EP2331627A1 - Utilisation de composés précurseurs siliciés d'un acide organique comme catalyseurs pour la réticulation de mélanges polymères chargés et non chargés - Google Patents
Utilisation de composés précurseurs siliciés d'un acide organique comme catalyseurs pour la réticulation de mélanges polymères chargés et non chargésInfo
- Publication number
- EP2331627A1 EP2331627A1 EP09780352A EP09780352A EP2331627A1 EP 2331627 A1 EP2331627 A1 EP 2331627A1 EP 09780352 A EP09780352 A EP 09780352A EP 09780352 A EP09780352 A EP 09780352A EP 2331627 A1 EP2331627 A1 EP 2331627A1
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- EP
- European Patent Office
- Prior art keywords
- silicon
- group
- acid
- containing precursor
- organic acid
- 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.)
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
Definitions
- the invention relates to the use of a silicon-containing precursor compound of an organic acid, in particular an olefinic silicon-containing precursor compound of an organic acid and / or a tetracarboxylic silane, for the production of unfilled and / or filled polymer compounds, polymers or filled plastics, such as granules or finished products, from thermoplastic base polymers and / or monomers and / or prepolymers of the thermoplastic base polymers.
- a finished product is an article, for example a shaped body, in particular a cable, hose or tube.
- the invention further relates to a masterbatch containing the silicon-containing precursor compound.
- polyethylene (PE) and its co-polymers For the production of filled and unfilled polymer compounds, in particular polyethylene (PE) and its co-polymers, it is known to crosslink silane-grafted or silane-co-polymerized polyethylenes as silanol condensation catalysts.
- Organotin compounds or aromatic sulphonic acids (Borealis Ambicat®) use.
- a disadvantage of the organotin compounds is their significant toxicity, while the sulphonic acids are noticeable by their pungent odor, which continues through all process stages to the end product.
- the polymer compounds crosslinked with sulphonic acids are generally unsuitable for use in the food sector or in the field of drinking water supply, for example for the production of drinking water pipes.
- Typical tin silanol condensation catalysts are dibutyltin dilaurate (dibutyltindilaurate, DBTDL) and dioctyltin dilaurate (diocytyltindilaurate, DOTL), which act as a catalyst via their coordination sphere. It is known, for the production of moisture keitsvernetzbaren polymers grafting silanes in the presence of radical formers on polymer chains and to perform after shaping the moisture crosslinking in the presence of said Silanhydrolysekatalysatoren and / or silanol condensation catalysts.
- the moisture crosslinking of polymers with hydrolyzable unsaturated silanes is used worldwide for the production of cables, pipes, foams, etc. Processes of this type are known under the name Sioplas process (DE 19 63 571 C3, DE 21 51 270 C3, US 3,646,155) and monosil process (DE 25 54 525 C3, US 4,117,195). While in the monosil process the crosslinking catalyst is already added during the first processing step, in the Sioplas process the addition of the crosslinking catalyst takes place only in the subsequent, the shaping step.
- vinyl-functional silanes can be co-polymerized with the monomers and / or prepolymers directly to the base polymer or coupled to polymers via grafting to the polymer chains.
- EP 207 627 discloses further tin containing catalyst systems and co-polymers modified therewith based on the reaction of dibutyltin oxide with ethylene-acrylic acid co-polymers.
- JP 58013613 uses Sn (acetyl) 2 as a catalyst and JP 05162237 teaches the use of tin, zinc or cobalt carboxylates together with bonded hydrocarbon groups as silanol condensation catalysts, such as dioctyltin maleate, monobutyltin oxide, dimethyloxybutyltin or dibutyltin diacetate.
- JP 3656545 uses for networking zinc and aluminum soaps, such as zinc octylate, aluminum laurate.
- JP 1042509 also discloses the use of organic tin compounds for cross-linking silanes, but also alkyl titanate esters based on titanium chelate compounds.
- the object of the present invention is to develop novel silane hydrolysis and / or silanol condensation catalysts which do not have the stated disadvantages of the known catalysts of the prior art and are preferably silane-grafted, silane-co-polymerized polymers, monomers or prepolymers or generally thermoplastic Disperse or homogenize polymers.
- the silane hydrolysis catalysts and / or silanol condensation catalysts are preferably liquid, wax-like to solid and / or applied or encapsulated on a carrier material.
- silicon-containing precursor compounds of an organic acid can be used as silane hydrolysis catalyst and / or silanol condensation catalyst, in particular as a catalyst for crosslinking silanols or with other functional groups of substrates capable of condensation, for example with OH-Si or HO substrate.
- a general requirement of the precursor compound is that it be hydrolyzable, especially in the presence of moisture, and thus release the free organic acid, especially under the process conditions of the monosil and / or Sioplas process.
- the silicon-containing precursor compound of the organic acid is hydrolyzed under heat, better in the molten state in the presence of moisture, and at least partially or completely releases the organic acid.
- the use of the silicon-containing precursor compound of an organic acid can be carried out in a monosil, sioplas or co-polymerisation process.
- it can be used for grafting onto an olefinic polymer, for co-polymerisation with monomers, prepolymers and / or thermoplastic base polymers.
- the silicon-containing precursor compound of an organic acid is also capable of adhesion promoter, in particular for the formation of Si-O-Si bonds or Si-O substrate.
- the use according to the invention of the precursor compound as catalyst allows a simple and economical conversion of thermoplastic base polymers, monomers and / or prepolymers of the base polymers into polymer compounds, without exhibiting the disadvantages mentioned, such as toxicity and odor impairment of the catalysts of the prior art. Depending on the use, no more alcohols are released during the production of polymer compounds or polymers.
- the silicon-containing precursor compound can be a carboxysilane, in particular an olefinic carboxysilane and / or a tetracarboxysilane.
- the carboxysilane, the silicon-containing precursor compound of an organic acid may be in liquid or preferably solid phase and is thereby preferably inert to hydrolysis with atmospheric moisture.
- the olefinic carboxysilane according to the invention is a so-called all-in-one package, since it can be co-polymerized or grafted and can simultaneously act as adhesion promoter and / or silane hydrolysis catalyst and / or silanol condensation catalyst.
- the hydrolysis to the organic acid occurs only with the supply of heat and moisture.
- the at least one silicon-containing precursor compound corresponds to an organic acid of the general formula I and / or II, (A) z SiR 2 x (OR 1 ) 4-zx (I)
- a independently of one another in formula I and / or II stands for a monovalent olefin group
- a as a bivalent radical in formula II stands for a divalent olefin group
- R 1 independently corresponds to a carbonyl-R 3 group, wherein R 3 corresponds to a substituted or unsubstituted hydrocarbon radical, in particular having 1 to 45 carbon atoms and
- R 2 independently of a substituted or unsubstituted hydrocarbon group.
- an unsaturated carboxylate radical especially a tetracarboxysilane
- grafting or co-polymerizing may be carried out in the presence of an organofunctional silane compound, such as an unsaturated alkoxysilane of general formula III.
- organofunctional silane compound such as an unsaturated alkoxysilane of general formula III.
- A is preferably, independently of one another, in formula I and / or II a monovalent olefin group, such as in particular
- R 9 is identical or different and R 9 is a hydrogen atom or a methyl group or a phenyl group
- the group M is a group from the series -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 -, -O (O) C (CH 2 ) 3 - or -C (O) O- (CH 2 ) 3 -
- k is 0 or 1 such as vinyl, allyl, 3-methacryloxypropyl and / or acryloxypropyl, n-3-pentenyl, n-4-butenyl or
- Isoprenyl 3-pentenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl, betulaprenoxy, cis / trans-polyisoprenyl, or
- A is a divalent olefin radical in formula II, such as the corresponding alkenylenes, for example 2-pentenylene, 1,3-butadienylene, iso-3-butenylene, pentenylene, hexenylene, hexenedienylene, cyclohexenylene, terpenylene, squalanylene, Squalene, polyterpenylene, cis / trans polyisoprenylene.
- alkenylenes for example 2-pentenylene, 1,3-butadienylene, iso-3-butenylene, pentenylene, hexenylene, hexenedienylene, cyclohexenylene, terpenylene, squalanylene, Squalene, polyterpenylene, cis / trans polyisoprenylene.
- R 2 in formula I and / or II independently of one another is a hydrocarbon group, in particular a substituted or unsubstituted linear, branched and / or cyclic alkyl, alkenyl, alkylaryl, alkenylaryl and / or aryl group having 1 to 24 C atoms, preferably having 1 to 18 carbon atoms. In particular with 1 to 3 C atoms in the case of alkyl groups.
