Classifications

• • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
  • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents

Definitions

• the present invention relates to a novel method for the reversible crosslinking of, for example, adhesive or coating compositions.
• the reversible cross-linking method allows a very fast cross-linking even at room temperature and a
• DE 198 32 629 and DE 199 61 940 describe processes in which adhesives based on epoxy, urea, (meth) acrylate or isocyanate are thermally decomposed.
• the adhesive formulation from DE 199 61 940 contains a thermally unstable substance, which is activated when heated.
• the adhesive layer in DE 198 32 629 is destroyed by a particularly high energy input. The deactivation of the adhesive layer is irreversible in both cases.
• a layer is a shape memory layer that can be thermally flexible or cured.
• the other layer is a dry adhesive, the different
• Dihydrothiopyran group via a hetero-Diels-Alder reaction can be found in Sinnwell et al. (Chem. Comm., 2008, 2052-2054). This method can be used to realize AB diblock copolymers. Fast variants of this hetero-Diels-Alder linkage for the synthesis of AB block copolymers having a dithioester group present after a RAFT polymerization and a dienyl end group are described in Inglis et al. (Angew Chem .. Int, Ed., 2009, 48, pp. 2411-14) and in Inglis et al. (Macromol.Rapd Commun., 2009, 30, p.1792-98). The analogue production of
• Multiarm star polymers are found in Sinnwell et al.
• No. 6,933,361 describes a system for the production of easily repairable, transparent moldings.
• the system consists of two multifunctional monomers, the polymerize to a high density network by a Diels-Alder reaction.
• One functionality is a maleimide and the other functionality is a furan.
• Switching such a high density network is used to repair the same.
• the networking takes place
• 10.1039 / b9py00316a describes star polymers for use as flow improvers in oils. These are controllable by means of a reversible Diels-Alder reaction,
• the object of the present invention is to provide a novel reversible crosslinking method which is disclosed in US Pat
• the object is a reversible
• Binder for various polymers can be used.
• the mechanism also provides new reversibly crosslinkable formulations. Surprisingly, it was found that the tasks set by a
• Hetero-Diels-Alder reaction is crosslinkable, can be solved.
• formulations of the invention contain a
• Component A containing at least two dienophiles
• Component A or B is present as a polymer. It may be in the component with at least three
• the component having at least three functionalities is an oligomer or a low molecular weight substance and the component having two functionalities is a polymer.
• both components are polymers.
• both components have at least three functionalities, regardless of which of the two Components is a polymer.
• both components are polymers having at least three functionalities.
• these polymers may be different or the same polymers, differing only in functional groups.
• the polymers may be polyacrylates,
• Star polymers can have over 30 arms.
• Composition of the arms may vary and be composed of dissimilar polymers. Again, these arms may in turn have branching points.
• Comb polymers can have a block structure and variable comb arms.
• (meth) acrylates is alkyl esters of acrylic acid and / or the
• Methacrylic acid A particular aspect of the invention is that the
• Formulation is crosslinkable at room temperature and the crosslinking at a higher temperature to at least 50% can be reversed.
• the dienophile is a
• the dienophile is a dithioester.
• the dienophile is a compound with the
• Electron-withdrawing group, at R m is a Regionige organic group, preferably based on branched or linear alkylic, aromatic or a combination of alkylic and aromatic multifunctional
• R m may also be a polymer.
• the number of dithioester groups n is a number between 2 and 20, preferably between 2 and 10 and
• the group Z is a 2-pyridyl group. , a phosphoryl group or a
• Crosslinking catalyst crosslink very quickly. Equally surprisingly, it has been found that these networks can be used even at very low temperatures of e.g. just over 80 ° C again easy and almost completely in one
• Thermoplastics can be recycled. Moreover, it has been found, surprisingly, that subsequent crosslinking, without further addition of crosslinker and / or catalyst, e.g. can be done again by pure cooling. In addition, it is a special
• Property loss of the network can be performed.
• component B is a radical radical by atom transfer
• Halogen atoms This substitution can be carried out, for example, by adding dieno functionalized mercaptans.
• Another aspect of the present invention is the process for reversible crosslinking.
• a formulation of at least two different components A and B by means of a Diels-Alder or a hetero-Diels-Alder reaction at
• preferably at least 90% and particularly preferably at least 99% of the crosslinking sites are dissolved again by means of a retro-Diels-Alder reaction or a retro-hetero-Diels-Alder reaction.
• a temperature above 80 ° C. preferably within 5 minutes, at most within 10 minutes, at least 90% by weight, preferably at least 95% by weight and more preferably at least 98% by weight of the formulation in one of the
• Solvents at most 5% by weight, preferably at most 2% by weight and particularly preferably at most 1% by weight of the formulation could be dissolved.
• formulation and all related percentages in this case refer only to components A and B.
• formulation ingredients such as those in a coating or adhesive composition
