PLASTICIZER COMPOSITION CONTAINING POLYMERIC DICARBOXYLIC ACID ESTERS AND DICARBOXYLIC ACID DIESTERS

Abstract

The present invention relates to a plasticizer composition containing at least one polymeric dicarboxylic acid ester and at least one dicarboxylic acid diester, to molding compounds containing a thermoplastic polymer or an elastomer and such a plasticizer composition, and to the use of said plasticizer compositions and molding compounds.

Claims

1.-24. (canceled)

25. A plasticizer composition comprising a) one or more compounds of the formula (I), ##STR00002## in which X is in each case an unbranched or branched C.sub.2-C.sub.8-alkylene group or an unbranched or branched C.sub.2-C.sub.8-alkenylene group, comprising at least one double bond, Y is in each case an unbranched or branched C.sub.2-C.sub.12-alkylene group or an unbranched or branched C.sub.2-C.sub.12-alkenylene group, comprising at least one double bond, a is an integer from 1 to 100 and R.sup.1 independently of one another are selected from unbranched or branched C.sub.1-C.sub.12-alkyl radicals, where the groups Y present in the compound(s) (I) can be identical or different from one another and where if the compound(s) (I) comprise more than one group X, these may be identical or different from one another, and b) one or more compounds of the formula (II),
R.sup.2OC(O)ZC(O)OR.sup.3(II) in which Z is an unbranched or branched C.sub.2-C.sub.8-alkylene group or an unbranched or branched C.sub.2-C.sub.8-alkenylene group, comprising at least one double bond, and R.sup.2 and R.sup.3, independently of one another, are selected from branched and unbranched C.sub.4-C.sub.12-alkyl radicals.

26. The plasticizer composition according to claim 25, where the weight-average molar mass of the compounds (I) is in the range from 500 to 15 000 g/mol.

27. The plasticizer composition according to claim 25, where, in the compound of the formula (I), X is in each case a branched or unbranched C.sub.2-C.sub.6-alkylene group and Y is in each case a branched or unbranched C.sub.2-C.sub.5-alkylene group.

28. The plasticizer composition according to claim 25, where, in the compound of the formula (I), the groups Y are not all identical and if in the compound of the formula (I) a plurality of groups X are present, these are identical.

29. The plasticizer composition as claimed in claim 25, where, in the compounds of the formula (I), R.sup.1 is, independently of the others, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, isooctyl or 2-ethylhexyl.

30. The plasticizer composition according to claim 25, where, in the compounds of the formula (I), R.sup.1 are both methyl, both ethyl, both n-propyl, both isopropyl, both n-butyl, both isobutyl or both n-pentyl.

31. The plasticizer composition according to claim 25, where, in the compounds of the formula (II), Z is an unbranched C.sub.2-C.sub.5-alkylene group.

32. The plasticizer composition according to claim 25, where, in the compounds of the formula (II), R.sup.2 and R.sup.3 are both 2-ethylhexyl, both isononyl or both 2-propylheptyl.

33. The plasticizer composition according to claim 25, where the plasticizer composition comprises a further plasticizer different from the compounds (I) and (II) which is selected from phthalic acid alkyl aralkylesters, trimellitic acid trialkylesters, benzoic acid alkylesters, dibenzoic acid esters of glycols, hydroxybenzoic acid esters, monoesters of saturated monocarboxylic acids, monoesters of hydroxymonocarboxylic acids, esters of unsaturated monocarboxylic acids, esters of saturated hydroxydicarboxylic acids, amides and esters of aromatic sulfonic acids, alkylsulfonic acid esters, glycerol esters, isosorbide esters, phosphoric acid esters, citric acid diesters, citric acid triesters, alkylpyrrolidone derivatives, 2,5-furandicarboxylic acid esters, 2,5-tetrahydrofurandicarboxylic acid esters, epoxidized vegetable oils, epoxidized fatty acid monoalkyl esters, 1,3-cyclohexanedicarboxylic acid dialkyl esters, 1,4-cyclohexanedicarboxylic acid dialkyl esters, polyesters of aliphatic and/or aromatic polycarboxylic acids with at least dihydric alcohols different from compounds (I).

34. The plasticizer composition according to claim 25, where the content of compounds of the formula (I) in the plasticizer composition is 10 to 99% by weight.

35. The plasticizer composition according to claim 25, where the content of compounds of the formula (II) in the plasticizer composition is 1 to 90% by weight.

36. The plasticizer composition according to claim 25, where the weight ratio between compounds of the formula (II) and compounds of the formula (I) is in the range from 1:100 to 10:1.