- Particularly suitable alkyl groups are ethyl, n-propyl and / or i-propyl groups.
- Suitable substituted hydrocarbons are in particular halogenated hydrocarbons, such as 3-halopropyl, for example 3-chloropropyl or 3-bromopropyl groups, which are optionally accessible to a nucleophilic substitution or which can be used in PVC.
- halogenated hydrocarbons such as 3-halopropyl, for example 3-chloropropyl or 3-bromopropyl groups, which are optionally accessible to a nucleophilic substitution or which can be used in PVC.
- Examples of these are methyl-, dimethyl-, ethyl- or methylethyl-substituted carboxysilanes based on capnic acid, myristic acid, oleic acid or lauric acid.
- Carbonyl-R 3 groups are understood to mean the acid radicals of the organic carboxylic acids, such as R 3 - (CO) -, which are bonded as a carboxyl group corresponding to the formulas to the silicon Si-OR 1 , as stated above.
- fatty acids are preferably used in the formula I and / or II with a hydrophobic hydrocarbon radical which are sufficiently hydrophobic, have no unpleasant odor after release and do not bloom from the polymers produced.
- Sufficiently hydrophobic is a KW residual, though the acid is dispersible in the polymer or a monomer or prepolymer.
- This blooming for example, makes stearic acid and palmitic acid in the silicon-containing precursors of organic acid of limited usefulness at higher concentrations. For example, even at a concentration above about 0.01% by weight of the liberated stearic acid or palmitic acid with respect to the overall composition of the polymer, waxy blooming is observed on the produced polymers.
- Preferred acid radicals in the formulas I and / or II result from the following acids, such as capnic acid, lauric acid, myristic acid but also behenic acid can be used expediently.
- the naturally occurring or synthetic unsaturated fatty acids can be converted to the precursor compounds of formula I and / or II. They can fulfill two functions, on the one hand they serve as silane hydrolysis catalyst and / or as silanol condensation catalyst and they can participate directly in the radical polymerization by their unsaturated hydrocarbon radicals.
- Further expedient acids from which the precursor compounds of the formula I and / or II can be prepared with R 3 -COO or R 1 O are glutaric acid, lactic acid (R 1 is (CH 3 ) (HO) CH-), citric acid (R 1 HOOCCH 2 C (COOH) (OH) CH 2 -), vulpinic acid, terephthalic acid, gluconic acid, adipic acid, where all carboxyl groups may also be Si-functionalized, benzoic acid (R 1 is phenyl), nicotinic acid (vitamin B3, B5).
- R 1 corresponds to corresponding radicals, such as starting from tryptohan, L-arginine, L-histidine, L-phenyalanine, L-leucine, preference being given to using L-leucine
- the silicon-containing precursor compound of an organic acid is active in particular in hydrolyzed form as silane hydrolysis and / or silanol condensation catalyst via the released organic acid and even in hydrolyzed or unhydrolyzed form for grafting onto a polymer and / or co-polymerization with a base polymer, polymer / Monomer or prepolymer or for crosslinking, for example as a primer suitable.
- the silanol compound formed in the condensation contributes to crosslinking by means of formed Si-O-Si siloxane bridges and / or Si-O substrate or carrier material.
- This crosslinking can be carried out with other silanols, siloxanes or in general with functional groups suitable for crosslinking on substrates, fillers and / or carrier materials.
- Preferred fillers and / or carrier materials are therefore aluminum hydroxides, magnesium hydroxides, pyrogenic Silica, precipitated silica, silicates and other of the following fillers and support materials.
- Very particularly preferred precursor compounds are vinylsilanthmyristate, vinylsilane laurate, vinylsilane tricaprate and corresponding allylsilane compounds of the abovementioned acids, and / or silanetetracarboxylates Si (OR 1 ) 4 , such as silane tetramyrate, silane tralaurate, silanetetracate, or mixtures of these compounds. It is expedient to use vinylsilanteresterarate, vinylsilane tripalmitate, alkylsilane stearate and / or alkylsilane tripalmitate in specific dosages.
- Silane stearates and / or palmitates should preferably be metered so that not more than 0.05 wt .-%, preferably between 0.01 wt .-% and 0 wt .-%, in particular 0.01 to less than 0.001 wt. % of released acid, such as stearic acid or palmitic acid, are present in the total composition in weight percent of the polymer compound or polymer produced.
- Particularly preferred silicon-containing precursor compounds are in any case those in which the acid or one of the organic acids has at least one hydrophobic group which allows solubilization or dispersibility with the plastic.
- These are, in particular, long-chain, branched or cyclic, nonpolar, in particular unsubstituted, hydrocarbon radicals, in particular having 6 to 22 C atoms, preferably having 8 to 14 C atoms, particularly preferably having 8 to 13 C atoms, having at least one carboxylic acid group.
- Suitable substituted hydrocarbon radicals are preferably halogen-substituted hydrocarbon radicals.
- the silicon-containing precursor compound I and / or II is preferably also or alternatively used for grafting onto a polymer and / or for co-polymerization with a monomer, prepolymer or base polymer and subsequent moisture crosslinking in the context of the present invention.
- the preparation of the carboxysilanes has long been known to the person skilled in the art.
- US 4,028,391 discloses processes for their preparation in which chlorosilanes are reacted with fatty acids in pentane.
- US 2,537,073 discloses another method.
- the acid may be refluxed directly in a non-polar solvent such as pentane with trichlorosilane or with a functionalized trichlorosilane to yield the carboxysilane.
- a non-polar solvent such as pentane with trichlorosilane or with a functionalized trichlorosilane
- tetracarboxysilanes for example, tetrachlorosilane is reacted with the appropriate acid in a suitable solvent (Zeitschrift für Chemie (1963), 3 (12), 475-6).
- Further processes relate to the reaction of the salts or anhydrates of the acids with tetrachlorosilane or functionalized trichlorosilanes.
- Organic acids are understood as meaning carboxylic acids which have no sulfate or sulphonic acid groups; in particular they are organic acids corresponding to R 3 -COOH; the silicon-free precursor compound may also be the anhydrides, esters or salts of these organic acids, particularly preferably they have via a long-chain, nonpolar, in particular substituted or unsubstituted hydrocarbon radical, where the hydrocarbon radical may be saturated or unsaturated, for example where R 3 is 1 to 45 C atoms, in particular 4 to 45 C atoms, preferably 8 to 45 C atoms , in particular having 6 to 22 carbon atoms, preferably having 8 to 22 carbon atoms, more preferably having 6 to 14 carbon atoms, particularly preferably having R 3 is 8 to 13 carbon atoms, where R 3 is 11 to 13 C atoms are particularly preferred, these are, for example, lauric acid or myristic acid; or hydrogen (R 3 ) and at least one carboxylic acid group (COOH). Explicitly excluded from the definition of organic
- those acids with long chain, hydrophobic hydrocarbon radicals are clearly preferred. These acids can also function as dispersing aids and / or processing aids.
- a general requirement of the silicon-containing precursor compound is that it be hydrolyzable under the process conditions of the monosil and / or Sioplas process, thus releasing the free organic acid.
- the hydrolysis should preferably occur only in the crosslinking step of the process, in particular after shaping, for example by entering the water bath or after shaping in the presence of moisture.
- the silicon-free precursor compounds are excluded from those which are hydrolyzed by hydrolysis to an inorganic and an organic acid. In the present case no silanol is detected as the inorganic acid.
- the silicon-containing precursor compound of an organic acid can be applied to a carrier material, incorporated in a carrier material and / or encapsulated.
- the silicon-containing precursor compound of an organic acid, in particular of the formula I and / or II, in a composition or a masterbatch may optionally be present with an organofunctional silane compound, optionally a free radical generator and optionally a further silanol condensation catalyst, if used as silane hydrolysis catalyst and / or is used as a silanol condensation catalyst and / or for grafting onto a polymer, for co-polymerisation or as an adhesion promoter.
- At least one silicon-containing precursor compound in particular an organic acid of the general formula I and / or II, is used as catalyst together with an organofunctional silane compound corresponding to an unsaturated or olefinic alkoxysilane, wherein the silane compound particularly preferably corresponds to a monounsaturated alkoxysilane.
- the silicon-containing precursor compound is used as a catalyst in a monosil, Sioplas and / or in a co-polymerization process or process.
