EP1991591A1 - Procede de modification de polyvinylbutyrals - Google Patents

Procede de modification de polyvinylbutyrals

Info

Publication number
EP1991591A1
EP1991591A1 EP06841564A EP06841564A EP1991591A1 EP 1991591 A1 EP1991591 A1 EP 1991591A1 EP 06841564 A EP06841564 A EP 06841564A EP 06841564 A EP06841564 A EP 06841564A EP 1991591 A1 EP1991591 A1 EP 1991591A1
Authority
EP
European Patent Office
Prior art keywords
reaction
carried out
polyvinyl alcohol
acetalated
aliphatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06841564A
Other languages
German (de)
English (en)
Inventor
Michael Frank
Sven KÖHNEN
Matthias Gutweiler
Kaoru Ikeda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Europe GmbH
Kuraray Co Ltd
Original Assignee
Kuraray Europe GmbH
Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Europe GmbH, Kuraray Co Ltd filed Critical Kuraray Europe GmbH
Priority to EP06841564A priority Critical patent/EP1991591A1/fr
Publication of EP1991591A1 publication Critical patent/EP1991591A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08F16/00—Homopolymers and 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
    • C08F16/02—Homopolymers and 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 alcohol radical
    • C08F16/04—Acyclic compounds
    • C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08F8/14—Esterification

