EP1330487A1 - Utilisation de composes beta-dicarbonyles silyles comme stabilisants de polymeres halogenes. - Google Patents

Utilisation de composes beta-dicarbonyles silyles comme stabilisants de polymeres halogenes.

Info

Publication number
EP1330487A1
EP1330487A1 EP01983655A EP01983655A EP1330487A1 EP 1330487 A1 EP1330487 A1 EP 1330487A1 EP 01983655 A EP01983655 A EP 01983655A EP 01983655 A EP01983655 A EP 01983655A EP 1330487 A1 EP1330487 A1 EP 1330487A1
Authority
EP
European Patent Office
Prior art keywords
radical
carbon atoms
use according
weight
aliphatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01983655A
Other languages
German (de)
English (en)
French (fr)
Inventor
Christian Prud'homme
Michel Gay
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1330487A1 publication Critical patent/EP1330487A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond

Definitions

  • the present invention relates to the use of silylated ⁇ -dicarbonylated compounds as stabilizers for halogenated polymers.
  • the subject of the invention is silylated compounds derived from ⁇ -dicarbonylated compounds whose boiling point is lower or equal, or even slightly higher than the forming temperature of halogenated polymers.
  • ⁇ -dicarbonylated compounds such as ⁇ -diketones or ⁇ -ketoesters
  • stabilizers for halogenated polymers such as polyvinyl chloride.
  • Acetylacetone is an example of this type of compound. Indeed, its boiling temperature is around 140 ° C. This ⁇ -diketone is very effective but it has the disadvantage of being volatile. However, in most cases, the forming temperatures of the halogenated polymers are sufficiently high for the acetylacetone to vaporize and escape from the polymeric composition.
  • the object of the present invention is therefore to remedy these problems by proposing a compound derived from a ⁇ -diketone or from a ⁇ -ketoester which remains as effective as the ⁇ -diketone or the initial ⁇ -ketoester and which does not risk to be removed from the polymer composition during the shaping of the latter.
  • R 1 identical or not, represent an aliphatic or aromatic radical; said radicals being chosen such that the silylated compound has a boiling point at least 30 ° C higher than the shaping temperature of said polymer;
  • R 3 represents an aliphatic radical R or a radical -OR ';
  • R 2 , R and R ′ which may or may not be identical, represent an aliphatic radical, linear or not, comprising 1 to 10 carbon atoms, or an aromatic radical, preferably comprising 6 carbon atoms, optionally substituted by at least one aliphatic radical comprising 1 to 10 carbon atoms; x is 1 or 2.
  • boiling temperatures are those measured at ambient temperature (20 ° C.) and at atmospheric pressure (10 5 Pa).
  • the stabilizing composition comprises at least one compound of formula (R 1 ) 4 .
  • the radical R 3 may represent an aliphatic radical R, in this case, the compound is a ⁇ -diketone.
  • the radical R 3 may represent a radical -OR '; in this case, the compound is a ⁇ -ketoester.
  • R 2 , R and R ′ which may or may not be identical, each represent an aliphatic radical, linear or not, comprising 1 to 10 carbon atoms, or an aromatic radical, preferably comprising 6 carbon atoms, optionally substituted by at least one radical aliphatic comprising 1 to 10 carbon atoms.
  • alkyl radicals such as methyl, ethyl, propyl and its isomers, butyl and its isomers, pentyl and isomers, hexyl and isomers.
  • aromatic radical there may be mentioned in particular benzyl, phenyl, toluyl, xylyl.
  • radicals are more particularly chosen so that the ⁇ -diketone (or the ⁇ -ketoester) from which the silylated compound is derived, has a boiling point such that the difference between the setting temperature does not form of said halogenated polymer and that of boiling of said ⁇ -diketone (or of said ⁇ -keto ester) is less than 30 ° C. It is specified that the difference between these two temperatures can be positive or negative.
  • the radical R or the radical R ' represents an aliphatic radical, preferably an alkyl radical comprising 1 to 10 carbon atoms.
  • the radical R 3 represents an aliphatic radical R as defined above.
  • radicals R 1 which may or may not be identical, they are first of all chosen so that the silylated compound has a boiling point at least higher minus 30 ° C relative to the forming temperature of said polymer.
  • the boiling point at least 60 ° C higher and even more advantageously at least 80 ° C.
  • these radicals represent an alkyl radical comprising 1 to 10 carbon atoms, or an aromatic radical comprising 6 carbon atoms, optionally substituted by at least one alkyl radical comprising 1 to 10 carbon atoms.
  • radicals R 1 which may or may not be identical, are chosen from the methyl, ethyl, propyl and isomers, butyl and isomers, pentyl and isomers, hexyl and isomers, benzyl, phenyl, toluyl, xylyl radicals.
  • the stabilizing composition can comprise one or more silylated compounds. More particularly, the silylated compound entering into the stabilizing composition is present at a content of between 0.05 and 2 parts by weight per 100 parts by weight of halogenated polymer. Preferably, the content of silylated compound is between 0.05 and 1 part by weight relative to the same reference.
  • the silylated compounds can be obtained by any means known to those skilled in the art.
  • the ⁇ -dicarbonyl compound with the halosilane, optionally in the presence of an amino base (such as pyridine, imidazole), preferably in stoichiometric amount, because its role is to capture the hydrochloric acid formed.
