FR2918670A1 - Use of (meth)acrylic telomers/oligomers as halogenated polyolefin resin plasticizer, which is e.g. vinyl polychloride, and to prepare finished products comprising e.g. pipes, electrical cables, electrical appliances, toys, films and sheets - Google Patents

Abstract

Use of (meth)acrylic telomers or oligomers as halogenated polyolefin resin plasticizer, where the molecular weight of the oligomers or the telomers is 500-10000 g/mol, preferably 1000-5000 g/mol, is claimed. An independent claim is included for a formulation of the halogenated polyolefin resin containing the plasticizing agent, where the plasticizer is the (meth)acrylic oligomer or telomer.

Description

DESCRIPTION OF THE INVENTION

TECHNICAL FIELD OF THE INVENTION

  [1] The present invention relates to the synthesis of low molecular weight (meth) acrylic telomers and oligomers and their uses as a polyvinyl chloride (PVC), poly (vinyl chloride) type halogenated polyolefin resin plasticizer. vinylidene (PVDC), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF).

  STATE OF THE ART [2] Halogenated polyolefin resins (PVC, PVDC, PVF, PVDF) are polymers obtained respectively from halogenated vinyl monomers, for example, vinyl chloride (VC), vinylidene chloride ( VDC), vinyl fluoride (VF) and vinylidene fluoride (VDF) or by mixing such monomers. [3] Halogenated polyolefin resins are used in a wide range of applications such as pipes, electrical cables, electrical components, toys, films, foils, food packaging, coatings, medical containers, etc. [4] Halogenated polyolefin resins have physico-chemical properties that vary depending on the additives used in their formulation. These additives may be plasticizers, stabilizers, fillers, pigments, etc. [005] The plasticizers, when they are added to the halogenated polyolefin resins, make it possible to improve their use (extrusion, molding, injection, calendering, etc.), their electrical insulation properties, their properties of adhesion, etc. Examples of such plasticizers include products such as diethyl hexyl phthalate (DEHP), di-butyl phthalate (DBP), di-isodecyl phthalate (DIDP), butyl benzyl phthalate (BBP), di-isononyl phthalate (DINP ), di-2-ethylhexyl adipate (DEHA). [006] However, the European Community (1999/815 / EG) and the US Environmental Protection Agency have banned the use of six phthalate plasticisers (di-isononyl phthalate (DINP), di-isodecyl phthalate (DIDP) , diethyl hexyl phthalate (DEHP), 40 dibutyl phthalate, benzyl butyl phthalate, di-n-octyl phthalate) in toys and other articles that can be placed in contact with the mouth of children under three years of age.25 [007] Thus, there is a strong need at the present time for synthesizing new plasticizer additives of halogenated polyolefin resins which have no toxicological risks.

OBJECT OF THE INVENTION

  [008] In order to solve this problem described in the state of the prior art, an object of the present invention proposes novel (meth) acrylic low molecular weight (oligomers or telomers) plasticizers which have on the one hand properties Compatibility with halogenated polyolefin resins allows these halogenated polyolefin resins to exhibit improved physicochemical properties in terms of elongation at break, hardness, as well as improved resin processing properties.

  Another object of the present invention resides in the process for the preparation of these new polymeric plasticizers according to radical polymerization techniques which make it possible to reduce the molar masses of such polymers.

  [10] A third object of the invention is halogenated polyolefin compositions plasticized with such low molecular weight polymeric agents.

  [11] Methacrylic polymers are known to be well compatible with halogenated polyolefin resins PVC, PVDC, PVF, PVDF (US5242976). This is mainly due to two reasons: Hydrogen bonds are established between the carbonyl groups of the acrylic ester groups and the hydrogen atoms located in beta halogen atoms of the halogenated polyolefin resins. Dipole - dipole interactions are established between the carbonyl groups of the acrylic esters and the halogen atoms of the halogenated polyolefin resins. However, the methacrylic type polymers have too high glass transition temperature values, which goes against plastification properties. Moreover, the high molecular weight polymeric structures have steric hindrances which give the halogenated polyolefin resins property losses in terms of hardness (increase), elongation at break (decrease) and implementation (difficulties). .