Definitions

  • the invention relates to a process for the modification of acetalated polyvinyl alcohols by reaction with epoxides.
  • Acetalized polyvinyl alcohols e.g. Polyvinyl butyral (PVB) also have increasing solution viscosities or melt viscosities with increasing molecular weight.
  • PVB Polyvinyl butyral
  • EP 1 403 289 A1 describes such a process for the reaction of ethylene-vinyl alcohol copolymers with glycidyl esters in an extrusion process.
  • the epoxides are added to the hydroxy functions to give a corresponding side chain.
  • These polymers contain between 5 and 55 mole percent ethylene units, with the remaining recurring units being vinyl acetate and vinyl alcohol groups.
  • the vinyl alcohol groups are not acetalized, so that with a degree of hydrolysis of these polymers of greater than 90%, a large number of free hydroxy functions are present.
  • relatively high conversions or degrees of substitution can be achieved by the reaction with the epoxides.
  • DE 42 019 41 A1 discloses the preparation of a coating system by reacting polyvinyl butyral with glycidyl ether as epoxide in organic solvents.
  • a similar process is disclosed in JP 2001-210426 for the reaction of polyvinyl acetals with aromatic epoxides. Again, the reaction is carried out in organic solvents.
  • reaction temperatures are usually limited to the boiling point of the solvent.
  • the present invention therefore provides a process for the preparation of modified, acetalated polyvinyl alcohols by reacting a melt of the acetalated polyvinyl alcohol with at least one epoxide of the general formula I.
  • acetalated polyvinyl alcohols is understood to mean the formal addition of epoxides to its hydroxyl functions.
  • the acetalated polyvinyl alcohol used is preferably one with at least one aliphatic aldehyde having 1 to 10 carbon atoms, in particular butyraldehyde. These compounds may still contain vinyl acetate groups, i. completely or partially saponified present.
  • the acetalization with one or more aldehydes takes place in a manner known to those skilled in the acid catalyzed in solution, preferably in an aqueous medium under acid catalysis.
  • the resulting still containing vinyl alcohol polyvinyl acetals are reacted according to the invention with at least one epoxide, wherein at least a portion of the vinyl alcohol groups reacted.
  • the acetalated polyvinyl alcohol used is in particular polyvinyl butyral.
  • the acetalated polyvinyl alcohols used in the process according to the invention preferably have a degree of acetalization of from 40 to 90% by weight, preferably of 65% by weight. 88% by weight.
  • these polymers may have a proportion of 0.01-30% by weight, preferably 0.01-20% by weight, particularly preferably 0.5-8% by weight and in particular 1-6% by weight residual acetate groups and a corresponding proportion of free alcohol functions.
  • the residual polyvinyl alcohol content of the acetalated polyvinyl alcohols used according to the invention is preferably between 10 and 30% by weight, in particular between 14 and 18% by weight or alternatively between 19 and 27% by weight.
  • Such polymers are available under the trade name Mowital from Kuraray Specialties Europe GmbH.
  • the acetalated polyvinyl alcohols are preferably in the form of a granulate, in particular granules produced by extrusion, e.g. used according to WO 2005/019312 A1.
  • Granulated products advantageously have a low moisture content and higher solids contents per volume or a higher bulk density.
  • the process according to the invention is preferably carried out continuously in the melt of the acetalated polyvinyl alcohol. This allows for economical production of the modified polyvinyl acetals. There have melt temperatures proven 150-270 0 C 1, in particular 170 to 250 0 C, or 190 to 250 0 C.
  • the reaction is preferably carried out in a tubular reactor, stirred tank or extruder.
  • the reaction times in the process according to the invention can be between 30 seconds and 5 minutes, in particular between 30 seconds and 2 minutes.
  • plasticizers are diesters of aliphatic diols, especially of aliphatic polyethers or polyether polyols, with aliphatic carboxylic acids, preferably diesters of polyalkylene oxides, in particular diesters of di-, tri- and tetraethylene glycol with aliphatic (C6-C10) -carboxylic acids, preferably 2-ethylbutyric acid and n-heptanoic acid, furthermore diesters of aliphatic or aromatic (C 2 -C 18) -dicarboxylic acids, preferably adipic, sebacic and phthalic acids, with aliphatic (C 4 -C 12) -alcohols, preferably dihexyl
  • the inventive method is preferably carried out in the presence or under the catalysis of metal salts, such as Zn, Fe and / or Sn salts.
  • metal salts such as Zn, Fe and / or Sn salts.
  • the addition of the catalytic system Zn (acac) 2 / CF 3 SO 3 H / DME according to EP 1 403 289 A1 has proved particularly suitable.
  • reaction may also be carried out in the presence of bases, particularly sterically hindered nitrogen bases, e.g. Bases of the general formulas IM to V
  • R 3 H, CH 3 or C 2 H 5 ).
  • the reaction is preferably carried out in the absence of an organic solvent or water.
  • Small amounts of solvent e.g. required in the addition of the catalyst, do not interfere and apply up to an addition of 5 wt.%, Based on the amount of the polymer, not as a solvent.
  • the process according to the invention reduces the viscosity of the unmodified starting products with barely changed molar weight, since the reaction preferably takes place without crosslinking of polymer chains.
  • the reaction is preferably up to a reduction in the viscosity of the polymers according to the invention of at least 10%, preferably of at least 20%, in particular of at least
  • the viscosity is determined according to DIN 53015 at 20 0 C (10 wt% in ethanol
  • the polymers produced according to the invention can be used as constituents of coating materials such as powder coatings or liquid coatings, for the production of ceramics, ceramic films or for the production of green sheets in ceramic applications, e.g. be used by the tape-cast process.
  • the polymers produced according to the invention furthermore have an improved dispersing behavior and can therefore be used in printing inks, screen printing pastes or metal pigment pastes.
  • the use in adhesives, in particular for the bonding of metal parts, e.g. in the automotive industry is also possible.
  • PV acetate content is understood to mean the percentage of acetyl groups resulting from the consumption of the amount necessary for the saponification of 1 g of substance.
  • the polyvinyl alcohol content is the percentage of hydroxyl groups that can be detected by the subsequent acetylation with acetic anhydride.
  • Flask neck and stopper are rinsed with 50 ml of e-water, covered with 5 ml of n-butanol and titrated the free acetic acid with 1 N sodium hydroxide solution against phenolphthalein. In the same way, a blank is treated.
