 Black

Example 33 In this example, the β-diketone acetoacetyl-3-cyclohexene of the formula γ-co-ch2-co-ch3 is used.

The following mixture is prepared: 17 146927 PVC prepared by suspension polymerization, "RS 8000" (same as used in Example 1) 100 g

Reinforcing agent (butadiene-styrene-methyl methacrylate copolymer) 10 g lubricant (rosin ester) 1.0 g epoxidized soybean oil 3.0 g calcium stearate 1.0 g zinc stearate 0.25 g acetoacetyl-3-cyclohexene 0.60 g

Samples are prepared and tested at 180 ° C in the manner described in Example 1. The following results are obtained:

Grades Gardner by time in minutes 0 7 14 21 30 40 50 01 1.5 2 3 4 6

Claims (2)

18 146927 Patent Claims. Bismuth- and antimony-free heat-stabilized resin based on a vinyl chloride polymer, characterized in that it, based on the weight of the polymer, contains a heat-stabilizing addition consisting of (a) 0.1-5% of one or more of the carboxylic acid salts of divalent metals usually used to stabilize these polymers, and (b) 0.05-5% of a β-diketo or β-ketoaldehyde compound of the general formula R1 - CO - CHR2 - CO - R3 (I) Wherein R and R, which may be the same or different, each represent a straight or branched alkyl or alkenyl group of up to 30 carbon atoms, an aralkyl group of 7-36 carbon atoms or an aryl group or cycloalkyl or alkenyl group of less than 14 carbon atoms, the above-mentioned aryl groups being optionally substituted by a methoxy group or a 1,3-dioxo-butyl group, and the groups also being modified by the presence of one or more chain linkers -CO-O- or -CO-, 1 3 or wherein R and R are together form a divalent alkylene group of 2-5 carbon atoms, while R is / CV CHL · CH-CH-- j 2 | 2 CH 2 CO / ch 2 3 2 in addition, for both groups R and R, the carbon atom attached to the carbonyl group is not ethylenically 3 1 3 or carbonyl unsaturated, and for one of groups R and R the carbon atom bonded to the carbonyl group is not aromatically unsaturated, and in addition, one of the groups R