WO2004003028A1 - Acetales de polyvinyle, leur production et leur utilisation - Google Patents

Acetales de polyvinyle, leur production et leur utilisation Download PDF

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Publication number
WO2004003028A1
WO2004003028A1 PCT/EP2003/006771 EP0306771W WO2004003028A1 WO 2004003028 A1 WO2004003028 A1 WO 2004003028A1 EP 0306771 W EP0306771 W EP 0306771W WO 2004003028 A1 WO2004003028 A1 WO 2004003028A1
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weight
formula
compound
polymer
structural units
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PCT/EP2003/006771
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German (de)
English (en)
Inventor
Robert Fuss
Hermann Schindler
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Kuraray Specialities Europe Gmbh
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Priority to AU2003246596A priority Critical patent/AU2003246596A1/en
Publication of WO2004003028A1 publication Critical patent/WO2004003028A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives 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; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/14—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
    • 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
    • C08F216/00—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
    • C08F216/38—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 by an acetal or ketal radical
    • 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
    • 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
    • C08F8/28—Condensation with aldehydes or ketones
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present application relates to polyvinyl acetals, processes for their preparation and their use.
  • plasticizers of any kind is required to achieve the desired properties in various applications.
  • films of polyvinyl acetals, especially polyvinyl butyrals for use as intermediate layers of automobile windows (front and side windows) and architectural (window) panes (structural glass panes).
  • plasticizers for polyvinyl acetals are esters of aliphatic mono- and dicarboxylic acids with mono- or polyhydric alcohols or Oligoalkylenglykolethern and various phthalates, as described for example in US 5,137,954 A.
  • the diesters of di-, tri- and tetraethylene glycols with aliphatic monocarboxylic acids and adipic acid dialkyl esters are preferably used.
  • Triethylene glycol di-e-ethylhexanoate (see DE-A-24 53 780 and WO 97/24230) is frequently used in the art because it is readily compatible with the polyvinyl acetal, but especially with polyvinyl butyral, albeit only at low polyvinyl alcohol contents and is also available at low cost.
  • additives have in common that these are mixtures of one or more compounds (plasticizers, additives, etc. plus polymer), which are more or less compatible with each other. This has the consequence that such mixtures or blends segregate or separate by migration (exudation of the plasticizer). The consequence is that the (mechanical) properties of the products change (disadvantageously). For example, foams on films by the plasticizer accumulates on the surface and thus the film loses its elasticity.
  • a further object of the present invention was to provide a process for the preparation of the polymers according to the invention which can be carried out in a simple manner, industrially and inexpensively.
  • polyvinyl acetals obtainable by a production process having all the features of patent claim 1.
  • Advantageous modifications of the method according to the invention are provided in the dependent claims on claim 1 under protection.
  • the polyvinyl acetals obtainable by the process according to the invention are characterized by Claimed product claims and the claims of the use category describe particularly advantageous -Einsatz concerninge the polyvinyl acetals of the invention.
  • R 1 is hydrogen or methyl, b.) 0 to 99.0% by weight 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% by weight of structural units of the formula (3)
  • R 3 , R 4 , R 5 and R 6 are each independently radicals having a molecular weight in the range of 1 to 500 g / mol, based in each case on the total weight of the polymer (A), and B.) 0.01 to 50.0 parts by weight of at least one hydroxy compound (B) of the formula (4)
  • R 7 is independently hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 8 is hydrogen or a
  • R 9 and R 10 are each independently hydrogen, COOH, an alkyl group of 1 to 10 carbon atoms or an optionally substituted aryl group of 6 to 12 carbon atoms, wherein per mole of hydroxyl groups containing the polymer (A ) and the hydroxy compound (B) in total 0.0005 to 0.5 mol of the compound (C), it is not readily predictable way to access polyvinyl acetals with improved properties, the comparable properties as the conventional " In particular, in the case of the polyvinyl acetals according to the invention, a change in the property profile due to separation, concentration, migration and / or exudation of components even after a prolonged period, such as one year, is not observed.
  • the process according to the invention makes it possible to produce the polyvinyl acetals according to the invention in a simple manner, industrially and cost-effectively.
  • the polyvinyl acetals according to the invention can be used in many ways. Their application is not limited to the known fields of use of conventional polyvinyl acetals, but due to their significantly improved long-term stability of their properties, they are also suitable for new applications, which are closed for the conventional polyvinyl acetals.