  • the acetate group fraction is determined by method a) before and after the reaction.
  • the proportion of acetate groups increases by the number of hydroxyl groups reacted with the epoxide.
  • the originally present number of hydroxyl groups is determined on the original material according to method b). The difference between these values corresponds to the proportion of vinyl alcohol groups in the polyvinyl acetal reacted with the epoxide.
  • the dosage of the polyvinyl acetal is carried out at the feed zone, the metering of the catalyst or the reagent system at heating zone 4.
  • the catalyst (Zn (acac) TfO) is previously in situ by the equimolar reaction of 0.1 M Solution Zinc acetylacetonate (Zn (acac) 2) in DME (dimethoxyethane) with 0.1 M solution of trifluoromethanesulfonic acid (TfOH) (in DME). Further details of this catalyst system can be found in EP 1 403 289 A1
  • the casting slip was produced in a manner known to the person skilled in the art
  • Measuring Method To determine the theological properties, 10% strength by weight solutions in the azeotropic solvent mixture ethanol / toluene were prepared by the respective polymers and homogenized in a tumble mixer for 24 h.
  • the rheological characterization was carried out according to the cone-plate measuring principle (cone diameter 50 mm, opening angle 2 °) with the rotation rheometer UDS 200 from. Anton Paar (Austria).
  • the control of the rotating cone is shear stress controlled, the measurement temperature was 20 0 C.
  • the viscosity was applied against the shear stress.
  • Fig. 1 shows the average viscosity of the respective binder solutions at a shear stress of 20 Pa * s, wherein the binder solutions over the entire measuring range had a constant viscosity (Newtonian behavior).
  • the solution with B45H (Comparative Example 4) showed a viscosity in the range of 0.07 to 0.08 Pa * s.
  • the solution of the inventively modified PVB according to Example 9 shows a solution viscosity of 0.045 Pa * s and is thus well below the value of the solution with Mowital B45H.
  • Measuring method In order to assess the dispersing action of the binders, various Al 2 O 3 suspensions (40% by weight of azeotropic ethanol / toluene mixture 60% by weight of Al 2 O 3 ) were prepared. The respective binder or dispersant was gradually added thereto and homogenized for several hours. In the preparation of the films, first the dispersant (in this case the PVB) was pre-dissolved in the solvent and then the powder was added. The respective suspension was characterized by means of a rotational viscometer. The suspension viscosity at a shear rate of 100 1 / s was used as reference value.
  • Fig. 2 shows the viscosities of various suspensions depending on the solids content of the suspension.
  • Suspensions with the PVB binders according to the invention have a reduced compared to the fish oil often used as a dispersant Viscosity. Furthermore, the polymers produced according to the invention have a better dispersing action compared to Mowital B45H, since the viscosity values of correspondingly prepared suspensions are lower than those of the suspensions prepared with Mowital B45H.
  • FIG. 3 A comparison of the dispersing properties of the investigated dispersants is shown in FIG. 3. The better the dispersing effect, the lower the viscosity of the relevant Al 2 O 3 suspension. A significantly thinner and thus better dispersed suspension is achieved when using the present invention with epoxypropane modified PVB type instead of B45H or fish oil.
  • the suspensions (casting slip) prepared as described above were degassed and cast on a 4 m long Folieng embstrom with standing Doppelcrog hassleschuh after the Doctor Blade process.
  • the resulting films gave a thickness of 200 microns and showed no cracks, blisters or defects in the optical evaluation.
  • the density of the cast Al 2 O 3 films was determined by buoyancy measurement according to Archimedes. The green film densities were all in the range customary for film casting between 60 and 70 percent of the theoretical density.
  • Suitable tensile specimens were punched out of the respective green sheets in the form of so-called "dogbones.” For each type of film, 10 tensile specimens were punched transversely and 10 specimens parallel to the casting direction in order to determine a possible anisotropic behavior of the green body The maximum measuring range was 100 N, the loading speed was 10 mm / min., Ambient air was measured at room temperature.
  • the green sheets with B45H (Comparative Example 2) as binder show a typical course for green sheets according to the prior art, wherein the specimens at a tension of 4.98 ⁇ 0.04 MPa and an elongation of 5.9 ⁇ 0.71 percent tear
  • films with polyvinyl alcohols according to the invention modified according to Example 9 as binder show a significantly lower tensile strength of 1.4 ⁇ 0.02 MPa.
  • a tensile stress of 1, 5 MPa is not achieved during the entire measurement. After an elongation of 16.25 ⁇ 0.65%, the sample finally breaks.
  • the products according to the invention have a significant plastic content compared to films of the prior art.
  • polyvinyl alcohols modified according to the invention have distinct softening properties as binders. Because of this property, it would be conceivable to reduce or completely omit the proportion of plasticizers added to the casting slip and thereby achieve similar mechanical properties to films of the prior art, the proportion of organic additives then being reduced.
  • FIG. 5 shows the burnout behavior of the binder from Comparative Example 4 and Example 9 and green films produced therewith.
  • the mass loss of the respective binder was determined as a function of the temperature in air by means of thermal analysis (type: STA 409, Netzsch). The heating rate used was 5 K / min. It can be seen here that the binder according to the invention or green films produced therewith have a significantly more uniform binder burn-out in comparison with binders according to the prior art
  • the modified acetalated polyvinyl alcohols prepared according to the invention are thus suitable for producing ceramic green films.
  • an improved dispersing effect and a higher solids content are achieved, and correspondingly considerable performance advantages are achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un procédé servant à modifier des alcools polyvinyliques acétalisés par réaction avec des époxydes dans les polymères en fusion. L'invention concerne également l'utilisation de ces produits, par exemple dans des applications céramiques.
EP06841564A 2005-12-21 2006-12-21 Procede de modification de polyvinylbutyrals Withdrawn EP1991591A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06841564A EP1991591A1 (fr) 2005-12-21 2006-12-21 Procede de modification de polyvinylbutyrals