37. A molding material comprising at least one polymer and the plasticizer composition as defined in claim 25.

38. The molding material according to claim 37, where the polymer is a thermoplastic polymer which is selected from homopolymers or copolymers which comprise at least one monomer in polymerized-in form which is selected from C.sub.2-C.sub.10-monoolefins, 1,3-butadiene, 2-chloro-1,3-butadiene, vinyl alcohol and C.sub.2-C.sub.10-alkylesters thereof, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, glycidyl acrylate, glycidyl methacrylate, acrylates and methacrylates of C.sub.1-C.sub.10-alcohols, vinyl aromatics, acrylonitrile, methacrylonitrile, maleic anhydride and ,-ethylenically unsaturated mono- and dicarboxylic acids, homopolymers and copolymers of vinylacetates, polyvinyl esters, polycarbonates, polyesters, polyethers, polyether ketones, thermoplastic polyurethanes, polysulfides, polysulfones, polyethersulfones, cellulose alkylesters, and mixtures thereof.

39. The molding material according to claim 38, where the thermoplastic polymer is selected from polyvinyl chloride (PVC), polyvinylbutyral (PVB), homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of styrene, polyacrylates, thermoplastic polyurethanes (TPU) or polysulfides.

40. The molding material according to claim 38, where the thermoplastic polymer is polyvinyl chloride (PVC).

41. The molding material according to claim 40, where the content of the plasticizer composition in the molding material is 5.0 to 300 phr.

42. The molding material according to claim 38, comprising at least one thermoplastic polymer different from polyvinyl chloride, where the content of the plasticizer composition in the molding material is 0.5 to 300 phr.

43. The molding material according to claim 37, where the polymer is an elastomer, selected from the group consisting of natural rubbers, synthetic rubbers and mixtures thereof.

44. The molding material according to claim 43, where the content of the plasticizer composition in the molding material is 1.0 to 60 phr.

45. A process for producing moldings and films which comprises utilizing the molding material as defined in claim 37, wherein the molding or film is a housing of electrical devices, computer housings, tools, pipelines, cables, hoses, wire sheathings, window profiles, plastic profiles for conveyor belts, components for automobile construction, tires, furniture, foam for upholstery and mattresses, covers, sealants, composite films, self-adhesive films, laminating films, tarpaulins, roofing sheets, records, synthetic leather, packaging containers, adhesive tape films or coatings.

46. A molding or film comprising the plasticizer as claimed in claim 25, wherein the molding or film is a medicinal product, a hygiene product, a food packaging, a product for interiors, a toy and childcare articles, a sport and leisure product, clothing or fibers for fabric.

Description

DESCRIPTION OF THE FIGURES

[0268] FIG. 1 shows the plasticizer compatibility of flexible PVC films comprising 100 phr of the plasticizer composition used according to the invention and, as comparison, flexible PVC films comprising exclusively the commercially available plasticizer Plastomoll DOA or Palamoll 632. The loss in dry weight [percent] as a function of test time (storage time) [days] is shown.

EXAMPLES

[0269] The following feed materials are used in the examples;

TABLE-US-00001 Feed material Manufacturer Suspension PVC, INOVYN ChlorVinyls Limited, trade name Solvin 271 SP London, UK Polyester plasticizer based on adipic BASF SE, Ludwigshafen, acid, 1,2-propanediol and acetic acid, Germany trade name Palamoll 632 Di(2-ethylhexy) adipate, BASF SE, Ludwigshafen, trade name Plastomoll DOA Germany BaZn stabilizer, Reagens S.p.A., Bologna, trade name Reagens SLX/781 Italy

Determination of Molar Mass

[0270] The number-average and the weight-average molar mass was measured by means of gel permeation chromatography (GPC). The GPC was carried out on a GPC System Infinity 1100 instrument from Agilent Technologies, consisting of pump, column heating, columns and with a DRI Agilent 1200 detector. The eluent is THF, which flows at a flow rate of 1 ml/min through a column combination of two Agilent PLgel mixed-E columns heated to 35 C. The samples, dissolved in THF in a concentration of 2 mg/ml, are filtered prior to injection over a Macherey-Nagel PTFE-20/25 (0.2 m) filter. 100 l were injected. The measurement values obtained were evaluated via a calibration curve which was obtained beforehand with narrowly distributed polystyrene standard from Polymer Laboratories with molecular weights of M=162 to M=50 400.

I) Preparation of the Plasticizer Plastomoll DOA (di(2-ethylhexyl)adipate)

[0271] The preparation was carried out by esterification of 782 g of 2-ethylhexanol (commercially available product, available for example from Oxea, Oberhausen) (20% excess with regard to adipic acid) with 365 g of adipic acid (commercially available product, available for example from BASF SE, Ludwigshafen) and 0.42 g of isopropyl butyltitanate as catalyst (commercially available product, available for example from DuPont, Wilmington, US) in a 2 l autoclave with N.sub.2 bubbling (10 I/h) at a stirrer speed of 500 rpm and a reaction temperature of 2300 C. The water of reaction formed was removed from the reaction mixture continuously with the N.sub.2 stream. The reaction time was 180 min. Then, the 2-ethylhexanol excess was distilled off at a vacuum of 50 mbar. 1000 g of the crude di(2-ethylhexyl) adipate were neutralized with 150 ml of 0.5% strength sodium hydroxide solution by stirring for 10 minutes at 80 C. A two-phase mixture was formed with an upper organic phase and a lower aqueous phase (waste liquor with hydrolyzed catalyst). The aqueous phase was separated off and the organic phase was after-washed twice with 200 ml of water. For further purification, the neutralized and washed di(2-ethylhexyl) adipate was stripped with steam at 180 C. and a vacuum of 50 mbar for 2 h. The purified di(2-ethylhexyl) adipate was then dried for 30 min at 1500 C./50 mbar by passing through an N.sub.2 stream (2 I/h), then stirred with activated carbon for 5 min and filtered off with suction over a suction filter with filter auxiliary Supra-Theorit 5 (temperature 80 C.).