- a monosil, Sioplas and / or in a co-polymerization process or process is particularly suitable.
- the Silanhydrolyse- and / or Silanol condensation catalyst effective only if additional moisture is added. Therefore, the final crosslinking of the unfilled or filled polymer generally takes place in a known manner in a water bath, in a steam bath, or by atmospheric moisture at ambient temperatures (so-called "ambient curing").
- the organofunctional silane compound is particularly suitable for grafting onto a polymer and / or for co-polymerizing with a monomer, prepolymer or base polymer and subsequent moisture crosslinking in the context of the present invention.
- Preferred organofunctional silane compounds are unsaturated alkoxysilanes, particularly preferably of the general formula III, such as vinylalkoxysilane,
- R 7 are the same or different and R 7 is a hydrogen atom or a methyl group or a phenyl group
- the group E is a group from the group -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 -, -O (O) C (CH 2 ) 3 - or -C (O) O- (CH 2 ) 3 -
- q is 0 or 1, such as vinyl, allyl, n-3-pentyl, n-4-butenyl, 3-methacryloxypropyl and / or acryloxypropyl, or isoprenyl, hexenyl, cyclohexenyl, terpenyl, squalanyl , Squalenyl, polyterpenyl, betulaprenoxy, cis /
- R 5 is independently methyl, ethyl, n-propyl or iso-propyl,
- R 4 is independently a substituted or unsubstituted hydrocarbon group, in particular a substituted or unsubstituted linear, branched and / or cyclic alkyl, alkenyl, alkylaryl, alkenylaryl and / or aryl group having 1 to 24 carbon atoms , in particular having 1 to 16 C atoms, preferably having 1 to 8 C atoms.
- the substituted groups are especially hydrophobic.
- alkyl groups are ethyl, n-propyl, i-propyl, n-butyl, i-butyl, cyclohexyl, n-octyl, i-octyl, hexadecyl and substituted Alkyl group are in particular a haloalkyl group having chlorine, bromine substituents, preferably for nucleophilic substitution suitable haloalkyl groups, such as 3-chloropropyl or 3-bromopropyl groups.
- B particularly preferably comprises at least one olefin group, such as polyethylene, polypropylene, propylene copolymer or ethylene copolymer, especially if the composition contains no components of group b), optionally together with a free radical generator and further stabilizers and / or additives ,
- organofunctional silane compounds of the general formula III to vinylthmethoxysilane, vinyltriethoxysilane, vinylmethyldialkoxysilane, vinylthethoxymethoxysilane (VTMOEO), vinyltri-i-propoxysilane, vinyltri-n-butoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane (MEMO) and / or vinylethoxydimethoxysilane and / or allylalkoxysilanes such as allylthethoxysilane.
- VTMOEO vinylthethoxymethoxysilane
- MEMO 3-methacryloxypropyltriethoxysilane
- MEMO 3-methacryloxypropyltrimethoxysilane
- vinylethoxydimethoxysilane and / or allylalkoxysilanes such as allylthethoxysilane.
- the organofunctional silane compounds used may also be unsaturated siloxanes, such as preferably oligomeric vinylsiloxanes or mixtures of the abovementioned compounds.
- Preferred organofunctional silane Compounds contain either a vinyl or methacrylic group, since these compounds are reactive towards radicals and suitable for grafting onto a polymer chain or co-polymerizing with monomers, prepolymers.
- the at least one silicon-containing precursor compound in particular of the formula I and / or II, if appropriate together with a free-radical generator and / or an organofunctional silane compound, in a monosil process, Sioplas process and / or in a co-polymerization process.
- a free-radical generator and / or an organofunctional silane compound in a monosil process, Sioplas process and / or in a co-polymerization process.
- thermoplastic base polymers in a Monosil or Sioplas process or in a co-polymerization process together with monomers and / or prepolymers of thermoplastic base polymers.
- the hydrolysis of the precursor compound is preferably carried out after the shaping, in particular with the addition of heat, in the presence of moisture. Preferably of added moisture.
- the use of the silicon-containing precursor compound can also be carried out together with other silanol condensation catalysts comprising dibutyltin dilaurate, dioctyltin dilaurate; Dioctyltin di (2-ethylhexanoate) ((C 8 H 17) 2 Sn (OOCC 7 H 15) 2), dioctyltin di (isooctyl mercaptoacetate) ((C 8 H 17) 2 Sn (SCH 2 CO 2 C 8 H 17) 2), dibutyltin dicarboxylate ((C 4 H 9) 2 Sn (OOC-R) 2), monobutyltin ths - (2-ethylhexanoate) ((C4H9) Sn (OOCC7H15) 3), dibutyltin dineodecanoate ((C4H9) 2Sn (OOCC9H19) 2), laurylstannoxane ([(C4H)
- ABS acrylonitrile-butadiene-styrene
- PA polyamides
- PMMA polymethyl methacrylate
- PC polycarbonate
- PE polyethylene
- PP polypropylene
- PS polystyrene
- PVC polyvinyl chloride
- EVA ethylene-vinyl acetate copolymers
- EPM EPDM or EPM
- / or celluloid or silane-co-polymerized polymers understood and as monomers and / or prepolymers precursors of these base polymers, such as ethylene, propylene.
- Other thermoplastic base polymers are mentioned below.
- thermoplastic base polymers are a silane-grafted base polymer, a silane-co-polymerized base polymer and / or monomer and / or prepolymer of these base polymers, or else silane block co-prepolymers or block co-prepolymers and / or mixtures thereof.
- the thermoplastic base polymer is a nonpolar polyolefin such as polyethylene, polypropylene or a polyvinyl chloride or a silane-grafted polyolefin and / or silane-co-polymerized polyolefin and / or a copolymer of one or more olefins and one or more co-monomers contain polar groups.
- thermoplastic base polymer can also act partially or completely as a carrier material, for example in a masterbatch comprising as carrier material a thermoplastic base polymer or a polymer and the silicon-containing precursor compound of an organic acid and optionally an organofunctional silane compound and / or a free radical generator.
- silane-co-polymerized thermoplastic base polymers are also ethylene-silane copolymers, for example, ethylene-vinyltrimethoxysilane copolymer, ethylene-vinyltriethoxysilane copolymer, ethylene-dimethoxyethoxysilane copolymer, ethylene-gamma-trimethoxysilane copolymer, ethylene gamma (meth) acryloxypropyltriethoxysilane co-polymer, ethylene-gamma-acryloxypropyltriethoxysilane co-polymer, ethylene-gamma-acryloxypropyltriethoxysilane co-polymer, ethylene-gamma (meth) acryloxypropyltrimethoxysilane co-polymer, ethylene-gamma-acryloxypropyltrimethoxysilane co-polymer and / or ethylene-triacetoxysilane co-polymer
- Thermoplastics such as, in particular, a pure PE type can be used as non-polar thermoplastic base polymers, for example PE-LD, PE-LLD, PE-HD, m-PE.
- Polar groups carrying base polymers give z. B. improved fire behavior, d. H. lower flammability and flue gas density, and increase the Grestoffabilityfried.
- Polar groups are z. B. hydroxyl, nitrile, carbonyl, carboxyl, acyl, acyloxy, carboalkoxy or amino groups and halogen atoms, in particular chlorine atoms.
- Non-polar are olefinic double bonds or C-C triple bonds.
- Suitable polymers are in addition to polyvinyl chloride co-polymers of one or more olefins and one or more co-monomers containing polar groups, for.
- vinyl acetate vinyl propionate, (meth) acrylic acid, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, acrylonitrile.
- the co-polymers are the polar groups, for example in amounts of 0.1 to 50 mol%, preferably from 5 to 30 mol%, based on the polyolefin units.
- Particularly suitable base polymers are ethylene-vinyl acetate copolymers (EVA).
- EVA ethylene-vinyl acetate copolymers
- a suitable commercial co-polymer contains 19 mole% vinyl acetate and 81 mole% ethylene building blocks.
- Particularly suitable base polymers are polyethylene, polypropylene, and corresponding silane-modified polymers.
- silicon-containing precursor compounds of an organic acid in a composition or a masterbatch in particular silane-grafted, silane-co- polymerized and / or silane-crosslinked PE, PP, polyolefin copolymer, EVA, EPDM, EPM advantageously available.