  • an amino base such as pyridine, imidazole
  • This reaction generally takes place in the presence of a solvent chosen from ethers, aliphatic hydrocarbons (pentane for example), or aromatic (toluene for example).
  • halosilane and the ⁇ -dicarbonylated compound are used, advantageously, in stoichiometric amount, or even in the presence of a slight excess of halososilane.
  • reaction temperature can be easily determined by a person skilled in the art. For purely illustrative purposes, the temperature varies between 20 and 100 ° C.
  • the stabilizing composition used for the stabilization of halogenated polymers may also comprise at least one organometallic stabilizer comprising a metal chosen from columns HA, IIB and IIIB of the periodic table of elements (published in the bulletin of the chemical company of France - January 1966).
  • organometallic stabilizer comprising a metal chosen from columns HA, IIB and IIIB of the periodic table of elements (published in the bulletin of the chemical company of France - January 1966).
  • calcium, barium, zinc, cadmium, lead, retain are suitable, as well as their associations.
  • the stabilizer comprises at least calcium, zinc or their mixtures.
  • the organometallic stabilizers are chosen more particularly from the metal salts of aliphatic carboxylic acids, saturated or not, aromatic or not, optionally carrying one or more hydroxyl groups, or also chosen from aromatic alcoholates or not.
  • organometallic stabilizers include the salts of maleic, acetic, diacetic, propionic, hexanoic, 2-ethyl hexanoic, decanoic, undecanoic, lauric, myristic, palmitic, stearic, oleic, ricinoleic, behenic (docosanoic) acids.
  • hydroxystearic hydroxy-undecanoic
  • benzoic phenylacetic, paratertiobutylbenzoic and salicylic
  • phenolates alcoholates derived from naphthol or phenols substituted by one or more alkyl radicals, such as nonylphenols.
  • the stabilizing composition advantageously has an organometallic stabilizer content of between 10 and 200 ppm, expressed as metal, relative to the weight of halogenated polymer.
  • the content of organometallic stabilizer is between 30 and 150 ppm expressed as metal, relative to the weight of halogenated polymer. It should be noted that these ranges represent more particularly the total content of this metal present in the stabilizing composition.
  • the composition advantageously has an organometallic stabilizer content of between 30 and 600 ppm, expressed as metal, relative to the weight of halogenated polymer. Again, it should be noted that these values represent more particularly the total content of this metal present in the stabilizing composition.
  • the stabilizing composition can comprise other additives conventional in the field, or else be used with additives conventional in the field.
  • these products can be used in a purified form or not.
  • the following commercial products can be advantageously used:
  • the content of free or chelated ⁇ -diketone is usually between 0.05 and 1 part by weight per 100 parts by weight of halogenated polymer. Note that if a ⁇ -diketone chelated with calcium or zinc is present, the content of this chelated compound is such that the total content of zinc or calcium is included in the ranges indicated above.
  • Polyols comprising 2 to 32 carbon atoms and having two to nine hydroxyl groups can also be used as additives in this field.
  • diols C3-C 30 such as propylene glycol, butanediol, hexanediol, dodecanediol, neopentyl glycol, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerin, mixtures of glycerol oligomers having a degree of polymerization from 2 to 10.
  • Another family of polyols which can be suitably used, is constituted by partially acetylated polyvinyl alcohols.
  • hydroxyl compounds comprising isocyanurate groups, alone or in combination with the abovementioned polyols, such as for example tris (2-hydroxyethyl) isocyanurate.
  • the amount of polyol used is generally between 0.05 and 5 parts by weight per 100 parts by weight of polymer. More particularly, it is less than 2 parts by weight per 100 parts by weight of halogenated polymer.
  • compounds of the organic phosphite type such as, for example, trialkyl, aryl, triaryl, dialkylaryl or diarylalkyl phosphites, for which the term alkyl denotes hydrocarbon groups of monoalcohols or of C 8 -C 2 polyols, and the term aryl denotes aromatic groups of phenol or of phenol substituted by alkyl groups of C ⁇ -Ci 2.
  • mineral phosphites such as calcium phosphites.
  • compounds of the Ca (HP ⁇ 3) (H 2 ⁇ ) type as well as phosphite - hydroxy - aluminum - calcium complexes can be used.
  • the content of additive of this type is usually between 0.1 and 2 parts by weight per 100 parts by weight of halogenated polymer.
  • the stabilizing composition can comprise, or be used with compounds of the epoxide type. These compounds are generally chosen from epoxy polyglycerides, or esters of epoxy fatty acids, such as epoxidized linseed, soybean or fish oils.
  • the amount of compounds of this type usually varies between 0.5 and 10 parts by weight per 100 parts by weight of halogenated polymer.
  • sulfates, and / or carbonates, of aluminum and / or magnesium in particular of the hydrotalcite type.
  • These are more particularly compounds of formula Mg 1 . x Al x (OH) 2 A n - ⁇ / n .mH 2 O, in which x is between 0 excluded and 0.5, A n_ represents an anion such as carbonate in particular, n varies from 1 to 3 and m is positive.