  [12] Thus, according to one aspect of the present invention, it has been found that the use of (meth) acrylic oligomers or telomers makes it possible to impart to the halogenated polyolefin resins in which they have been introduced improved properties of hardness ( decrease), elongation at break (increase) and implementation (facilitation). [013] The (meth) acrylic oligomers according to the invention are prepared according to polymerization reactions by methods well known to those skilled in the art and that are oligomerization, telomerization or fragmentation addition polymerization. The length of the macromolecular chains is adjusted by the presence of transfer agents. According to the invention, macromolecular chain lengths are sought

  such as obtaining liquid or viscous oligomers at room temperature. To do this, the molar masses of the oligomers are between 500 g / mol and 10,000 g / mol and preferably between 1000 g / mol and 5000 g / mol. [014] Oligomerization, telomerization or addition polymerization

  Fragmentation is defined as a method of reacting, under the polymerization conditions, one or more monomers (M) and one or more telogens (T). The products of the T- (M) n type reaction are called telomers or oligomers and have a molar mass of between 500 and 10,000 g / mol. [015] The monomers M are chosen from the family of methacrylic and acrylic compounds and correspond to the following structure:

  H <R1 H Wherein: In which:

  R1 represents a hydrogen atom or a methyl group

  R2 represents a hydrogen atom, a linear, cyclic or branched C1-C30 alkyl group optionally substituted by a halogen atom, a hydroxy, alkoxy, cyano, amino or epoxy group. By way of example, it may be, for example, acrylic acid, methyl acrylate, ethyl, propyl, n-butyl, isobutyl, tert-butyl or 2-ethylhexyl, glycidyl, hydroxyalkyl acrylates,

  acrylonitrile, or a mixture of such monomers. It may also be, for example, methacrylic acid, methyl methacrylate, ethyl, propyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, glycidyl, methacrylates of hydroxyalkyl, or a mixture of such monomers. [016] The telogen agents (T) used according to the invention are classified into five sub-families: mercaptans, phosphites, alcohols, alkyl halides, addition-fragmentation agents. [017] The mercaptans used as transfer agent according to the invention have the following general formula:

  R3uSH wherein R3 is selected from:

  - a linear or branched alkkyl group of 1 to 18 carbon atoms - a cycloalkyl group of 3 to 8 carbon atoms

an aryl group

  a hydroxyalkyl group of 2 to 8 carbon atoms

  a carboxyalkyl group of 2 to 8 carbon atoms

  a mercaptoaliphatic group of 2 to 8 carbon atoms By way of example, it is possible according to the invention to use methyl mercaptan, ethyl mercaptan, butyl mercaptan, mercaptoethanol, thioacetic acid,

  mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, thiomalic acid, benzyl mercaptan, phenyl mercaptan, cyclohexyl mercaptan, 1-thioglycerol, 2,2'-dimerc: aptodiethyl ether, 2,2 trimercaptodipropyl ether, 2,2'-dimercaptodiisopropyl ether, 3,3'-dimercaptodipropyl ether, 2,2'-dimercaptodiethyl sulfide, 3,3'-dimercaptodipropyl sulfide, bis (béta.-mercaptoethoxy) methane, bis (.beta.-mercaptoethylthio) methane, ethane 1,2-dithiol, propane 1,2-dithiol, butane 1,4-dithiol, 3,4-dimercaptobutanol-1, trimethylolethane tri (3-mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate), trimethyloipropane trithioglycolate, pentaerythritol tetrathio glycolate, octanethiol, decanethiol, dodecanethiol, octadecylthiol or a combination thereof. [018] The phosphites used as transfer agent according to the invention have the following structure:

O R 4 H 1 P = O 1 OR 4 in which:

  R4 represents a hydrogen atom or an aryl or linear or branched alkyl group of 1 to 12 carbon atoms.

  For example, it is preferentially used according to dimethyl phosphite, diethyl phosphite, diisopropyl phoshite and dibutyl phosphite or a combination of these products. [019] The alcohols used as transfer agent according to the invention have the following general structure:

R6 R5uCuOH 1 R7 in which

  R5 R6 R7 are chosen from a hydrogen atom, an aryl group or linear or branched alkyl of 1 to 18 carbon atoms.

  By way of example, methanol, ethanol, isopropanol, n-butanol, n-propanol, isobutanol, t-butanol, pentanol and hexanol are preferably used according to the invention. benzyl alcohol, ottanol, decanol, dodecanol, octadecanol or a combination thereof. [20] The alkyl halides used as transfer agent according to the invention have the following general structure: wherein R8 R9 are the same or different and are selected from a hydrogen atom, a chlorine atom or a atom of bromine. By way of example, bromotrichloromethane, carbon tetrachloride, chloroform or a combination of these products are preferably used according to the invention. [21] The fragmentation additives used as the transfer agent according to the invention have the following general structure: Z 1 R 10 wherein Z is selected from a sulfur atom or a peroxide group T is selected from a benzyl group or a CO2-Rlo group Rio is chosen from a hydrogen atom, a linear or branched alkyl or aryl group of 1 to 12 carbon atoms. [022] The initiation (initiation) of the telomerization, oligomerization or addition-fragmentation polymerization reactions is of radical type or of the redox type.