- the silane-grafted polymers can be filled with fillers or be present unfilled and, optionally, after molding, then wetted keitsvernetzt. The same applies to the silane-co-polymerized, filled with fillers or unfilled polymers, which can optionally be wetted keitsvernetzt after shaping, then moist.
- the invention also provides the use of a silicon-containing precursor compound of an organic acid, in particular of the formula I and / or II, in the preparation of unfilled Si-crosslinked and / or in the preparation of filled Si-crosslinked polymer compounds; and / or correspondingly filled silicon crosslinked or unfilled Si-crosslinked polymers based on thermoplastic base polymers.
- Si-crosslinking is understood to mean the formation of a Si-O-substrate bond or Si-O-Si bond, for example between silanols, such as the hydrolyzed organofunctionalized silane (III), silicates, silicic acids or derivatives.
- Suitable substrates are all functionalized substrates capable of condensation, in particular the fillers, support materials, pigments mentioned, or hydrolysis and / or condensation products of the organofunctional silanes etc.
- Another object of the invention provides for the use of at least one silicon-containing precursor compound of an organic acid in the production of articles, in particular moldings, preferably of cables, hoses or pipes, more preferably of drinking water pipes or hoses in the medical field.
- the silicon-containing precursor compound of an organic acid may be liquid, waxy to solid, preferably waxy to solid or bound, incorporated or encapsulated onto a support material.
- the precursor compound is easily anhydrous be stored and dosed easily. Unwanted hydrolysis and / or condensation prior to use, especially in a monosil, Sioplas or co-polymerization process can be prevented.
- the silicon-containing precursor compound of an organic acid of the general formula I and / or II, the organofunctional silane compound and optionally the free-radical initiator may be applied to a support material, as described, for example, in EP 0 426 073 is described.
- the silicon-containing precursor compound I and / or II itself can itself be used as support material, in particular for an organofunctional silane, for example for supporting a silane of the general formula III, for example vinylthethoxysilane, vinylthmethoxysilane, vinyltris (methoxyethoxy) silane, vinyl (co) oligomers or other liquid silanes of the formula III.
- an organofunctional silane for example for supporting a silane of the general formula III, for example vinylthethoxysilane, vinylthmethoxysilane, vinyltris (methoxyethoxy) silane, vinyl (co) oligomers or other liquid silanes of the formula III.
- the at least one silicon-containing precursor compound of an organic acid can be applied to a carrier material, incorporated into a carrier material and / or encapsulated.
- a carrier material incorporated into a carrier material and / or encapsulated.
- the silicon-containing precursor compound of an organic acid solid or free-flowing.
- This can also be provided, for example, in a composition or a masterbatch, optionally with an organofunctional silane compound and / or optionally a free-radical generator and, in particular at least one further silane hydrolysis and / or silanol condensation catalyst, as a solid, free-flowing formulation. This can be done for example on and / or in a carrier material and / or filler as a carrier.
- the support may be porous, particulate, swellable or optionally foamy.
- Polyolefins such as PE, PP, EVA are particularly suitable as support material or polymer blends and as fillers inorganic or mineral, which may be advantageous reinforcing, stretching and flame retardant.
- the carrier materials and fillers are specified below.
- Preferred free-radical formers are organic peroxides and / or organic peresters or mixtures thereof, such as preferably tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, 3-Di (2-t-butylperoxy-isoproyl) benzene, 2,5-dimethyl-2,5-bis (te / t-butylperoxy) hexyne (3), di-t-t-amyl peroxide, 1, 3 , 5-tris (2-te / t-butylperoxy-isopropyl) benzene, 1-phenyl-1 th / t- butylperoxyphthalid, alpha, alpha '-bis (te / t-butylperoxy) diisopropyl benz
- n-butyl-4,4-di (tert-butylperoxy) valerate ethyl 3,3-di (tert-butylperoxy) butyrate and / or 3,3,6,9, 9-hexamethyl-1,2,4,5-tetraoxa-cyclononane.
- composition or a masterbatch can be carried out together with at least one stabilizer and / or further additive and / or additives or mixtures thereof.
- Metal deactivators, processing aids, inorganic or organic pigments, fillers, support materials, adhesion promoters may optionally be used as stabilizer and / or as further additives.
- titanium dioxide TiO 2
- talc clay, quartz, kaolin, aluminum hydroxide, magnesium hydroxide, bentonite, montmorillonite, mica (muscovite mica), calcium carbonate (chalk, dolomite), paints, pigments, talc, carbon black, SiO 2, precipitated silica, fumed silica
- Aluminum oxides such as alpha and / or gamma-alumina, alumina hydroxides, boehmite, barite, barium sulfate, lime, silicates, aluminates, aluminum silicates and / or ZnO or mixtures thereof.
- the carrier materials or additives such as pigments, fillers, powdered, particulate, porous, swellable or possibly foamy, are preferably present.
- Preferred metal deactivators are, for example, N, N'-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine and tris (2-tert-butyl-4-thio (-) 2 '-methyl-4-hydroxy-5'-te / t.-butyl) phenyl-5-methyl) phenyl phosphite.
- the use, in particular in a composition or a masterbatch, can be carried out together with further components, such as at least one thermal stabilizer, for example pentaerythrityl tetrakis [3- (3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 4,4'-bis- (1, 1-dimethylbenzyl) -diphenylamine.
- at least one thermal stabilizer for example pentaerythrityl tetrakis [3- (3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 4,4'-bis- (1, 1-dimethylbenzyl) -diphen
- the fillers used are generally inorganic or mineral and may advantageously have a reinforcing, stretching and flame retardant effect. They carry at least on their surfaces groups which can react with the alkoxy groups, the hydroxyl groups of the silanols or the unsaturated silane compound or the hydrolyzed compound of the formula I and / or II. As a result, the silicon atom having the functional group bonded thereto can be chemically fixed on the surface. Such groups on the surface of the filler are especially hydroxyl groups.
- preferably used fillers are metal hydroxides with a stoichiometric proportion or, in their different dehydration stages, with a substoichiometric proportion of hydroxyl groups up to oxides with comparatively few remaining, but detectable by DRIFT-IR spectroscopy or NIR spectroscopy hydroxyl groups.
- fillers used are aluminum trihydroxide (ATH), aluminum oxide hydroxide (AIOOH.aq), magnesium dihydroxide (MDH), brucite, huntite, hydromagnesite, mica and montmorillonite.
- ATH aluminum trihydroxide
- AIOOH.aq aluminum oxide hydroxide
- MDH magnesium dihydroxide
- brucite huntite, hydromagnesite, mica and montmorillonite.
- calcium carbonate talc and glass fibers can be used.
- so-called "char former” such as ammonium polyphosphate, stannates, borates, talc, or such can be used in combination with other fillers.
- the carrier material is preferably a porous polymer selected from the group consisting of polypropylene, polyolefins, low-carbon alkenylene-ethylene copolymer, ethylene-vinyl acetate copolymer, high density polyethylene, low density polyethylene or linear low density polyethylene.
- the porous polymer may have a pore volume of 30 to 90% and in particular granulated or can be used in pellet form.
- the carrier material may also be a filler or additive, in particular a nanoscale filler.
- Preferred support materials, fillers or additives are aluminum hydroxide, magnesium hydroxide, fumed silica, precipitated silica, wollastonite, calcined variants, chemically and / or physically modified, for example kaolin, modified kaolin, in particular ground, exfoliating materials, such as sheet silicates, preferably special kaolins, a calcium silicate , a wax, such as a polyolefin wax based on LDPE ("low density polyethylene”), or a carbon black.
- LDPE low density polyethylene
- the support material may encapsulate or physically or chemically bond the silicon containing precursor compound and / or the organofunctional silane compound and / or the free radical generator, especially as a masterbatch. It is advantageous if the loaded or unloaded carrier material is swellable, in particular in a solvent.
- the amount of the silicon-containing precursor compounds is in the range of 0.01% by weight to 99.9% by weight, preferably between 0.01% by weight to 70% by weight, particularly preferably between 0.1% by weight % to 50% by weight, particularly preferably between 0.1% by weight to 30% by weight, based on the total weight comprising the carrier material, of the organofunctional silane compound and / or of the free-radical former.
- the support material is therefore usually present at 99.99 to 70% by weight, based on the total weight (ad 100% by weight).
- ATH aluminum trihydroxide, Al (OH) 3
- magnesium hydroxide Mg (OH) 2
- fumed silica which is produced on an industrial scale by continuous hydrolysis of silicon tetrachloride in a oxyhydrogen flame.
