EP1861432A1 - Procede de production d'acetals polyvinyliques - Google Patents

Procede de production d'acetals polyvinyliques

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Publication number
EP1861432A1
EP1861432A1 EP06722622A EP06722622A EP1861432A1 EP 1861432 A1 EP1861432 A1 EP 1861432A1 EP 06722622 A EP06722622 A EP 06722622A EP 06722622 A EP06722622 A EP 06722622A EP 1861432 A1 EP1861432 A1 EP 1861432A1
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EP
European Patent Office
Prior art keywords
reaction phase
formula
mol
polymer
post
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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Application number
EP06722622A
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German (de)
English (en)
Inventor
Bernd Papenfuhs
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Papenfuhs Bernd
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Individual
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Filing date
Publication date
Priority claimed from DE102005012924.2A external-priority patent/DE102005012924B9/de
Application filed by Individual filed Critical Individual
Publication of EP1861432A1 publication Critical patent/EP1861432A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/6342—Polyvinylacetals, e.g. polyvinylbutyral [PVB]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/48—Isomerisation; Cyclisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a term-shortened process for the preparation of polyvinyl acetals and their use.
  • Polyvinyl acetals which are usually obtained by acetalization of the corresponding polyvinyl alcohols, have been known for a long time and are produced in large quantities for various fields of application, in terms of quantity the thermoplastic processing (extrusion) to films for the safety composite glass production is most important.
  • polyvinyl formal polyvinyl acetoacetal
  • polyvinyl butyral polyvinyl butyral
  • modified polyvinyl acetals which in addition to the three units vinyl acetate, vinyl alcohol and vinyl acetal contain further monomer units.
  • polyvinyl acetals For the preparation of polyvinyl acetals, an aqueous solution of polyvinyl alcohol (PVA) or a PVA copolymer is reacted with the aldehyde (s) in the presence of an acidic catalyst, the products precipitating out of the reaction solution.
  • PVA polyvinyl alcohol
  • This polymer precipitation usually takes place at temperatures of up to 30 ° C. during the so-called precipitation phase or pre-reaction phase.
  • the reason for setting a relatively low temperature for polymer precipitation is the thereby possible prevention of product clogging (undesirable coagulation of the polyvinyl acetal precipitate).
  • the dosing order can also be reversed or an addition of subsets of the components in the
  • the polymer precipitate is usually washed, alkaline stabilized and finally dried.
  • thermoplastic processability For specifically influencing the theological or melt rheological behavior and thus the thermoplastic processability are in particular the polyvinyl acetals (usually polyvinyl butyrals) intended for the production of safety composite glass films are subjected to a thermal aftertreatment, as described in JP 56092142 A.
  • the acidic polyvinyl acetal suspension to temperatures is heated by at least 50 0 C, where the polymers undergo a stereochemical rearrangement, "heat modifier" which can be described as.
  • the progress of this hot-modification can be based on a decrease in at 100 ° C certain melt indices or an increase in the solution viscosities.
  • the hot modification which is also indispensable for the production of the mechanical strength of the safety composite glass films available by extrusion, causes long occupation times of the acetalization reactors, ie a reduction of the production capacity, and high cost-intensive energy consumption.
  • the object of the present invention was therefore to provide a less energy and time-consuming process for the preparation of polyvinyl acetals, the polymers in a thermoplastic
  • the relatively low temperature of the precipitation phase can therefore surprisingly be used not only to prevent the polymer clumping, but also for an energy and time-saving polyvinyl acetal Modiflzierung. It is much more effective in its polymer property-affecting effect than the hot-modification, and will be hereinafter referred to as "cold-modifier" for distinction.
  • An extension of the low-temperature precipitation phase or the cold-Modifizierang therefore offers the ability to significantly shorten the occupancy of the acetalization reactors and thus the duration of polyvinyl acetal production.
  • This shortening of the acetalization runtime not only greatly reduces the energy needs to be expended.
  • an increase in production capacity is associated with an extremely high capital expenditure, because the low pH values required for the production of polyvinyl acetals, a high
  • the inventive method of prolonged cold modification under disproportionately shortened hot-modification also does not require the adversely affecting additive surface-active additives.
  • the process according to the invention therefore consists in the acid-catalyzed reaction of at least one polymer A which, based on its total weight,
  • R 1 is hydrogen or methyl, b) 0 to 99.0 mol% of structural units of the formula (2)
  • R 2 is hydrogen or an alkyl radical having 1 to 6 carbon atoms, c) 0 to 70.0 mol% of structural units of the formula (3)