  • products of this type can be used, having undergone a surface treatment with an organic compound. It would not even depart from the scope of the present invention to use a product of the hydrotalcite type doped with zinc, having possibly undergone a surface treatment with an organic compound.
  • PAIcamizer® 4 marketed by the company Kyowa.
  • NaA type zeolites are particularly suitable, as described in US Pat. No. 4,590,233.
  • the content of this type of compound generally varies between 0.1 and 5 parts by weight per 100 parts by weight of halogenated polymer.
  • compositions can also comprise (or be used with) titanium dioxide, preferably in rutile form, possibly having undergone a surface treatment, preferably mineral.
  • the particle size of titanium dioxide is between 0.1 and 0.5 ⁇ m.
  • titanium dioxides Rhoditan® RL18, Rhoditan® RL90, sold by Rhodia Chimie the titanium dioxides KRONOS 2081® and 2220® sold by Kronos.
  • the formulations based on halogenated polymers can likewise comprise other white or colored pigments.
  • the colored pigments there may be mentioned in particular cerium sulfide.
  • the quantity of pigment introduced into the formulation varies within wide limits and depends in particular on the coloring power of the pigment and on the desired final coloration.
  • the amount of pigment can vary from 0.1 to 20 parts by weight per 100 parts by weight of halogenated polymer, preferably from 0.5 to 15 parts by weight relative to the same reference.
  • the formulation may include phenolic antioxidants, UV stabilizers such as 2-hydroxybenzophenones, 2-hydroxybenzotriazoles or sterically hindered amines, commonly known as Hais.
  • the content of this type of additive generally varies between 0.05 and 3 parts by weight per 100 parts by weight of halogenated polymer.
  • lubricants can also be used which will facilitate implementation, chosen in particular from glycerol monostearates or even propylene glycol, fatty acids or their esters, montanate waxes, poylethylene waxes or their oxidized derivatives, paraffins, metallic soaps, functionalized polymethylsiloxane oils such as, for example, ⁇ -hydroxypropylenated oils.
  • the amount of lubricant entering the halogenated polymer formulation generally varies between 0.05 and 2 parts by weight per 100 parts by weight of halogenated polymer. It is also possible to use plasticizers chosen from alkyl phthalates. The most generally used compounds are chosen from di (ethyl-2-hexyl) phthalate, esters of linear C 6 -C 12 diacids, trimellitates or also phosphate esters.
  • the amount of plasticizer used in the formulations varies over a wide range, depending on the desired rigid or flexible character. As an indication, the content varies from 0 to 100 parts by weight per 100 parts by weight of halogenated polymer.
  • halogenated polymers which can be stabilized by the composition comprising at least one silylated compound
  • the latter are more especially chlorinated polymers.
  • the invention is particularly well suited for the stabilization of formulations based on polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • polyvinyl chloride is meant compositions in which the polymer is a homopolymer of vinyl chloride.
  • the homopolymer can be chemically modified, for example by chlorination.
  • copolymers of vinyl chloride can also be stabilized using the composition according to the invention.
  • These are in particular polymers obtained by copolymerization of vinyl chloride with monomers having an ethylenically polymerizable bond, such as for example vinyl acetate, vinylidene chloride; maleic, fumaric acids or their esters; olefins such as ethylene, propylene, hexene; acrylic or methacrylic esters; styrene; vinyl ethers such as vinyldodecyl ether.
  • the copolymers contain at least 50% by weight of vinyl chloride units and preferably at least 80% by weight of such units.
  • PVC alone or in admixture with other polymers is the most widely used chlorinated polymer in stabilized formulations according to the invention.
  • any type of polyvinyl chloride is suitable, whatever its method of preparation.
  • the polymers obtained for example by using bulk, suspension, emulsion processes can be stabilized using the composition according to the invention, and this regardless of the intrinsic viscosity of the polymer.
  • the shaping of the halogenated polymer comprising the stabilizing composition can be done by any means known to those skilled in the art.
  • this operation can be carried out in a mixer fitted with a blade and counter-blade system operating at a high speed.
  • the mixing operation is carried out at a temperature below 130 ° C.
  • the composition is formed according to the usual methods in the field such as injection, extrusion blow molding, extrusion, calendering or even rotational molding.
  • the temperature at which the shaping is carried out generally varies from 150 to 220 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP01983655A 2000-11-03 2001-10-30 Utilisation de composes beta-dicarbonyles silyles comme stabilisants de polymeres halogenes. Withdrawn EP1330487A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0014128 2000-11-03
FR0014128A FR2816313A1 (fr) 2000-11-03 2000-11-03 Utilisation de composes beta dicarbonyles silyles comme stabilisants de polymeres halogenes
PCT/FR2001/003369 WO2002036674A1 (fr) 2000-11-03 2001-10-30 Utilisation de composes beta-dicarbonyles silyles comme stabilisants de polymeres halogenes.