- the silicon tetrachloride is vaporized and then reacts spontaneously and quantitatively within the flame with the water resulting from the oxyhydrogen gas reaction.
- the fumed silica is an amorphous modification of the silica in the form of a loose, bluish powder.
- the particle size is usually in the range of a few nanometers, the specific surface area is therefore large and is generally from 50 to 600 m 2 / g.
- Precipitated silicas are generally prepared from soda water solutions by neutralization with inorganic acids under controlled conditions. After separation from the liquid phase, washing and drying, the crude product is finely ground, z. B. in steam jet mills.
- Precipitated silica is also a broad amorphous silica which typically has a specific surface area of 50 to 150 m 2 / g. Precipitated silica has a certain porosity, in contrast to fumed silica, for example approx. 10% by volume.
- the uptake of the vinylalkoxysilanes and / or the silicon-containing precursor compound or mixtures thereof can therefore be effected both by adsorption on the surface and by absorption in the pores.
- Calcium silicate is generally produced industrially by fusing quartz or diatomaceous earth together with calcium carbonate or oxide or by precipitating aqueous sodium metasilicate solutions with water-soluble calcium compounds. The carefully dried product is usually porous and can absorb water or oils up to five times the weight.
- Porous polyolefins such as polyethylene (PE) or polypropylene (PP), as well as copolymers, such as ethylene copolymers with low carbon alkenes, for example, propene, butene, hexene, octene, or ethylene vinyl acetate (EVA), are prepared by specific polymerization techniques and procedures.
- the particle sizes are generally between 3 and ⁇ 1 mm, and the porosity can be more than 50% by volume. so that the products may suitably be capable of absorbing large quantities of unsaturated organosilane / mixtures, for example of general formula III, and / or the silicon-containing precursor compound or mixtures thereof, without losing their free-flow properties.
- Suitable waxes are in particular polyolefin waxes based on "low density polyethylene” (LDPE), preferably branched, with long side chains.
- LDPE low density polyethylene
- the melting and solidification point is generally between 90 and 120 ° C.
- the waxes can generally be mixed well in a low-viscosity melt with the unsaturated organosilanes, such as vinylalkoxysilane, and / or the silicon-containing precursor compound or mixtures thereof.
- the solidified mixture is generally sufficiently hard that it can be granulated.
- Soot in its various forms of trade is suitable for. B. for the production of black cable sheathing.
- the following methods are available:
- mineral carriers or porous polymers are generally preheated, eg. B. in a heating cabinet at 60 0 C, and placed in a cylindrical container, which was purged with dry nitrogen and filled.
- a vinylalkoxysilane and / or vinylcarboxysilane are then added and the container placed in a rolling device which rotates for about 30 minutes. After this time, usually from the carrier and the liquid, highly viscous or waxy alkoxysilane and / or carboxysilane, a free-flowing, superficially dry granules has formed, which expediently stored under nitrogen in opaque containers becomes.
- the heated carrier may be placed in a dry nitrogen purged and filled mixer, e.g. As a ploughshare mixer type L ⁇ DIGE or a propeller mixer type HENSCHEL.
- the mixer can now be put into operation and the olefinic alkoxysilane and / or carboxysilane, especially of formula I, or mixtures of these are sprayed after reaching the maximum mixing power through a nozzle. After completion of the addition is generally homogenized for about 30 minutes and then the product, for. B. filled by means of a dry nitrogen operated pneumatic conveying, in opaque, filled with nitrogen containers.
- Wax / polyethylene wax in pelleted form with a melting point of 90 to 120 0 C or higher can be melted in portions in a heatable vessel with stirrer, reflux condenser and diesstechnikszugabevorides and kept in the molten state. Dry nitrogen is conveniently passed through the apparatus throughout the manufacturing process.
- the liquid vinylcarboxysilane / mixtures can be added to the melt by means of the liquid addition device and mixed with the wax by intensive stirring.
- the melt is then discharged to solidify in molds, and the solidified product is granulated.
- the melt may be dropped onto a chilled forming belt, on which it solidifies in a convenient pastille mold.
- the composition used consists of a selection of a silicon-containing precursor compound of an organic acid, in particular of the formula I and / or II, and optionally a monounsaturated alkoxysilane and / or a further silanol condensation catalyst, such as one of said tin compounds, and or a radical generator and optionally at least one stabilizer and / or additive and / or carrier material and / or additive and / or mixtures thereof.
- the composition used consists of a selection of a precursor compound of the formula I and / or II, where R 1 corresponds to a carbonyl-R 3 group with R 3 equal to 4 to 45 C atoms, preferably with 6 to 45 C atoms.
- Atoms in particular having 6 to 22 carbon atoms, preferably having 8 to 22 carbon atoms, more preferably having 6 to 14 carbon atoms, more preferably having R 3 is 8 to 13 carbon atoms, in particular with R 3 is 11 to 13 C-atoms, and optionally an olefinic alkoxysilane, in particular of the formula III, and / or a free-radical generator and / or a further silanol condensation catalyst and optionally at least one stabilizer and / or additive and / or carrier material and / or additive and / or mixtures thereof.
- the invention also provides a masterbatch, in particular for crosslinking thermoplastic base polymers, comprising at least one silicon-containing precursor compound of an organic acid and at least one free-radical initiator.
- an object of the invention is a masterbatch, in particular for the crosslinking of thermoplastic base polymers, comprising as component A at least one silicon-containing precursor compound of an organic acid, in particular the general formula I and / or II as defined above and a support material, and optionally as component B, a radical generator and optionally as component C an organofunctional silane compound, in particular an unsaturated alkoxysilane, preferably of the formula III, wherein b, a, B, R 4 and R 5 are as defined above, wherein at least one of above component A, -B and / or -C is supported or encapsulated.
- At least one of the components is applied to at least one carrier or a carrier material, incorporated or encapsulated by a carrier material.
- the masterbatch or one of component A, B and / or C may further comprise at least one additive, stabilizer, additive or mixtures thereof.
- the organofunctional silane compound is supported on and / or encapsulated in the silicon-containing precursor compound.
- Component A preferably contains at least one silicon-containing precursor compound of an organic acid, in particular of the general formula I and / or II corresponding to the above definition, to 0.01 to 99.9% by weight in component A, in particular 0.01 up to 70% by weight, preferably 0.1 to 50% by weight, particularly preferably 0.1 to 30% by weight, and ad 100% by weight of a carrier material or in alternatives additionally at least one stabilizer, an additive, an additive or mixtures thereof ad 100 wt .-% of component-A.
- the radical generator of component B is usually present at 0.05 to 10 wt .-% in the component-B, ad 100 wt .-% of the component-B at least one additive, carrier material, stabilizer, additive or mixtures thereof.
- the organofunctional silane compound, in particular of the formula III, of the component C is usually present at 60 to 99.9 wt .-% in the component-C, wherein ad 100 wt .-% of the component-C at least one additive, carrier material Stabilizer, additive or mixtures of these.
- Suitable radical formers, additives, stabilizers, additives and support materials are described above.
- Suitable carrier materials are, in particular, those mentioned above, such as PE, PP and others of the abovementioned. The same applies to the radical generator and the stabilizer.
- Component A and B or -A and C are preferably present in the masterbatch separately if they are to be used in two process steps. When used concurrently, components A, B and / or C may be present together in a physical mixture, for example as a powder, granules, pellets, or also formulated together in a single formulation, for example as a pellet or tablet.
- a preferred masterbatch comprises, for example, 6% by weight of a silicon-containing precursor compound of an organic acid, for example a fatty acid, in particular myristic acid or lauric acid, on a polymeric carrier material such as PE-HD, PE-HD ad 100% by weight. with 94 wt .-% of the masterbatch (component-A) is present.
- Further masterbatches comprise silicon-containing precursor compounds of an organic acid based on behenic acid, L-leucine, capnic acid, oleic acid, lauric acid and / or myristic acid, optionally mixed on a carrier material, for example PE-HD.
- Component-C may preferably be an unsaturated alkoxysilane, in particular of the formula III, or oligomeric siloxanes prepared therefrom, preferably vinyltrimethoxysilane or vinyltriethoxysilane, together with a free-radical generator and a stabilizer, optionally with further additives.
- a carrier material for example as granules.