  • the polymers according to the invention are obtainable by a process in which a mixture of
  • the sum of the parts by weight of A.) and B.) is preferably 100 parts by weight.
  • the polymer (A) contains, based in each case on its total weight a) 1.0 to 99.9% by weight of structural units of the formula (1) b.) 0 to 99.0% by weight of structural units of the formula (2)
  • the respective structural units are of course different from one another, in particular, in the context of the present invention, the structural unit of the formula (3) does not comprise the structural units of the formula (1) or (2).
  • the radical R 1 is in each case independently of one another hydrogen or methyl, preferably hydrogen.
  • the radical R 2 denotes hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably an alkyl radical having 1 to 6 carbon atoms, suitably a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl , tert-butyl, n-pentyl or an n-hexyl group, advantageously a methyl or an ethyl group, in particular a methyl group.
  • the radicals R 3 , R 4 , R 5 and R 6 are each independently radicals having a molecular weight in the range of 1 to 500 g / mol, suitably hydrogen, an optionally branched, aliphatic or cycloaliphatic radical having 1 to 16 carbon atoms, optionally may contain one or more carboxylic acid, carboxylic anhydride, carboxylic acid ester, carboxylic acid amide and / or sulfonic acid groups.
  • control 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. proved to be particularly favorable.
  • structural units (3) derived from acrylamidopropenylsulfonic acid (AMPS) also lead to very particularly advantageous results according to the invention.
  • the total number of structural units of the formula (2) is preferably in the range of 0.1 to 40 mol%, preferably in the range of 0.5 to 25.0 mol%, especially in the range of 1.0 to 15.0 mol -%, in each case based on the total number of structural units of the formula (1) and (2).
  • a polymer (A) is used, which contains based on the total number of structural units of the formula (1) and (2) 1.0 to 2.0 mol% of structural units of the formula (2)
  • a polymer (A) is used which, based on the total number of structural units of the formula (1) and (2) contains 3.0 to 7.0 mol% of structural units of the formula (2).
  • a polymer (A) is used which, based on the total number of structural units of the formula (1) and (2) contains from 10.0 to 15.0 mol% of structural units of the formula (2).
  • the polymer (A) based in each case on its total weight, contains> 50.0% by weight, expediently> 60.0% by weight, advantageously> 70.0% by weight , In particular> 80.0 wt .-% of Strakmrillonen of formula (1) and / or (2).
  • polymers (A) which, based in each case on their total weight, are> 85.0% by weight, expediently> 90.0% by weight, advantageously> 95.0% by weight, in particular> 99.0% by weight of structural units of the formula (1) and / or (2).
  • the polymer (A) may have a syndiotactic, isotactic and / or atactic chain structure. Furthermore, it can be present both as a random and as a block copolymer.
  • the viscosity of the polymer (A) is according to the invention of minor importance, in principle, both low molecular weight and high molecular weight polymers (A) can be used. Nevertheless, it has been found within the scope of the present invention to be particularly favorable that the polymer (A) has a viscosity in the range from 1 to 70 mPas, preferably in the range from 2 to 40 mPas, in particular in the range from 3 to 30 mPas (measured as 4% by weight aqueous solution according to Hoppler at 20 ° C., DIN 53015).
  • 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.
  • 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 radical R 7 denotes hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-butyl Pentyl or an n-hexyl group, in particular a methyl group.
  • the radical R 7 is hydrogen.
  • the radicals R 7 can each be selected independently of one another, ie each repeating unit -CHR 7 -CH 2 -O- can have a different radical R 7 .
  • the above definition of the hydroxy compound (B) includes both polyethylene glycol (monoether) and polypropylene glycol (monoether) and polyethylene glycol-co-propylene glycol (monoether). The latter can have both a statistical and a block-like structure.
  • the radical R 8 denotes hydrogen or an alkyl radical having 1 to 10 carbon atoms, preferably a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-butyl Pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl, in particular a methyl group.
  • the radical R 8 is hydrogen.
  • n is a number greater than or equal to 2, preferably a number in the range from 2 to 1000, advantageously in the range from 3 to 300, advantageously in the range from 3 to 25, particularly preferably in the range from 3 to 10, in particular in the range from 4 to 6. Furthermore, particularly favorable results can be achieved if n is a number in the range of 10 to 20, in particular in the range of 12 to 15.
  • the compound (C) according to the invention has the formula (5)
  • the radicals R 9 and R 10 are each independently hydrogen, COOH, 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.