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP05112546A EP1801132A1 (fr) 2005-12-21 2005-12-21 Procédé pour modifier des butyrals polyvinyliques
EP06841564A EP1991591A1 (fr) 2005-12-21 2006-12-21 Procede de modification de polyvinylbutyrals
PCT/EP2006/070106 WO2007071770A1 (fr) 2005-12-21 2006-12-21 Procede de modification de polyvinylbutyrals

Publications (1)

Publication Number Publication Date
EP1991591A1 true EP1991591A1 (fr) 2008-11-19

Family

ID=36202433

Family Applications (2)

Application Number Title Priority Date Filing Date
EP05112546A Withdrawn EP1801132A1 (fr) 2005-12-21 2005-12-21 Procédé pour modifier des butyrals polyvinyliques
EP06841564A Withdrawn EP1991591A1 (fr) 2005-12-21 2006-12-21 Procede de modification de polyvinylbutyrals

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP05112546A Withdrawn EP1801132A1 (fr) 2005-12-21 2005-12-21 Procédé pour modifier des butyrals polyvinyliques

Country Status (6)

Country Link
US (1) US8178618B2 (fr)
EP (2) EP1801132A1 (fr)
JP (1) JP2009520856A (fr)
KR (1) KR20080079683A (fr)
CN (1) CN101331158B (fr)
WO (1) WO2007071770A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2028220B1 (fr) * 2006-04-17 2012-04-04 Kuraray Co., Ltd. Article moulé et méthode d'élaboration dudit article
JP5188774B2 (ja) * 2007-10-03 2013-04-24 株式会社クラレ 粉体塗料
EP2410027B1 (fr) * 2010-07-21 2013-01-02 Kuraray Europe GmbH Utilisation d'iso-acétal de polyvinyle dans des formules de couleurs d'impression
FR2974103B1 (fr) * 2011-04-12 2013-04-12 Saint Gobain Composition serigraphiable sur polyvinylbutyral
CN102604562A (zh) * 2012-02-29 2012-07-25 广州神州光电有限责任公司 一种用作贴装叠层陶瓷电容器介质薄膜的胶粘剂及其制法
CN108164621B (zh) * 2017-12-27 2020-07-07 吉晟光电（深圳）有限公司 一种基于聚乙烯醇缩丁醛的改性聚合物及其制备工艺与应用
JP6789416B2 (ja) * 2017-12-27 2020-12-02 積水化学工業株式会社 細胞培養用足場材料からなる樹脂膜、細胞培養用容器及び細胞の培養方法

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
JPS638448A (ja) * 1986-06-27 1988-01-14 Nippon Synthetic Chem Ind Co Ltd:The 樹脂組成物
TW203065B (fr) * 1990-10-24 1993-04-01 Hoechst Ag
DE4201941A1 (de) * 1992-01-24 1993-08-12 Angyal Paul V Lacksystem mit einem filmbildner auf polyvinylbutyralbasis zur erzeugung abziehbarer, filmfoermiger beschichtungen und verfahren zur herstellung des filmbildners
EP0881066B1 (fr) * 1993-11-10 2002-04-17 Minnesota Mining And Manufacturing Company Stratifié adhésif
DE19640731A1 (de) * 1996-10-02 1998-04-16 Clariant Gmbh Wäßrige Polyvinylacetal-Dispersionen
JP4567833B2 (ja) * 2000-02-09 2010-10-20 積水化学工業株式会社 変性ポリビニルアセタール樹脂及びインク組成物
US7811646B2 (en) * 2001-05-14 2010-10-12 Kuraray Co., Ltd. Modified ethylene-vinyl alcohol copolymer and method for the production thereof
JP3751903B2 (ja) * 2002-05-14 2006-03-08 株式会社クラレ 変性エチレン−ビニルアルコール共重合体の製造方法
JP2004339370A (ja) * 2003-05-15 2004-12-02 Kyoto Elex Kk 感光性樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007071770A1 *

Also Published As

Publication number Publication date
CN101331158A (zh) 2008-12-24
US8178618B2 (en) 2012-05-15
KR20080079683A (ko) 2008-09-01
WO2007071770A1 (fr) 2007-06-28
EP1801132A1 (fr) 2007-06-27
US20090176937A1 (en) 2009-07-09
CN101331158B (zh) 2011-08-24
JP2009520856A (ja) 2009-05-28

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