  • R 3 , R 4 , R 5 and R 6 each independently of one another, have radicals with a molecular weight in the range from 1 to 500 g / mol, with at least one compound B of the formula (4)
  • R 7 and R 8 are each independently hydrogen, COOH, COOM, an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group with
  • M is a metal cation or an optionally alkylated ammonium cation
  • the inventive method therefore allows a significant increase in the production capacity of polyvinyl acetals, the resulting products have no disadvantages in terms of performance.
  • the polyvinyl acetal powders obtained according to the invention are even distinguished from the prior art by an increased bulk density, which brings about savings in the logistics sector.
  • thermoplastic processing of the more compact polymer powders also higher extruder throughputs are possible or at unchanged throughputs higher quality products accessible because the extrudates are less damaged by milder extrusion conditions.
  • Another important advantage of the teaching according to the invention is the improved energy balance of the new process compared to the prior art, since it enables a shortening of the energy-intensive post-reaction phase (hot modification).
  • the total number of structural units of the formula (2) of the polymer A is preferably in the range of 0 to 40.0 mol%, suitably in the range of 0 to 25.0 mol%, in particular in the range of 0 to 5.0 mol%, in each case based on the Total number of structural units of the formulas (1) and (2).
  • the polymer A contains, in each case based on its total weight, greater than 50.0 mol%, advantageously greater than 60.0 mol%, advantageously greater than 70.0 mol%, in particular greater than 80.0 mol% of structural units of the formula ( 1) and / or (2).
  • Particularly advantageous results can be achieved with polymers A which, based in each case on their total weight, are greater than 85.0 mol%, advantageously greater than 90.0 mol%, advantageously greater than 95.0 mol%, in particular greater than 99.0 mol% of structural units of the formula ( 1) and / or (2) contain. It has been found according to the invention as very particularly favorable that polymer A contains more than 95.0 mol% of structural units of the formula (1).
  • Particularly preferred structural units of the formula (3) are derived from straight-chain or branched olefins having 2 to 18 carbon atoms, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, (meth) acrylamides and / or ethylene sulfonic acid.
  • olefins in particular those having a terminal C-C double bond, which preferably have 2 to 6 carbon atoms, in particular ethylene, have proven to be very particularly favorable.
  • structural units (3) derived from acrylamidopropenylsulfonic acid (AMPS) also lead to very particularly advantageous results according to the invention.
  • polymer A may contain syndiotactic, isotactic and / or atactic compounds which may be present both as random and as block copolymers.
  • the viscosity of the polymer A is according to the invention of subordinate
  • both low molecular weight and high molecular weight compounds can be used as polymer A.
  • compounds having viscosities in the range from 1.0 to 70.0 mPas, preferably in the range from 2.0 to 40.0 mPas and in particular in the range from 25.0 to 35.0 mPas are used (measured as 4.0 % By weight aqueous solution according to Hoppler at 20 ° C., DIN 53015).
  • a specific form of the embodiment is furthermore that polymer A contains no compounds which have structural units of the formula (3).
  • the preparation of the polymers A to be used according to the invention can be carried out in a manner known per se in a two-stage process.
  • a first step the corresponding vinyl ester is radically polymerized in a suitable solvent, usually water or an alcohol, such as methanol, ethanol, propanol and / or butanol, using a suitable radical initiator. If the polymerization is carried out in the presence of free-radically copolymerizable monomers, the corresponding vinyl ester copolymers are obtained.
  • the vinyl ester (co) polymer is then saponified in a second step, usually by transesterification with methanol, wherein the degree of saponification can be adjusted in a known manner, for example by varying the catalyst concentration, the reaction temperature and / or the reaction time.
  • the degree of saponification can be adjusted in a known manner, for example by varying the catalyst concentration, the reaction temperature and / or the reaction time.
  • the radicals R 7 and R 8 are each independently of one another hydrogen, COOH, COOM, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. These alkyl and aryl radicals may be substituted by one or more carboxyl, hydroxyl, sulfonic acid groups and / or halogen atoms, such as fluorine, chlorine, bromine, iodine.
  • the radical M denotes a metal cation or an optionally alkylated ammonium cation.
  • Particularly favorable metal cations are derived from elements of the PSE with a Electronegativity less than 2.0, preferably less than 1.5, and include in particular Li + , Na + , K + , Rb + Cs + Be 2+ Mg 2+ Ca 2+ , Sr 2+ Ba 2+ and Al 3+ .
  • Ammonium cations particularly suitable for the purposes of the present invention include NH 4 + , H 3 NCH 3 + , H 3 NC 2 H 5 + , H 3 NC 3 H 7 + , H 3 NC 4 H 9 + , H 2 N ( CH 3 ) 2 + , H 2 N (C 2 Hs) 2 + H 2 N (C 3 H 7 ) 2 + , H 2 N (C 4 Hg) 2 + , HN (CH 3 ) 3 + , HN (C 2 Hs) 3 + , HN (C 3 H 7 ) 3 + , HN (C 4 Hg) 3 + , N (CH 3 ) /, N (C 2 H 5 ) /, N (C 3 H 7 ) / and N (C 4 H 9 ) /.