- the silicon-containing precursor compounds of an organic acid for example in a composition or a masterbatch, are used as silane hydrolysis catalyst and / or silanol condensation catalyst in a monosil, sioplas or co-polymerisation process, in particular for producing filled and / or unfilled polymer compounds which crosslink or uncrosslinked, and / or crosslinked filled and / or unfilled polymers based on thermoplastic base polymers.
- Crosslinking in the sense of the invention means in particular the formation of an Si-O substrate bond or Si-O filler, Si-O support material or Si-O-Si bridging, i. the condensation of a Si-OH group with a condensable further group of a substrate.
- the invention also relates to the use of a silicon-containing precursor compound of an organic acid, in particular of the formula I and / or II, in the preparation of a silicon-containing polymer, polymer compound, an unfilled crosslinked polymer and / or a filled crosslinked polymer.
- the use is preferably carried out in a monosil, Sioplas and / or in a Co Polymehsations vide.
- the silicon-containing precursor compound I and / or II can also be used for grafting onto a polymer and / or for co-polymerization with a monomer, prepolymer or base polymer and subsequent moisture crosslinking in the context of the present invention.
- silane-grafted, silane-co-polymerized and / or crosslinked, in particular siloxane-crosslinked, filled or unfilled polymers Preference is given to the use for producing silane-grafted, silane-co-polymerized and / or crosslinked, in particular siloxane-crosslinked, filled or unfilled polymers.
- the aforementioned polymers may also comprise block copolymers.
- the fillers are preferably also crosslinked with the silicon-containing compounds, in particular via a Si-O filler / carrier material bond. Suitable fillers are, in particular, the abovementioned fillers or support materials.
- the invention also provides the use of the silicon-containing precursor compound in the preparation of a polymer, polymer compound such as an unfilled crosslinked polymer and / or a filled crosslinked polymer, cable compounds, a filled plastic, molded article and / or article.
- Corresponding shaped articles and / or articles are cables, hoses, pipes, such as drinking water pipes, or articles which are used in the food industry or in the field of hygiene articles, in the field of medical technology, for example as a medical instrument or part of a medical instrument, Braunüle, trocar, stent, clot - Rethever, vascular prosthesis, as a component on a catheter, to name a few, can be used.
- the moisture-crosslinked unfilled or filled polymer compounds according to the invention are advantageously prepared by mixing the respective educt components, correspondingly prepared in the melt, with exclusion of moisture.
- the respective educt components correspondingly prepared in the melt, with exclusion of moisture.
- the usual heatable homogenizers z.
- Buss co-kneader or twin-screw extruder Alternatively, a single-screw extruder may be used.
- the components can be used individually or in each case
- Partial mixtures in the given ratio continuously to a Temperature above the melting point of the thermoplastic polymer base heated extruder can be supplied. Suitably, the temperature will rise towards the end of the screw to adjust a lower viscosity and thereby allow intimate mixing.
- the extrudates are expediently still liquid supplied to a device for forming granules or moldings, such as pipes or hoses.
- the final crosslinking of the unfilled or filled polymer generally takes place in a known manner in a water bath, in a steam bath, or by atmospheric moisture at ambient temperatures (so-called "ambient curing").
- the invention also provides an article containing a silicon-containing precursor compound of an organic acid, in particular of the formula I and / or III, and / or their hydrolysis and / or condensation products, in particular a shaped article of a polymer, such as a crosslinked filled or crosslinked unfilled Polymer; preferably a cable, flame retardant cable, for example, filled with Mg (OH) 2 , Al (OH) 3 or exfoliating materials such as sheet silicates; or a pipe, for example a drinking water pipe, a hose in the medical sector or articles which are used in the food sector or in the field of hygiene articles, in the field of medical technology, for example as a medical instrument or part of a medical instrument, hose, Braunüle, trocar, stent, clot Rethever, vascular prosthesis, as a component on a catheter, just to name a few, can be used.
- a silicon-containing precursor compound of an organic acid in particular of the formula I and / or III, and / or their hydrolysis and
- a composition may suitably be used as composition which comprises an organofunctional silane compound, in particular of the formula III, a free-radical former, and a silicon-containing precursor compound of an organic acid and optionally a further silanol condensation reagent. and optionally a stabilizer.
- the inorganic filler is usually fed directly to the treatment unit and processed with the polymer to the final product.
- the filler may also be introduced into the unit at a later time, e.g. B. in twin-screw extruder or co-kneader.
- the graft polymer produced using the silicon-containing precursor compound of an organic acid enables a marked improvement in the compatibility of nonpolar polymer and polar filler such as aluminum hydroxide or magnesium hydroxide.
- a graft polymer in particular Sioplas material, optionally granulate, pack, especially moisture protected, store and then deliver this as a base material to a processor, such as a cable producer or pipe manufacturer, in turn, by incorporation of Produces fillers filled plastic end products.
- alkenyltricarboxysilane 1 mol of an alkenyltrichlorosilane, or generally an alkenyltrihalosilane, is reacted directly with 3 mol or an excess of the organic mono-carboxylic acid or reacted in an inert solvent, in particular at elevated temperature.
- an alkyltricarboxysilane corresponding to 1 mol of an alkyltrichlorosilane with 3 mol or an excess of an organic mono- Carboxylic reacted directly or reacted in an inert solvent.
- the reaction preferably takes place at elevated temperature, for example up to the boiling point of the solvent or around the melting point of the organic fatty acid or of the organic acid.
- tetracarboxysilanes 1 mol of tetrahalosilane, in particular tetrachlorosilane or tetrabromosilane, is reacted with 4 mol or an excess of at least one mono-carboxylic acid, for example a fatty acid or fatty acid mixture.
- the reaction can be carried out directly by melting or in an inert solvent, preferably at elevated temperature.
- the clear liquid was transferred to a one-necked flask and the toluene was removed by rotary evaporation.
- the oil bath temperature was about 80 0 C set.
- the vacuum was adjusted stepwise to ⁇ 1 mbar.
- the product was a clear liquid.
- the liquid was characterized by NMR ( 1 H, 13 C, 29 Si) as Vinyltricaprylsilan.
- the vacuum was adjusted stepwise to ⁇ 1 mbar.
- the product was an oily yellow liquid with a slightly pungent odor.
- the liquid was essentially characterized by NMR ( 1 H, 13 C, 29 Si) as hexadecyltricarprylsilane.
- Reaction Dynasylan® VTC with myristic acid 40.5 g of myristic acid and 130 g of toluene are introduced into the reaction flask, mixed and heated to about 60 0 C. 9.5 g of Dynasylan® VTC are added dropwise within 15 minutes by means of a dropping funnel. Upon addition, the temperature in the flask is increased by about 10 0 C. After the addition is stirred for 15 minutes and then the temperature of the oil bath to 150 0 C increased. During the stirring, a gas evolution (HCL gas) is observed. It was stirred until no more gas evolution was observed (Gasabgangshahn) and stirred for 3h.
- HCL gas gas evolution
- Dynasylan PTCS reaction with myristic acid 40,5g Myhstin yarn and 150g of toluene are charged to the reaction flask, mixed and heated to about 60 0 C.
- Dynasylan® PTCS is removed within 15 minutes dropwise.
- the temperature in the flask increases by about 10 0 C.
- the temperature of the oil bath is raised to 150 0 C and stirred for 3 h.
- a gas evolution, HCL gas is observed. It was stirred until no more gas evolution was observed at the gas outlet cock.
- Dynasylan ® SILFIN 24 (vinyl trimethoxy (VTMO), peroxide, and
- the grafting took place on the twin-screw extruder (ZE 25) from Berstorff. Strands were made in the trials.
- the PE crosslinker preparation was in each case drummed for 1 h, whereby it was previously predried at 70 ° C. for about 1 h.
- the grafted strands were granulated after extrusion.
- the granules were packaged and sealed in bags coated with an aluminum layer immediately after granulation. Before welding, the granules were overlaid with nitrogen.
- the silane-grafted polyethylene was in a laboratory kneader (from Thermo Haake, 70 cm 3.) Kneaded with the respective catalyst (temperature profile: 140 ° C / 3 min; 2 min to 210 0 C; 210 ° C / 5min, Kneterfitiere: 30 rpm). Subsequently, the mixture was pressed at 200 0 C to plates. The crosslinking was carried out in a water bath at 80 ° C. crosslinked ( 4 h). The gel contents of the crosslinked plates were determined (8h, p-xylene, Soxhlett extraction).