  [23] The radical-initiating telomerization reactions use a radical generator which can be of peroxide, perester, percarbonate and diazo type. It is possible to mention essentially hydrocarbon peroxides, such as ditertiobutyl peroxide, dicumylperoxide or benzoyl peroxide, dialkyl peroxydicarbonates, such as diethyl or diisopropylperoxydicarbonate or din-propylperoxydicarbonate, peracids or peresters, such as the perpivalate of t- butyl; tert-amyl perpivalate or t-butyl peroxybenzoate. Among the diazo compounds, there can be mentioned essentially 2,2 'azobisisobutyrontrile, 2,2'azobis (2,4-dimethylvaleronitrile) and 2,2'azobis (2-cyclopropylpropionitrile).

  [24] Redox primed telomerization reactions employ redox priming methods well known to those skilled in the art. Thus, it is necessary to use a polar solvent to solubilize the catalyst. Nitriles are preferably used, and among these are aliphatic nitriles such as acetonitrile, propionitrile and butyronitrile. In this case, the solvent is miscible with the reagents and does not compete with the tetogenic agent during the transfer reactions. The catalyst is preferably a metal powder in particular, iron, copper and magnesium, or a metal salt in which the metal is likely to pass to a higher oxidation state including cuprous chloride, ferrous chloride, potassium ferricyanide. Another solution is to use a reducible metal salt with a reducing agent such as benzoin, this metal salt may be ferric chloride. The oligomerization or telomerization reaction temperatures are between 50.degree. C. and 150.degree. C. and essentially depend on the nature of the initiator and the reactivity of the monomers and telogens.

  [26] The reaction times are between 1 h and 24 h and depend essentially on the nature of the initiator and the reactivity of the monomers and telogens.

  [27] The molecular weight of the oligomers or telomers obtained according to the invention is regulated by the concentration ratios between the monomer (M) and the transfer agent (T). Thus, the length of the macromolecular chains can be adjusted at will. It is preferred that this ratio be between 0.01 and 100, which makes it possible to obtain DPn values (degree of polymerization by number) of the order of 5 to 100. Of course, this ratio is directly related to the concentration ratio. molar monomer / transfer agent pair and transferability (transfer constant) of the telogen agent.

  The oligomers or telomers obtained according to the present invention are in the form of a viscous liquid, which is fundamental for their application as a plasticizer of halogenated polyolefin resins. This is the consequence of two elements: • the molecular weight of the telomeres which is low and which is between 500 g / mol and 10000 g / mol and preferably between 1000 g / mol and 5000 g / mol 15 • the value of the transition glassy telomere which is between -70 C and +50 C and preferably between -50 C and 20 C.

  The halogenated polyolefin resins can be formulated in the presence of (meth) acrylic oligomers or telomers in the following respective proportions, from 20 to 99% by weight of halogenated polyolefin resin, from 1 to 80% of oligomers, or (meth) acrylic telomeres • from 1 to 50% of additives, such as pigments or fillers, stabilizers, antioxidants, processing additives and lubricants

  By way of example, through the use of these oligomers or telomers, PVC resins have been formulated and have improved properties in terms of elongation at break, hardness, as well as improved resin implementation properties

  [031] Moreover, the use of these oligomers or telomers according to the present invention can be applied to any other halogenated polyolefin resin requiring the improvement of such properties, for example these products can be used in other Halogenated polyolefin resins such as PVDC, PVF or PVDF. [032] Examples: The examples below are given for illustrative purposes only and therefore have no limiting character of the present invention. [33] Example 1: In a 500 ml two-neck flask equipped with a condenser and an inlet of argon, 30 g (0.348 mol) of metyl acrylate, 11 g (0.086 mol. butyl acrylate, 3.9 g (0.04 mol) butanethiol and 100 ml toluene. The solution is swept by a stream of argon for 15 minutes and is heated to 70 ° C. Then 2.13 g (0.013 mol) of azobis-isobutyronitrile (AIBN) is introduced.