  • Very particularly preferred compounds B for the purposes of the present invention include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 2-ethoxybutyraldehyde, paraldehyde, 1,3,5-trioxane, capronaldehyde, 2-ethylhexanal, pelargonaldehyde, glucose,
  • glyoxylic acid HCO-COOH is used as compound B.
  • the amounts of compound B can in principle be chosen as desired in the context of the present invention. In general, between 0.1 and 300% by weight, preferably between 25 and 150% by weight, advantageously between 40 and 99% by weight and in particular between 57.5 and 77.5% by weight of compound B, in each case based on polymer A. ,
  • the reaction of the starting compounds A and B is preferably carried out in at least one solvent.
  • a particularly useful solvent in this context is water.
  • an at least 8.0% strength aqueous solution of polymer A is used.
  • Suitable acids include both organic acids, such as acetic acid and mineral acids, such as hydrochloric acid, sulfuric acid and / or nitric acid, with the use of hydrochloric acid being particularly useful in the art.
  • the process according to the invention is preferably carried out by initially introducing an aqueous solution of the polymer A, then adding the compound B and finally metering in the acid catalyst at precipitation temperature.
  • the polyvinylacetal suspension obtained by phase separation is further stirred in the low-temperature region of the precipitation until it has reached the desired extent of the so-called cold-modification of the polymer before heating to the post-reaction phase.
  • the quotient X / Y where X is the time duration of the post-reaction phase (hot modification) and Y is the time duration of the pre-reaction phase (cold modification), gives a numerical value between 0.05 and 2.5.
  • the quotient X / Y gives a numerical value between 0.1 and 1.0, more advantageously between 0.3 and 0.9, and most advantageously between 0.45 and 0.75.
  • the pre-reaction phase (cold-modification) is carried out at temperatures of at most 30 0 C and the post-reaction phase (hot-modification) at a temperature of at least 5O 0 C.
  • a minimum temperature of the post-reaction phase of 72 ° C. is very advantageous.
  • the so-called intermediate reaction phase during which the heating of the acidic polyvinylacetal suspension to the temperature of the post-reaction phase or hot-modification takes place, is kept as short as possible (according to the technical limitations of the relevant plant), since an unnecessarily slow heating the acetalization Total life extended and thus impaired erfmdungshiele increase in production capacity.
  • the total acetalization run time is according to the invention preferably a maximum of 250 minutes (sum of the time duration of the pre-, post- and intermediate reaction phase or heating phase).
  • the polymer suspension is cooled as quickly as possible and the (acidic) mother liquor is filtered off.
  • the resulting polyvinyl acetal is preferably acid-free washed, preferably with demineralized water, optionally stabilized by an alkaline aftertreatment and dried.
  • the process according to the invention can be carried out both under reduced pressure and under overpressure. Preferably, however, the implementation is carried out at atmospheric pressure.
  • the process can be carried out in the presence of additives which are advantageous for the respective polyvinyl acetal application.
  • additives which are advantageous for the respective polyvinyl acetal application.
  • oxidation stabilizers antioxidants
  • surfactant ie surface-active additives.
  • Particularly preferred fields of application of the polyvinyl acetals obtainable by the process according to the invention include the use as extrusion raw material for the production of laminated safety glass films and as binders, in particular as binders for printing inks and coatings, as, preferably temporary, binders for ceramics and as binders for thermally developable, photosensitive layers.
  • the polymers are used particularly advantageously for producing adhesives, peelable coatings, fibers and ion-conducting intermediate layers for electrochromic systems.
  • the inventive reduction of manufacturing costs also makes new, extended areas of application accessible; for example in the field of additives for construction chemicals (tile adhesive, mortar, cementitious materials and the like) or in the field of emulsion and suspension polymerization.
  • Comparative Examples Ia to 3 a describe the preparation of polyvinyl acetals according to the prior art, whereas Comparative Examples Ib to 3b make it clear that an analogous to Examples 1 to 3 shortening the total acetalization run time does not provide sufficiently modified products, if they by simple Reduction of the hot-modification was accomplished.
  • b was a polyvinyl alcohol having a content of acetyl groups of 0.9 mol%, a content of vinyl alcohol groups of 99.1 mol% and a Höppler viscosity of 26.5 mPas (measured as 4.0% aqueous solution according to DUST 53015) was used.
  • the polymer raw material for Example 3 or Comparative Examples 3a, b was a polyvinyl alcohol mixture having a content of acetyl groups of 1.0 mol%, a content of vinyl alcohol groups of 99.0 mol% and a Höppler viscosity of 26.1 mPas used.
  • the mixture in question was 90% a polyvinyl alcohol having an acetyl group content of 0.9 mol%, a content of vinyl alcohol groups of 99.1 mol%, a Höppler viscosity of 28.2 mPas and 10% of a polyvinyl alcohol containing acetyl groups of 1.9 mol%, a content of vinyl alcohol groups of 98.1 mol% and a Höppler viscosity of 10.3 mPas (viscosities in each case measured as 4.0% aqueous solution according to DIN 53015).