[0272] The thus obtained di(2-ethylhexyl) adipate has a density at 20 C. of 0.925 g/cm.sup.3, a dynamic viscosity at 20 C. of 14.0 mPa-s, a refractive index nD20 of 1.4470, an acid number of 0.04 mg KOH/g, a water content of 0.03% and a purity according to GC of 99.93%.

II) Preparation and Testing of Flexible PVC Films Produced Using Plasticizer Compositions According to the Invention and Using Commercially Available Plasticizers

[0273]

TABLE-US-00002 Formulation Additive phr PVC (homopolymeric suspension PVC, trade name 100 Solvin 271 SP) Plasticizer composition according to the invention 100 BaZn stabilizer, trade name Reagens SLX/781 2 Plasticizer composition Palamoll 632 Plastomoll DOA Example Content/% Content/% 1 80 20 2 60 40 3 50 50 C1 100 0 C2 0 100

II.a) Preparation of Flexible PVC Films

[0274] 150 g of PVC (homopolymeric suspension PVC, trade name Solvin 271 SP); 150 g of plasticizer composition and 2 g of Ba/Zn stabilizer, trade name Reagens SLX/781 were mixed using a handmixer at room temperature. The mixture was then plasticized on an oil-heated laboratory mixing roll mill (Collin, Automatikwalzwerk model 150, diameter: 252 mm, width: 450 mm) and processed to give a rolled sheet. The temperature of the two rollers was in each case 180 C.; the spinning speeds were 15 revolutions/min (front roller) and 12 revolutions/min (rear roller); the rolling time was 5 minutes.

[0275] This gave a rolled sheet with a thickness of 0.53 mm. The cooled rolled sheet was then pressed at a temperature of 190 C. and a pressure of 150 bar over the course of 180 s on a press of the type laboratory plate press 400 P from Collin to give a flexible PVC film with a thickness of 0.50 mm.

II.b) Testing the Compatibility of the Plasticizer in the Flexible PVC Films

Purpose of the Investigation

[0276] The test serves for the quantitative measurement of the compatibility of plasticizers in flexible PVC formulations. It is carried out at elevated temperature (70 C.) and 100% relative atmospheric humidity. The data obtained are evaluated against the storage time.

Sample Bodies

[0277] Sample bodies (films) with a size of 751100.5 mm are used for the test. The films are perforated along the broad side, inscribed (soldering iron) and weighed.

Test Instruments

[0278] Heraeus drying cabinet at 70 C., analytical balance, temperature measuring device Testotherm with sensor for measuring inside the drying cabinet.

Procedure

[0279] The temperature inside the drying cabinet is set to the required 70 C. The ready weighed films are suspended on a wire frame and placed into a glass tank filled approx. 5 cm with water (demin. water). It should be ensured that the films do not touch each other. The lower edges of the films must not hang in the water. The glass trough is sealed steam-tight with a polyethylene film so that the steam that is formed later in the glass trough is unable to escape. The water level in the glass beaker is monitored daily and any missing water is replaced.

Storage Time

[0280] After 7, 14 and 28 days, in each case 2 films are removed from the glass trough and climatized for 1 hour freely hanging in the air. Then, the films are cleaned on the surface with methanol. The films are then dried freely hanging for 16 h at 70 C. in a drying cabinet with forced convection. After removal from the drying cabinet, the films are climatized freely hanging for 1 hour and then weighed. The arithmetic mean of the weight losses of the films is given in each case.

Results

[0281] FIG. 1 shows the results of the compatibility tests of PVC films which have been produced using the plasticizer compositions according to the invention (examples 1 to 3) and also using the pure polymer or monomer plasticizers (comparative examples 1 and 2). The loss in dry weight [percent] as a function of test time (storage time) [days] is shown.

[0282] As can be seen very readily in FIG. 1, the pure polymer plasticizer Palamoll 632 has very poor compatibility with PVC. The weight loss in the compatibility test after 28 days is around 27%. Even the addition of only 20 phr of Plastomoll DOA leads, for an identical total plasticizer content of 100 phr, to a significant reduction in the weight loss of plasticizer by almost half and therefore to a considerable improvement in compatibility. By further increasing the addition of Plastomoll DOA for an identical total plasticizer content, it is possible to reduce the weight loss virtually down to the low weight loss of the pure Plastomoll DOA.