  • Preferred compounds (C) include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 2-ethoxybutyraldehyde, paraldehyde, 1,3,5-trioxane, capronaldehyde, 2-ethylhexanal, pelargonaldehyde, 3,5,5- Trimethylhexanal, 2-formyl-benzoesulfonic acid, acetone, ethyl methyl ketone, butyl ethyl ketone and / or ethyl hexyl ketone.
  • glyoxylic acid HCO-COOH is used as compound (C).
  • the proportions of the starting compounds (A), (B) and (C) are selected according to the invention such that from 0.0005 to 0.5 mol per mole of hydroxyl groups which contain the polymer (A) and the hydroxy compound (B) in total the compound (C) is used.
  • the compounds (B) and (C) are preferably used in a compound (C) / compound (B) ratio greater than or equal to one.
  • the reaction of the starting compounds (A), (B) and (C) is preferably carried out in at least one inert solvent, the term "inert solvent” being those solvents which do not react with the compounds present in the reaction system under the respective reaction conditions particularly useful solvent in this context is water.
  • reaction is conveniently carried out in the presence of acidic catalysts.
  • suitable acids include both organic acids, such as, for example, acetic acid and mineral acids, such as hydrochloric acid, sulfuric acid and / or nitric acid, the use of hydrochloric acid, sulfuric acid and / or nitric acid having proven particularly useful in the art.
  • the reaction is preferably carried out by initially charging a mixture of components (A) and (B) in aqueous solution, adding compound (C) to this solution, and then dropping the acidic catalyst.
  • the reaction temperature can be varied over a wide range, but often the temperature is in the range of -20.0 ° C to 100.0 ° C, preferably in the range of 0.0 ° C to 80.0 ° C.
  • the reaction can take place both at low pressure and at overpressure. Preferably, however, it is carried out at atmospheric pressure.
  • the reaction can also take place under air, it has proven favorable in the context of the present invention to carry out the reaction under a protective gas atmosphere, preferably nitrogen and / or argon, wherein preferably a low oxygen content is present.
  • the solubility behavior of the polymers according to the invention can be adjusted via the degree of acetalization. This increases in the course of the reaction, whereby the solubility of the resulting product in the aqueous medium decreases.
  • HLB hydrophilic-lipophilic balance
  • the product separates from the aqueous phase, visible first by clouding of the solution and finally by complete precipitation from the same.
  • the "finalized” final product is no longer soluble in water and is separated as a solid and, after appropriate work-up, recovered as a pure product.
  • the reaction continues until the total consumption of the same.
  • the product is completely water-soluble or shows a temperature-dependent cloud point with increasing acetalization, ie the solubility of the polymer in water - at a given temperature - depends on the level of the reaction.
  • organic solvents eg. As alcohols, such as ethanol, but can be completely dissolved again.
  • the property profile of the polyvinyl acetals according to the invention differs markedly both from conventional polyvinyl acetals which contain no plasticizer and from those polyvinyl acetals which have been plasticized at the same degree of conversion (degree of acetalization) by the addition of plasticizer.
  • the polyvinyl acetals of the present invention at the same degree of acetalization, have a lower glass transition temperature, an increased shape-changing ability, a lower entropy elasticity elastic properties, lower hardness and usually increased adhesion.
  • the polyvinyl acetals which were plasticized with the same degree of conversion (degree of acetalization) by the addition of plasticizer, they are characterized in particular by improved long-term stability of their properties, especially in the polyvinyl acetals according to the invention a change in the property profile by separation, concentration, migration and / or Exudation of components by atmospheric influences even after a long time, such as a year, not observed.
  • atmospheric influences are understood as meaning all the factors that may occur when using the polyvinyl acetals according to the invention, in particular outdoors, such as sunlight, oxygen, ozone, other gaseous components of air, temperature, humidity, precipitation, dust deposits, etc ..
  • the products of the invention can be processed in a conventional manner and show novel and special properties in many applications.
  • the solubility in pure water is adjustable as desired over the HLB value.
  • the objects and moldings produced therefrom may, in their solubility, interact with the special conditions of their interaction be adapted to passing media.
  • the solubility can be optimized to specific pH ranges without the objects losing their properties, such as flexibility and resilience. This is particularly advantageous when packaging household chemicals or agrochemicals.