  • the polymer was filtered off with suction, washed with distilled water to neutral reaction of the filtrate and dried at 40 0 C in a vacuum.
  • the polyvinyl acetal obtained had a content of 20.2% by weight of vinyl alcohol units and 1.2% by weight of vinyl acetate units. Comparative Example Ia
  • reaction mixture was stirred only for a total of 60 minutes in the temperature range between 14 0 C and 15 ° C, but maintained at the reheating temperature of 65 0 C for 180 minutes.
  • the polyvinyl acetal obtained had a content of 20.1% by weight of vinyl alcohol units and 1.2% by weight of vinyl acetate units.
  • Example 1 In contrast to the procedure described in Example 1, the reaction mixture was stirred only for a total of 60 minutes in the temperature range between 14 ° C and 15 ° C and held for 90 minutes at the reheating temperature of 65 0 C; the total run time of the acetalization thus corresponded to that of Example 1.
  • the polyvinyl acetal obtained had a content of 20.2% by weight of vinyl alcohol units and 1.2% by weight of vinyl acetate units.
  • Polyvinyl alcohol was placed in a 10 liter glass reactor and diluted with 1147 g of distilled water. The mixture was then heated with stirring until reaching 90 0 C internal temperature and then cooled. At 4O 0 C 538 ml of 20% hydrochloric acid were added within 5 minutes, the temperature decreased by only 1 ° C. At 14 ° C were within 5 minutes 373.1 g of n-butyraldehyde are added dropwise. The product precipitated from the reaction solution as a colorless precipitate 2 minutes before the end of the aldehyde addition.
  • the polyvinyl acetal obtained had a content of 20.9% by weight of vinyl alcohol units and 1.1% by weight of vinyl acetate units.
  • the polyvinyl acetal obtained had a content of 20.8% by weight of vinyl alcohol units and 1.2% by weight of vinyl acetate units.
  • Example 2 In contrast to the procedure described in Example 2, the reaction mixture was stirred only for a total of 60 minutes in the temperature range between 14 ° C and 15 ° C and 90 minutes at the reheating temperature of 65 ° C. held; the total run time of the acetalization thus corresponded to that of Example 2.
  • the polyvinyl acetal obtained had a content of 20.9% by weight of vinyl alcohol units and 1.2% by weight of vinyl acetate units.
  • the polymer was filtered off with suction, washed with distilled water to neutral reaction of the filtrate and dried at 40 0 C in a vacuum.
  • the polyvinyl acetal obtained had a content of 20.0% by weight of vinyl alcohol units and 1.2% by weight of vinyl acetate units. Comparative Example 3 a
  • reaction mixture was stirred only for a total of 60 minutes in the temperature range between 14 ° C and 15 0 C (by shortening the metering break between the two hydrochloric acid additions by 30 minutes), but 180 minutes on the Post-heating temperature of 65 ° C held.
  • the polyvinyl acetal obtained had a content of 19.9% by weight of vinyl alcohol units and 1.1% by weight of vinyl acetate units.
  • Example 3 In contrast to the procedure described in Example 3, the reaction mixture was stirred only for a total of 60 minutes in the temperature range between 14 ° C and 15 ° C (also by shortening the dosing interval between the two hydrochloric acid additions by 30 minutes) and 90 minutes on the Reheating temperature maintained at 65 ° C; the total run time of the acetalization thus corresponded to that of Example 3.
  • the polyvinyl acetal obtained had a content of 19.9% by weight of vinyl alcohol units and 1.2% by weight of vinyl acetate units.
  • the polyvinyl acetal was dissolved in an ethanol / benzyl alcohol (9: 1) mixture.
  • the vinyl acetate units were saponified with an excess of alcoholic potassium hydroxide.
  • the excess potassium hydroxide solution was back titrated with hydrochloric acid.
  • the content of vinyl acetate units was calculated on the basis of the hydrochloric acid consumption.
  • the viscosity of the saponified polyvinyl acetates used as starting material was determined analogously to the determination of the dynamic viscosity of the polyvinyl acetals; however, only 4.0% solution in distilled water was used for the measurement.
  • Acetylation of the hydroxyl groups with acetic anhydride in the presence of Pyridine determined. To this was weighed 1500 g +/- 0.001 g of polyvinyl acetal and 10 ml of a pyridine / acetic anhydride mixture (77:23) added. After about 14 hours of storage of the well-sealed sample at 50 ° C, 25 ml of 1.2-dichloroethane and 3 ml of distilled water were added at room temperature and allowed to stand for one hour. After filling the sample with distilled water to a total volume of 160 ml was titrated with rapid stirring against sodium hydroxide solution.
  • the resulting films were conditioned for 24 hours at 23 ° C. and a relative humidity of 50% before measuring the melt index.
  • the measurement was carried out with a melt index tester (manufacturer: Göttfert, type: MP-D) at 100 ° C with a load of 21.6 kg using a 2 mm nozzle according to ISO 1133.
  • the comparative examples show the advantages of the process according to the invention:
  • the preparation of sufficiently modified polyvinyl acetals following the prior art requires a considerably longer total acetalization run time AG (see Comparative Examples Ia to 3a), whereas an adaptation of the AG by means of a shortened post-reaction phase X or reduced Hot modification to inadequately modified polymers results (see Comparative Examples Ib to 3b).