- a catalyst masterbatch wherein the catalyst masterbatch contained 98 wt% PE-HD and 2 wt% catalyst (organic acid). The results can be found in Table 1.
- a HAAKE laboratory kneader is kneaded with 49.0 g of PE with 1.0 g of catalyst, organic acid or silicon-containing precursor compound.
- PE-HD Silfin 24 A mixture of 95% by weight PE-HD Silfin 24 is prepared with 5% by weight of the masterbatch comprising the catalyst. The processing took place on a HAAKE laboratory kneader. A mixture of 95 wt .-% PE-HD Silfin 24 mixture with 5 wt .-% masterbatch are kneaded, then pressed at 200 0 C to plates and last in a water bath at 80 0 C crosslinked.
- polyethylene was chemically modified with various vinyl silanes with the addition of peroxide (grafted, speed: 30 1 / min, TempProfil: 3 min at 140 0 C, 2 min from 140 0 C to 200 ° C, 10 min 200 0 C. ).
- peroxide grafted, speed: 30 1 / min, TempProfil: 3 min at 140 0 C, 2 min from 140 0 C to 200 ° C, 10 min 200 0 C.
- ATH aluminum trihydroxide
- the kneaded sample was pressed into a plate and then crosslinked in a water bath at 80 0 C.
- the gel content of the cross-linked samples after different storage times was measured.
- the produced carboxy-silanes were used as catalysts in the Sioplas process.
- wt .-% of a grafted with Dynasylan ® SILFIN 24 wt .-% polyethylene 5 of the catalyst concentrate according to the invention Karl-MB
- a masterbatch with 1 g of the respective catalyst and 49 g of PE-HD was prepared in the kneader (Temp. Profile: 5 min at 200 0 C). From this 2.5 g were then kneaded together with 47.5 g of the extruded Dynasylan ® SILFIN 24 PE-HD (temp.
Abstract
L'invention concerne l'utilisation d'un composé précurseur silicié d'un acide organique, en particulier d'un composé précurseur silicié oléfinique d'un acide organique et/ou d'un tétracarboxylsilane, pour produire des mélanges polymères ou des polymères non chargés et/ou chargés ou des plastiques chargés, tels que granulés ou produits finis, à partir de polymères de base thermoplastiques, de monomères et/ou de prépolymères des polymères de base thermoplastiques. Un produit fini est un article, par exemple un corps moulé, en particulier un câble, un tuyau ou un tube. L'invention concerne en outre un mélange maître contenant ce composé précurseur silicié.
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DE102008041919A DE102008041919A1 (de) | 2008-09-09 | 2008-09-09 | Verwendung von Silicium enthaltenden Vorläuferverbindungen einer organischen Säure als Katalysator zur Vernetzung von gefüllten und ungefüllten Polymer-Compounds |
PCT/EP2009/058718 WO2010028875A1 (fr) | 2008-09-09 | 2009-07-09 | Utilisation de composés précurseurs siliciés d'un acide organique comme catalyseurs pour la réticulation de mélanges polymères chargés et non chargés |
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US (1) | US20110144277A1 (fr) |
EP (1) | EP2331627A1 (fr) |
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CN (1) | CN102149763A (fr) |
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DE102008041918A1 (de) * | 2008-09-09 | 2010-03-11 | Evonik Degussa Gmbh | Silanolkondensationskatalysatoren zur Vernetzung von gefüllten und ungefüllten Polymer-Compounds |
DE102009027090A1 (de) | 2009-06-23 | 2010-12-30 | Evonik Degussa Gmbh | Magnetische Partikel und Polyethylen enthaltendes Kompositmaterial |
DE102010002358A1 (de) * | 2010-02-25 | 2011-08-25 | Evonik Degussa GmbH, 45128 | Carboxyfunktionalisierte Silicium enthaltende Vorläuferverbindung verschiedener organischer Carbonsäuren |
EP2690115B1 (fr) * | 2012-07-24 | 2018-02-21 | Borealis AG | Composition de polyoléfine reticulée lentment et partiellement pour améliorer la résistance d'articles aux désinfectants |
US10040888B1 (en) | 2013-06-14 | 2018-08-07 | Cooper-Standard Automotive Inc. | Composition including silane-grafted polyolefin |
US10100139B2 (en) | 2013-08-01 | 2018-10-16 | Cooper-Standard Automotive Inc. | Hose, composition including silane-grafted polyolefin, and process of making a hose |
CN111853380A (zh) | 2014-07-02 | 2020-10-30 | 库博标准汽车配件有限公司 | 软管、耐磨组合物和软管制造工艺 |
CN105025695A (zh) * | 2015-07-28 | 2015-11-04 | 苏州驭奇材料科技有限公司 | 具有阻燃特性的宽频电磁波吸收复合体及其制造方法 |
EP3551003A1 (fr) | 2016-12-10 | 2019-10-16 | Cooper-Standard Automotive, Inc. | Semelles de chaussure, compositions, et leurs procédés de fabrication |
CN110291168A (zh) | 2016-12-10 | 2019-09-27 | 库珀标准汽车公司 | 微致密密封件、制造其的组合物和方法 |
CA3143366A1 (fr) * | 2019-06-27 | 2020-12-30 | Dow Global Technologies Llc | Procede de fabrication d'un melange homogene de polyolefine et d'acide organique liquide |
Family Cites Families (55)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2537073A (en) | 1946-07-16 | 1951-01-09 | Montclair Res Corp | Substituted silicon acylates |
BE794718Q (fr) | 1968-12-20 | 1973-05-16 | Dow Corning Ltd | Procede de reticulation d'olefines |
GB1346588A (en) | 1970-10-14 | 1974-02-13 | Dow Corning Ltd | Cross linked polyolefin sheets and films and the preparation thereof |
US4028391A (en) | 1973-12-26 | 1977-06-07 | Owens-Corning Fiberglas Corporation | Method of preparing organosilicon carboxylates |
JPS5234923B2 (fr) | 1974-10-02 | 1977-09-06 | ||
GB1526398A (en) | 1974-12-06 | 1978-09-27 | Maillefer Sa | Manufacture of extruded products |
JPS5813613A (ja) | 1981-07-16 | 1983-01-26 | Dainichi Nippon Cables Ltd | ポリオレフインの架橋方法 |
GB8514330D0 (en) | 1985-06-06 | 1985-07-10 | Bp Chem Int Ltd | Polymer composition |
US4870111A (en) * | 1987-02-24 | 1989-09-26 | Astro-Valcour, Incorporated | Moldable silane-crosslinked polyolefin foam beads |
JPS6442509A (en) | 1987-08-07 | 1989-02-14 | Kobe Steel Ltd | Method for killing slag foaming |
US5112919A (en) | 1989-10-30 | 1992-05-12 | Union Carbide Chemicals & Plastics Technology Corporation | Solid feeding of silane crosslinking agents into extruder |
ES2120423T3 (es) * | 1991-06-08 | 1998-11-01 | Huels Chemische Werke Ag | Mezclas de oligomeros de siloxano en forma de cadena y ciclicos, procedimiento para su fabricacion, asi como su uso. |
DE4119332A1 (de) * | 1991-06-12 | 1992-12-17 | Huels Chemische Werke Ag | Verfahren zur herstellung von methylidengruppen enthaltenden (alpha), (omega) -ungesaettigten oligomeren aus (alpha), (omega) -diolefinen in gegenwart von aluminiumorganischen verbindungen als katalysator |
JPH05162237A (ja) | 1991-12-12 | 1993-06-29 | Sumitomo Bakelite Co Ltd | 複合積層板の製造方法 |
DE4233021A1 (de) * | 1992-10-01 | 1994-04-07 | Huels Chemische Werke Ag | Organosilanpolykondensate |
DE19508088A1 (de) * | 1995-03-08 | 1996-09-12 | Huels Chemische Werke Ag | Verfahren zur Herstellung eines Oligomer-Gemisches aus alpha,omega-Diolefinen |
DE19624032A1 (de) * | 1996-06-17 | 1997-12-18 | Huels Chemische Werke Ag | Oligomerengemisch kondensierter Alkylalkoxysilane |