  • Films from the products according to the invention can be optimized for good solubility, for example at pH 2, which was previously not possible with commercial products. Also, the solubility in the alkaline is often not given. Again, the products of the invention represent a solution.
  • a particularly preferred field of application of the polyvinyl acetals according to the invention in the context of the present invention are fabrics, in particular films, preferably having a thickness in the range from 0.5 ⁇ m to 1 mm. These can - depending on the desired glass transition temperature Tg - small amounts, preferably less than 10% by weight based on the total amount of polyvinyl acetal, conventional plasticizers such as phthalates, trimellitates, acyclic aliphatic dicarboxylic acid esters, phosphates, fatty acid esters, especially triethylene glycol bis (2 -ethylbutyrat) and / or hydroxycarboxylic acid esters. Nevertheless, it has been found in the context of the present invention to be particularly favorable that the polyvinyl acetals contain no further additives.
  • the polyvinyl acetal films are used as a film composite which has at least one layer of the polyvinyl acetal according to the invention.
  • they are laminated to multilayer sandwich films for security interlayer, which can be used in the field of sound insulation.
  • the sound insulation in such glass composites is z. Zt. Achieved by z. B.
  • the intermediate film used are mixed with very large amounts of suitable plasticizer to the necessary low glass transition temperature of z. B. 10-20 ° C to reach.
  • the migration has already been pointed out above, especially in the case of solar radiation and the resulting harmful effects.
  • Another method consists of laminating such "sound insulation foils" on both sides with films of conventional polyvinyl acetal films which contain substantially less plasticizer, in order to optimize the sound barrier effect deteriorate.
  • a film of the polyvinyl acetal according to the invention has a substantially lower glass transition temperature with the same external plasticization as conventional polyvinyl acetal types. If you hide these two types with z. B. same plasticizer content, thus resulting in a migration-free composite film with adjusted sound insulation and temporally constant overall properties. Even better results can be achieved with a composite film which is obtainable by laminating various types of polyvinyl acetal according to the invention, which differ preferably in the glass transition temperature and are preferably free of plasticizer.
  • the following examples and the comparative example serve to illustrate the invention, without this being intended to limit it.
  • the polyvinyl alcohols used are described according to the nomenclature used by Kuraray Specialties Europe GmbH (KSE).
  • the number mentioned in the type designation at the first position indicates the viscosity of the 4% aqueous solution at 20 ° C as a relative measure of the degree of polymerization of the polyvinyl alcohols; the second number indicates the degree of hydrolysis (degree of saponification) of the type of polyvinyl acetate on which the type is based (partially hydrolyzed and fully hydrolyzed polyvinyl alcohol types).
  • the usual fluctuations in the characteristic data given by the company Kuraray Specialties Europe GmbH apply, ie, the viscosity may have a fluctuation of ⁇ 0.5 mPa s, the degree of hydrolysis a fluctuation of ⁇ 1 mol%.
  • the precipitated solid is filtered off and washed sufficiently with water and made alkaline with 10 wt .-% sodium hydroxide solution. Excess liquor is removed by brief washing with water. Subsequently, the product is dried.
  • the product obtained has a residual acetate content of 1.59 mol% based on the total number of all OH groups in the originally used Mowiol and a residual Polyvmylalkoholgehalt of 20.14 mol- based on the total number of all OH groups in the originally used Mowiol.
  • the viscosity according to Hoppler according to DIN 53015 amounts to 10% by weight solution in ethanol 440 mPas and with a 5% strength by weight solution in butanol 113 mPa s.
  • the glass point (Tg) determined by DSC measurement is 70 ° C.
  • the precipitated solid is filtered off and washed sufficiently with water and made alkaline with 10 wt .-% sodium hydroxide solution. Excess liquor is removed by brief washing with water. Subsequently, the product is dried.
  • the product obtained has a residual acetate content of 1.09 mol% based on the total number of all OH groups in the originally used Mowiol and a residual polyvinyl alcohol content of 20.34 mol- based on the total number of all OH groups in the originally used Mowiol.
  • the viscosity according to Hoppler according to DIN 53015 is 173 mPa s for a 5% by weight solution in ethanol and 570 mPa s for a 5% strength by weight solution in butanol.
  • the glass point (Tg) determined by DSC measurement is 72 ° C.
  • the precipitated solid is filtered off and washed sufficiently with water and made alkaline with 10 wt .-% sodium hydroxide solution. Excess liquor is removed by brief washing with water. Subsequently, the product is dried.