  After 16 hours of reaction, the toluene is evaporated off under reduced pressure to obtain a viscous liquid having a molar mass equal to 900 g / mol with a yield of 95%.

  [34] Example 2: In a 500 ml two-neck flask equipped with a condenser and an inlet of argon, 10 g (0.116 mol.) Of methyl acrylate, 3.7 g (0.029 mol.) D are introduced. butyl acrylate and 175 g (2.92 mol) of isopropanol. The solution is swept by a stream of argon for 15 minutes and is heated to 70 ° C. Then 0.71 g (4.3 × 10 -3 mol) of azobis-isobutyronitrile (AIBN) is introduced. reaction, the isopropanol is evaporated by distillation under reduced pressure and a viscous liquid is obtained having a molar mass equal to 1400 g / mol with a yield of 95%.

  [35] Example 3: 62.5 parts by weight of PVC homopolymer resin and 37.5 parts by weight of the plasticizer obtained according to Example 1 are introduced into a HAAKE POLYLAB rheometer at a temperature of between 150 and 190 ° C. for 5 minutes. Then, the mixture is converted to 175 C to obtain a PVC sheet 5 mm thick. Subsequently, this PVC sheet is pressed under high pressure and high temperature to form a 3.5 mm PVC sheet 1 mm thick. Finally, this sheet is used to prepare test specimens for measuring elongation and hardness.

  [36] EXAMPLE 4 62.5 parts by weight of PVC homopolymer resin and 37.5 parts by weight of the plasticizer obtained according to Example 2 are introduced into a HAAKE POLYLAB rheometer at a temperature between 150 and 190 ° C. for 5 minutes. Then, the mixture is converted to 175 C to obtain a PVC sheet 5 mm thick. Subsequently, this PVC sheet is pressed under high pressure and high temperature to form a 1 mm thick PVC sheet. Finally, this sheet is used to prepare test specimens for measuring elongation and hardness.

  [037] Table of results: Elongation at hardness rupture (%) virgin PVC 10% 65 (SHORE D) Example 3 420% 90 (SHORE A) Example 4 400% 81 (SHORE A) It is clear that the oligomers Acrylic synthesized in Examples 1 and 2 give PVC plasticizing properties (strong increase in elongation at break, sharp decrease in hardness). 15

Claims (20)