DE19639782A1 (de) * | 1996-09-27 | 1998-04-02 | Huels Chemische Werke Ag | Glycidether-, Acryl- und/oder Methacryl-funktionelle Organopolysiloxan-haltige Zusammensetzungen auf Wasser-Basis, Verfahren zu deren Herstellung sowie deren Verwendung |
DE19818924A1 (de) * | 1998-04-28 | 1999-11-04 | Degussa | Oberflächenmodifizierte Füllstoffe, Verfahren zu deren Herstellung sowie deren Verwendung |
DE19834990B4 (de) * | 1998-08-03 | 2005-09-15 | Degussa Ag | Acryloxypropyl- oder Methacryloxypropyl-Gruppen enthaltende Siloxan-Oligomere, Verfahren zu ihrer Herstellung sowie deren Verwendung |
DE19848351A1 (de) * | 1998-10-21 | 2000-04-27 | Degussa | Vernetzbare Polymere, Verfahren zu deren Herstellung und Formkörper aus vernetzten Polymeren |
DE19849308A1 (de) * | 1998-10-27 | 2000-05-04 | Degussa | Aminopropyl-funktionelle Siloxan-Oligomere |
DE19904132C2 (de) * | 1999-02-03 | 2002-11-28 | Degussa | Zusammensetzung fluororganofunktioneller Silane und Siloxane, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE19929021A1 (de) * | 1999-06-25 | 2000-12-28 | Degussa | Funktionelle Organylorganyloxysilane auf Trägerstoffen in Kabelcompounds |
DE19961972A1 (de) * | 1999-12-22 | 2001-06-28 | Degussa | Organosilan- und/oder Organosiloxan-haltige Mittel für gefülltes Polyamid |
EP1195417B1 (fr) * | 2000-10-05 | 2009-10-14 | Evonik Degussa GmbH | Nanocapsules organosiliciés |
EP1195416A3 (fr) * | 2000-10-05 | 2005-12-28 | Degussa AG | Nanocapsules organosiliciés polymérisables |
DE10056344A1 (de) * | 2000-11-14 | 2002-05-16 | Degussa | n-Propylethoxysiloxane, Verfahren zu deren Herstellung und deren Verwendung |
JP3656545B2 (ja) | 2000-11-17 | 2005-06-08 | 日立電線株式会社 | シラン架橋ポリオレフィン成型物 |
DE10100384A1 (de) * | 2001-01-05 | 2002-07-11 | Degussa | Verfahren zur Modifizierung der Funktionalität von organofunktionellen Substratoberflächen |
EP1249470A3 (fr) * | 2001-03-30 | 2005-12-28 | Degussa AG | Composition fortement chargée en nano et/ou microcapsules hybrides à base de silice organique pâteuse pour des revêtements résistants aux rayures et à l'abrasion |
DE50210398D1 (de) * | 2001-03-30 | 2007-08-16 | Degussa | Siliciumorganische Nano-Mikrohybridsysteme oder Mikrohybridsysteme enthaltende Zusammensetzung für kratz- und abriebfeste Beschichtungen |
DE10132942A1 (de) * | 2001-07-06 | 2003-01-23 | Degussa | Siloxan-Oligomere, Verfahren zu deren Herstellung und deren Verwendung |
DE10141687A1 (de) * | 2001-08-25 | 2003-03-06 | Degussa | Siliciumverbindungen enthaltendes Mittel zur Beschichtung von Oberflächen |
DE10142555A1 (de) * | 2001-08-30 | 2003-03-20 | Degussa | Mittel für die Verbesserung der Scorch-Bedingungen bei der Herstellung gepfropfter und/oder vernetzter Polymere sowie gefüllter Kunststoffe |
DE10159952A1 (de) * | 2001-12-06 | 2003-06-18 | Degussa | Verwendung flüssiger oder auf Trägermaterial aufgebrachter ungestättigter Organosilan/-mischungen zur Herstellung von feuchtigkeitsvernetzten und gefüllten Kabelcompounds |
DE10212523A1 (de) * | 2002-03-21 | 2003-10-02 | Degussa | Lufttrocknende, silanhaltige Beschichtungsmittel |
DE10218871A1 (de) * | 2002-04-26 | 2003-11-13 | Degussa | Verfahren zur Imprägnierung von porösen mineralischen Substraten |
DE10238369A1 (de) * | 2002-08-22 | 2004-03-04 | Degussa Ag | Mittel als Haftvermittler für gefüllte und peroxidisch zu vernetzende Gummicompounds |
DE10327624B3 (de) * | 2003-06-20 | 2004-12-30 | Degussa Ag | Organosiliciumverbindungen, Verfahren zu ihrer Herstellung, sowie ihre Verwendung |
DE10362060B4 (de) * | 2003-10-21 | 2009-07-09 | Altana Coatings & Sealants Gmbh | Verpackungsmaterial mit einer Barriereschicht für Gase |
DE102004007456A1 (de) * | 2004-02-13 | 2005-09-01 | Degussa Ag | Hochgefüllte Polyolefin-Compounds |
DE102004037043A1 (de) * | 2004-07-29 | 2006-03-23 | Degussa Ag | Blockkondensate organofunktioneller Siloxane, deren Herstellung, Verwendung sowie deren Eigenschaften |
DE102004049427A1 (de) * | 2004-10-08 | 2006-04-13 | Degussa Ag | Polyetherfunktionelle Siloxane, polyethersiloxanhaltige Zusammensetzungen, Verfahren zu deren Herstellung und deren Verwendung |
DE102005004871A1 (de) * | 2005-02-03 | 2006-08-10 | Degussa Ag | Hochviskose wässrige Emulsionen von funktionellen Alkoxysilanen, deren kondensierten Oligomeren, Organopolysiloxanen, deren Herstellung und Verwendung zur Oerflächenbehandlung von anorganischen Materialien |
DE102005004872A1 (de) * | 2005-02-03 | 2006-08-10 | Degussa Ag | Wässrige Emulsionen von funktionellen Alkoxysilanen und deren kondensierten Oligomeren, deren Herstellung und Verwendung zur Oberflächenbehandlung |
DE102006013090A1 (de) * | 2006-03-20 | 2007-09-27 | Georg-August-Universität Göttingen | Kompositwerkstoff aus Holz und thermoplastischem Kunststoff |
DE102006033310A1 (de) * | 2006-07-17 | 2008-01-31 | Evonik Degussa Gmbh | Gemische aus siliciumhaltigen Kopplungsreagentien |
ES2725499T3 (es) * | 2007-04-20 | 2019-09-24 | Evonik Degussa Gmbh | Mezcla que contiene un compuesto de organosilicio y su uso |
DE102007038314A1 (de) * | 2007-08-14 | 2009-04-16 | Evonik Degussa Gmbh | Verfahren zur kontrollierten Hydrolyse und Kondensation von Epoxy-funktionellen Organosilanen sowie deren Condensation mit weiteren organofunktionellen Alkoxysilanen |
DE102007045186A1 (de) * | 2007-09-21 | 2009-04-09 | Continental Teves Ag & Co. Ohg | Rückstandsfreies, schichtbildendes, wässriges Versiegelungssystem für metallische Oberflächen auf Silan-Basis |
US20100015339A1 (en) * | 2008-03-07 | 2010-01-21 | Evonik Degussa Gmbh | Silane-containing corrosion protection coatings |
DE102008001808A1 (de) * | 2008-05-15 | 2009-11-19 | Evonik Degussa Gmbh | Beschichtungszusammensetzung |
DE102008001855A1 (de) * | 2008-05-19 | 2009-11-26 | Evonik Degussa Gmbh | Zweikomponenten-Zusammensetzung zur Herstellung von flexiblen Polyurethan-Gelcoats |
DE102009027090A1 (de) * | 2009-06-23 | 2010-12-30 | Evonik Degussa Gmbh | Magnetische Partikel und Polyethylen enthaltendes Kompositmaterial |
-
2008
- 2008-09-09 DE DE102008041919A patent/DE102008041919A1/de not_active Withdrawn
-
2009
- 2009-07-09 JP JP2011526430A patent/JP2012502149A/ja not_active Withdrawn
- 2009-07-09 CN CN2009801352170A patent/CN102149763A/zh active Pending
- 2009-07-09 US US13/058,290 patent/US20110144277A1/en not_active Abandoned
- 2009-07-09 WO PCT/EP2009/058718 patent/WO2010028875A1/fr active Application Filing
- 2009-07-09 EP EP09780352A patent/EP2331627A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO2010028875A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102008041919A1 (de) | 2010-03-11 |
US20110144277A1 (en) | 2011-06-16 |
WO2010028875A1 (fr) | 2010-03-18 |
CN102149763A (zh) | 2011-08-10 |
JP2012502149A (ja) | 2012-01-26 |
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