  • the Höppler viscosity in accordance with DIN 53015 is 854 mPas for a 10% by weight solution in ethanol and 2805 mPas for a 10% by weight solution in butanol.
  • the glass point (Tg) determined by DSC measurement is 66 ° C.
  • the precipitated solid is filtered off and washed sufficiently with water and made alkaline with 10 wt .-% sodium hydroxide solution. Excess liquor is removed by brief washing with water. Subsequently, the product is dried.
  • the Höppler viscosity according to DIN 53015 is 31.55 mPa s in the case of a 10% by weight solution in ethanol and 115 mPa s in the case of a 10% strength by weight solution in butanol.
  • the glass point (Tg) determined by DSC measurement is 62 ° C.
  • the precipitated solid is filtered off and washed sufficiently with water and made alkaline with 10 wt .-% sodium hydroxide solution. Excess liquor is removed by brief washing with water. Subsequently, the product is dried.
  • the Höppler viscosity according to DIN 53015 is 325 mPa s for a 10% by weight solution in ethanol and 945 mPa s for a 10% strength by weight solution in butanol.
  • the glass point (Tg) determined by DSC measurement is 69 ° C.
  • the precipitated solid is filtered off and washed sufficiently with water and made alkaline with 10 wt .-% sodium hydroxide solution. Excess liquor is removed by brief washing with water. Subsequently, the product is dried.
  • the Höppler viscosity according to DIN 53015 is 136 mPa s for a 5% strength by weight solution in ethanol and 453 mPa s for a 5% strength by weight solution in butanol.
  • the glass point (Tg) determined by DSC measurement is 71 ° C.
  • Polyvinyl alcohol Mowiof 26-88 (1080 g) is dissolved in E-water (6120 g) according to the known manner. After cooling the solution, 43.2 g of polyethylene glycol PEG 200 (corresponding to 4 mol% based on the polyvinyl alcohol used) and n-butyraldehyde (27.6 g, 4 mol%, based on the polyvinyl alcohol used) are stirred at 40 ° C. with stirring ) was added. At room temperature, a quantity of 200 ml of 20% strength by weight hydrochloric acid is metered in over a period of 120 minutes and then stirred for 120 minutes. With 10 wt .-% sodium hydroxide solution is then to pH 7 to 8 set.
  • the pH is monitored over a period of 2-3 hours and readjusted if necessary.
  • the product obtained has a viscosity of 19.63 mPa s (4 wt .-% water, Hoppler, DIN 53015) and 229 mPa s (8 wt .-% in water, Höppler, DIN 53015).
  • the cloud point at 4 wt .-% aqueous solution is 56 ° C, at 8 wt .-% aqueous solution 50 ° C.
  • the precipitation points at 4 wt .-% aqueous solution are 67 ° C, at 8 wt .-% aqueous solution 66 ° C.
  • the glass point (Tg) determined by DSC measurement is 70 ° C.
  • Example 7 was repeated, but without the addition of polyethylene glycol PEG 200.
  • the analytical data are as follows: viscosity 21.7 mPa s (4% by weight in water, Höppler, DIN 53015) or 270 mPa s (8% by weight in water, Höppler, DIN 53015).
  • the cloud point at 4 wt .-% aqueous solution is 61 ° C, at 8 wt .-% aqueous solution 72 ° C.
  • the precipitation points at 4 wt .-% aqueous solution are 69 ° C, at 8 wt .-% aqueous solution 75 ° C.
  • the glass point (Tg) determined by DSC measurement is 75 ° C.
  • Example 9 The procedure was as in Example 9, but using 15 wt .-% polyethylene glycol PEG 200, based on the polyvinyl alcohol used. The properties of a film obtained therefrom are also shown in Table 1.
  • the Höppler viscosity according to DIN 53015 is 6.7 mPa s for a 4% strength by weight aqueous solution and 39.8 mPa s for an 8% strength by weight aqueous solution.
  • the glass point (Tg) determined by DSC measurement is 60 ° C.
  • Example 11 1080 g of polyvinyl alcohol Mowiof 10-98 are dissolved in 6,120 ml of water. After the addition of 108 g of polyethylene glycol PEG 200, a mixture of 86.0 g of n-butyraldehyde and 52.5 g of acetaldehyde is added. By metering in 20% strength by weight hydrochloric acid solution until a pH of about 1 is reached (200 ml), the reaction is started at 20 ° C. After completion of the hydrochloric acid metering, the reaction solution is stirred for a period of 2 hours. With 10 wt .-% sodium hydroxide solution is made alkaline (455 ml).