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne l'élaboration d'un procédé de production d'acétals polyvinyliques nécessitant moins de temps et d'énergie. Le procédé de production d'acétals polyvinyliques selon l'invention consiste à faire réagir au moins un alcool polyvinylique ou un copolymère d'alcool vinylique en présence d'un catalyseur acide avec au moins un composé carbonyle de formule R<SUP>1</SUP>C(O)R<SUP>2</SUP>, dans laquelle R<SUP>1</SUP> et R<SUP>2</SUP> désignent indépendamment l'un de l'autre hydrogène COOH, COOM, un groupe alkyle éventuellement substitué présentant 1 à 10 atomes de carbone ou un groupe aryle éventuellement substitué présentant 6 à 12 atomes de carbone et M représente un cation métallique ou un cation ammonium éventuellement alkylé. Ce procédé se caractérise en ce que le résultat du quotient X/Y, X désignant la durée de la phase post-réactionnelle se déroulant à au moins 50 °C et Y désignant la durée de la phase pré-réactionnelle se déroulant à une température maximale de 30 °C, est une valeur numérique comprise entre 0,05 et 2,5, ce qui permet un net raccourcissement de la durée totale d'acétalisation et une économie d'énergie considérable. L'invention concerne également la production d'acétals polyvinyliques utilisés, en particulier, dans l'extrusion de feuilles pour la fabrication de verre de sécurité feuilleté.
EP06722622A 2005-03-21 2006-03-16 Procede de production d'acetals polyvinyliques Withdrawn EP1861432A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102005012924.2A DE102005012924B9 (de) 2005-03-21 2005-03-21 Verfahren zur Herstellung von Polyvinylacetalen
DE102006003437A DE102006003437A1 (de) 2005-03-21 2006-01-25 Verfahren zur Herstellung von Polyvinylacetalen
PCT/DE2006/000466 WO2006119720A1 (fr) 2005-03-21 2006-03-16 Procede de production d'acetals polyvinyliques

Publications (1)

Publication Number Publication Date
EP1861432A1 true EP1861432A1 (fr) 2007-12-05

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EP06722622A Withdrawn EP1861432A1 (fr) 2005-03-21 2006-03-16 Procede de production d'acetals polyvinyliques

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EP (1) EP1861432A1 (fr)
DE (1) DE102006003437A1 (fr)
WO (1) WO2006119720A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005012924B9 (de) * 2005-03-21 2014-08-14 Bernd Papenfuhs Verfahren zur Herstellung von Polyvinylacetalen
CN113845609B (zh) * 2021-08-26 2022-04-08 忠信（清远）光伏材料科技有限公司 一种聚乙烯醇缩丁醛的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1557261A1 (fr) 2004-01-22 2005-07-27 Kuraray Specialities Europe GmbH Acétal polyvinylique et son application

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See also references of WO2006119720A1

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