Publications (1)

Publication Number Publication Date
EP1330487A1 true EP1330487A1 (fr) 2003-07-30

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EP01983655A Withdrawn EP1330487A1 (fr) 2000-11-03 2001-10-30 Utilisation de composes beta-dicarbonyles silyles comme stabilisants de polymeres halogenes.

Country Status (10)

Country Link
US (1) US20060122296A1 (enExample)
EP (1) EP1330487A1 (enExample)
JP (1) JP2004513199A (enExample)
KR (1) KR20030051774A (enExample)
CN (1) CN1478124A (enExample)
AU (1) AU2002215089A1 (enExample)
CA (1) CA2427728A1 (enExample)
FR (1) FR2816313A1 (enExample)
MX (1) MXPA03003890A (enExample)
WO (1) WO2002036674A1 (enExample)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1950472B (zh) * 2004-03-15 2010-07-28 株式会社德山 涂料组合物
DE102008041918A1 (de) * 2008-09-09 2010-03-11 Evonik Degussa Gmbh Silanolkondensationskatalysatoren zur Vernetzung von gefüllten und ungefüllten Polymer-Compounds

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
DE4134325C2 (de) * 1991-10-17 1997-12-18 Henkel Kgaa Verfahren zur Stabilisierung von Polymerisaten des Vinylchlorids und Mittel zur Durchführung des Verfahrens
AU676689B2 (en) * 1992-11-06 1997-03-20 Rhone-Poulenc Chimie Beta-diketones, processes for making beta-diketones and use of beta-diketones as stabilizers for PVC

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0236674A1 *

Also Published As

Publication number Publication date
CN1478124A (zh) 2004-02-25
JP2004513199A (ja) 2004-04-30
CA2427728A1 (fr) 2002-05-10
MXPA03003890A (es) 2003-07-28
KR20030051774A (ko) 2003-06-25
FR2816313A1 (fr) 2002-05-10
WO2002036674A1 (fr) 2002-05-10
AU2002215089A1 (en) 2002-05-15
US20060122296A1 (en) 2006-06-08

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