  • the viscosity according to Hoppler according to DIN 53015 is 8.4 mPa e for a 4% strength by weight aqueous solution and 59 mPa s for an 8% strength by weight aqueous solution.
  • the glass point (Tg) determined by DSC measurement is 71 ° C.
  • Example 11 was carried out but without the addition of polyethylene glycol PEG 200.
  • the analytical data are as follows: Viscosity 10.8 mPa s (4 wt%, aqueous solution, Hoppler, DIN 53015) and 90.5 mPa s (8 wt%, aqueous solution, Hoppler).
  • the glass point (Tg) determined by DSC measurement is 85 ° C.
  • the Höppler viscosity according to DIN 53015 is 13.17 mPa s for a 4% strength by weight aqueous solution and 120.50 mPa s for an 8% strength by weight aqueous solution.
  • the cloud point at 4 wt .-% aqueous solution is -42 ° C, at 8 wt .-% aqueous solution -40 ° C.
  • the precipitation points at 4 wt .-% aqueous solution are -58 ° C, at 8 wt .-% aqueous solution -60 ° C.
  • Example 13 Example 13:
  • the Höppler viscosity according to DIN 53015 is 17.46 mPa s for a 4% strength by weight aqueous solution and 236.4 mPa s for an 8% strength by weight aqueous solution.
  • the cloud point at 4 wt .-% aqueous solution is -37 ° C, at 8 wt .-% aqueous solution -36 ° C.
  • the precipitation points at 4 wt .-% aqueous solution are -41 ° C, at 8 wt .-% aqueous solution -41 ° C.
  • the Höppler viscosity in accordance with DIN 53015 is 23.94 mPa s for a 4% strength by weight aqueous solution and 327.40 mPa s for an 8% strength by weight aqueous solution.
  • the cloud point at 4% by weight is -46 ° C, at 8% by weight -44 ° C.
  • the precipitation points at 4 wt .-% solution are -56 ° C at 8 wt .-% solution -60 ° C.
  • the Höppler viscosity in accordance with DIN 53015 is 23.94 mPa s for a 4% strength by weight aqueous solution and 327.40 mPa s for an 8% strength by weight aqueous solution.
  • the cloud point at 4 wt .-% aqueous solution is -70 ° C at 8 wt .-% aqueous solution -74 ° C. Precipitation points are not observed.

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Abstract

L'invention concerne un procédé de production d'acétals de polyvinyle, caractérisé en ce qu'il consiste à faire réagir un mélange constitué de A.) 50,0 à 99,5 parties en poids d'au moins un polymère (A) qui comporte, en pourcentage en poids sur la quantité totale de ce polymère (A), a.) 1,0 à 99,9 % en poids d'entités structurales de formule (1), b.) 0 à 99,0 % en poids d'entités structurales de formule (2) et c.) 0 à 70,0 % en poids d'entités structurales de formule (3) et de B.) 0,01 à 50,0 parties en poids d'au moins un composé hydroxy (B) de formule (4) avec C.) au moins un composé (C) de formule (5). Selon l'invention, pour une mole de groupes hydroxyle contenus au total dans le polymère (A) et le composé hydroxy (B), l'on utilise 0,0005 à 0,5 mole du composé (C). Dans lesdites formules, les groupes R1 à R10 ainsi que l'indice n ont leur signification indiquée dans la description. Cette invention se rapporte en outre aux acétals de polyvinyle productibles au moyen dudit procédé ainsi qu'à leur utilisation.
PCT/EP2003/006771 2002-06-28 2003-06-26 Acetales de polyvinyle, leur production et leur utilisation WO2004003028A1 (fr)

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WO2006114085A1 (fr) * 2005-04-27 2006-11-02 Bernd Papenfuhs Polyvinylacetales plastifies, leur fabrication et leur utilisation
US10889710B2 (en) * 2017-09-07 2021-01-12 Mitsubishi Chemical Corporation Resin composition

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DE10257131B4 (de) * 2002-12-05 2005-07-28 Kuraray Specialities Europe Gmbh Beschichtetes Material zur Tintenstrahlbedruckung, Verfahren zu seiner Herstellung

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US10889710B2 (en) * 2017-09-07 2021-01-12 Mitsubishi Chemical Corporation Resin composition

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