  1 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins, characterized in that the molar mass of the oligomers or telomers is between 500 g / mol and 10,000 g / mol; preferably between 1000 g / mol and 5000 g / mol.   2 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claim 1, characterized in that the (meth) acrylic monomer (s) used to synthesize the Oligomers and telomers have the following structure: ## STR2 ## wherein R 1 represents a hydrogen atom or a methyl group R 2 represents a hydrogen atom, a linear, cyclic or branched optionally substituted C 1 -C 30 alkyl group by a halogen atom, a hydroxy, alkoxy, cyano, amino or epoxy group. By way of example, it may be acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylate or acrylate. isobutyl, tert-butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyalkyl acrylates, acrylonitrile, methacrylic acid, methyl methacrylate, ethyl methacrylate propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, hydroxyalkyl methacrylates, or mixtures of such monomers. 30   3 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claims 1 and 2, characterized in that the oligomers or telomers are obtained by polymerization in the presence of selected chain transfer agents among mercaptans, phosphites, alcohols, alkyl halides and addition-fragmentation agents. R1 H WhereOr2 O 35'12   4 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claims 1, 2 and 3, characterized in that the mercaptan chain transfer agents have the following general structure: R3 · SH wherein: R3 is selected from: - a linear or branched alkyl group of 1 to 18 carbon atoms - a cycloalkyl group of 3 to 8 carbon atoms - an aryl group - a hydroxyalkyl group of 2 to 8 carbon atoms - a carboxyalkyl group of 2 to 8 carbon atoms - a mercaptoaliphatic group of 2 to 8 carbon atoms   5 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claim 4, characterized in that the mercaptan chain transfer agents are chosen from methyl mercaptan, ethyl mercaptan and butyl mercaptan, mercaptoethanol, thioacetic acid, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, thiomalic acid, benzyl mercaptan, phenyl mercaptan, cyclohexyl mercaptan, 1-thioglycerol, 2,2'-dimercaptodiethyl ether, 2,2'-dimercaptodipropyl ether, 2,2'-dimercaptodiisopropyl ether, 3,3'-dimercaptodipropyl ether, 2,2'-dimercaptodiethyl sulfide, 3,3'-dimercaptodipropyl sulphide, bis (beta-mercaptoethoxy) methane, bis (beta-mercaptoethylthio) methane, ethane dithiol-1,2, propane 1,2-dithiol, butane dithiol-1,4, 3,4-dimercaptobutanol-1, trimethylolethane tri (3-mercaptopropion ate), pentaerythritol tetra (3-mercaptopropionate), trimethylolpropane trithioglycolate, pentaerythritol tetrathio glycolate, octanethiol, decanethiol, dodecanethiol, octadecylthiol or a combination thereof.   6 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claims 1, 2 and 3, characterized in that the phosphite chain transfer agents have the following general structure: OR4 Wherein R 4 represents a hydrogen atom or an aryl or linear or branched alkyl group of 1 to 12 carbon atoms.   7 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claim 6, characterized in that the phosphite chain transfer agents are chosen from dimethyl phosphite and diethyl phosphite, diisopropyl phoshite and dibutyl phosphite or a combination of these products.   8 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claims 1, 2 and 3, characterized in that the alcohol-type chain transfer agents have the following general structure: R6 Wherein R 5 R 6 R 7 are selected from hydrogen, aryl or linear or branched alkyl of 1 to 18 carbon atoms.   9 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claim 8, characterized in that the chain transfer agents of the alcohol type are chosen from methanol, ethanol, methanol and methanol. isopropanol, n-butanol, n-propanol, isobutanol, t-butanol, pentanol, hexanol, benzyl alcohol, octanol, decanol, dodecanol, octadecanol or a combination of these products.   10 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claims 1, 2 and 3, characterized in that the alkyl halide chain transfer agents have the general structure wherein R 8 R 9 are the same or different and are selected from a hydrogen atom, a chlorine atom or a bromine atom.   11 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claim 10, characterized in that the alkyl halide chain transfer agents are chosen from bromotrichloromethane and tetrachloride. carbon, chloroform or a combination of these products.   12 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claims 1, 2 and 3, characterized in that the fragmentation agent-type chain transfer agents have the structure following general: wherein: Z is selected from a sulfur atom or a peroxide group Rio is selected from a hydrogen atom, an aryl group or linear or branched alkyl of 1 to 12 carbon atoms. T is chosen from a benzyl group or a CO2-Rio group.   13 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claims 1 to 12, characterized in that the products are obtained by radical polymerization using a radical or redox type polymerization initiator.   14 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to Claims 1 to 13, characterized in that the oligomerization or telomerisation reaction temperatures are between 50 ° C. and 150 ° C. and essentially depend on the nature of the initiator and the reactivity of the monomers and telogens.   15 - Use of (meth) acrylic oligomers or telomers as plasticizers of halogenated polyolefin resins according to claims 1 to 14, characterized in that the polymerization reaction times are between 1 h and 24 h and essentially depend on the nature of initiator and reactivity of monomers and telogens.   16 - Use of (meth) acrylic oligomers or telomers as plasticizers for 40 halogenated polyolefin resins according to claims 1 to 15, characterized in that the molar masses of the oligomers or telomers obtained according to the invention are regulated by KT Zù Rio the concentration ratios between the monomer (M) and the transfer agent (T). It is preferred that this ratio be between 0.01 and 100, which makes it possible to obtain DPn (number of polymerization by number) values of the order of 5 to 100.   17 - Formulation of halogenated polyolefin resins containing a plasticizer, characterized in that this plasticizer is a (meth) acrylic oligomer or telomer as defined in claims 1 to 16.   18 - Formulation of halogenated polyolefin resins containing a (oligomeric) oligomeric or telomeric plasticizer according to claim 17, characterized in that the halogenated polyolefinic resin is chosen from polyvinyl chloride (PVC) and polyvinylidene chloride (PVDC), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF).   19 - Formulation of halogenated polyolefin resins containing a (oligomeric) oligomeric or telomeric type plasticizer according to claims 17 and 18, characterized in that the composition of the formulation comprises (expressed in percent by weight): from 20 to 99% halogenated polyolefin resin • from 1 to 80% of (meth) acrylic oligomers or telomers according to claims 1 to 12 • from 1 to 50% of additives, such as pigments or fillers, stabilizers, antioxidants, additives of implementation and lubricants   20 - Use of a formulation of halogenated polyolefin resins containing an oligomer or telomere (meth) acrylic type plasticizer according to claims 17 to 19 for the manufacture of finished products such as, for example, pipes, electrical cables, electrical components, toys , films, sheets, food packaging, coatings, medical containers.