• composition additionally includes, in addition to the formulation
• additives specially selected for the respective application, such as, for example, fillers, pigments, additives, compatibilizers,
• Co-binders plasticizers, impact modifiers, thickeners, defoamers, dispersing additives, rheology improvers, adhesion promoters, scratch-resistant additives, catalysts or
• Stabilizers act.
• components A and B are first brought together in the process.
• the components A and / or B are at least one polymer according to the listing listed above.
• the crosslinking reaction may be carried out at room temperature within 10 minutes, preferably within 5 minutes, more preferably within 2 minutes, and most preferably within one minute.
• a crosslinking catalyst can be added after mixing components A and B.
• These crosslinking catalysts are usually strong acids such as trifluoroacetic acid or sulfuric acid or strong Lewis acids such as e.g. boron trifluoride,
• Zinc dichloride titanium dichloride diisopropylate or
• the crosslinking can also be accelerated without a catalyst, for example thermally.
• the activation temperature is below the temperature needed for the retro (hetero) Diels-Alder reaction.
• the formulation contains, independently of the activation of the
• Crosslinking reaction a further catalyst which lowers the activation temperature of the retro-Diels-Alder or the retro-hetero Diels-Alder reaction.
• Catalysts may be, for example, iron or an iron compound.
• formulations or processes according to the invention can be used in a wide variety of fields of application.
• the following list exemplifies some preferred applications, without limiting the invention in any way.
• Such preferred fields of application are adhesives, sealants, molding compounds, lacquers, paint, coatings,
• compositions that are thermally applied and crosslink on the substrate.
• an electrically conductive ink is used
• obtained e.g. can be processed by bubble-jet method.
• compositions which are e.g. porous
• adhesives or sealants is the use in food packaging that occurs during
• Heating for example, can be solved automatically in a microwave or open.
• the weight average molecular weights of the polymers were determined by GPC (gel permeation chromatography). The measurements were carried out with a PL-GPC 50 Plus from Polymer Laboratories Inc. at 30 ° C. in tetrahydrofuran (THF) against a series of polystyrene standards (about 200 to 1-10 6 g / mol). The NMR analyzes were carried out on a Bruker AM 400 MHz
• Electrospray ionization source measured.
• the instrument was m / z range 195-1822 using a
• the LXQ was operated on a 1200 HPLC system (Agilent, Santa Clara, CA, USA) consisting of a degasser (G1322A), a binary pump (G1312A), and an autosampler (G1367B) followed by a thermostatted column space (G1316A).
• Example 1 Synthesis of bis (bromo) polymethyl methacrylate 50 equivalents of methyl methacrylate (MMA), 1 equivalent of 1,2-bis (bromoisobutyryloxy) ethane, 0.105 equivalents
• Cyclopentadienyl-terminated poly (methyl methacrylate) (PMMA-CP 2 ) is precipitated twice in cold hexane. The more than 95% double functionalization with cyclopentadienyl groups is detected by ESI-MS. The m / z values are each smaller by about 29.6 g mol -1 compared with the measurement of the product from example 1.
• Tetrapropylammonium bromide 1.52 g (10 mmol) and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) in 10 mL acetonitrile is stirred at reflux for 12 h. Subsequently, all volatiles such as the solvent are removed under vacuum and the residue dissolved in a little methylene chloride. The solution is washed with sodium chloride solution extracted by shaking, dried over magnesium sulfate, filtered and the solvent removed in vacuo. The crude product (2) is obtained in qunatitativen amounts as a white solid and used without further purification in the second stage.
• Step 2 (4- ((Pyridine-2-carbonothioylthio) methyl) benzoic acid hydrochloride) (3a): A mixture of 1.9 g (8.51 mmol) of Step 1 (2) and 0.78 g (24, 3 mmol) sulfur are stirred in 10 mL tetrahydrofuran (THF) using a magnetic stirrer in a 50 mL round bottom flask. After addition of 2.72 g (24.3 mmol) of potassium tert-butoxide, the solution becomes dark brown. The mixture is stirred at room temperature for a further 12 hours. Thereupon, 2.6 g (12.15 mmol) of 4-
• Tris (hydroxymethyl) propane (TMP, (4)), 0.118 g (0.402 mmol) of 4- (dimethylamino) -pyridinium-4-tosylate (DPTS) and 0.025 g (0.201 mmol) of dimethylaminopyridine (DMAP) are dissolved in 10 mL of methylene chloride , 0.581 g (2.01 mmol) of the product from stage 2 (3) are dissolved in 3 ml of dimethylformamide (DMF) and slowly added dropwise to the solution. After stirring for 10 minutes, 0.622 g (3.01 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 2 ml of dichloromethane are added.
• DMF dimethylformamide
• trifunctional crosslinker was carried out by means of 1 R or 13 C NMR spectroscopy and by ESI-MS measurements. The latter gave an average molecular weight of the product m / z exp of 970.08 g-mol -1 . The theoretical molecular weight of
• Crosslinker m / z th eor is 970, 12 g-mol -1 .
• Example 4 Reversible Crosslinking Step 1: Crosslinking Reaction: PMMA-Cp 2 from Example 2 and the trifunctional crosslinker from Example 3 are mixed in a molar ratio of 2 to 3 and mixed in
• Trifluoroacetic acid (TFA) is added and the mixture is shaken at room temperature for 10 minutes.
• TFA Trifluoroacetic acid
• Polymer from stage 1 is mixed with toluene and shaken for 5 minutes.
• the toluene phase remains colorless.
• Step 3 Second Crosslinking Reaction: The toluene from Step 2 is removed in vacuo and the residual solid dissolved in chloroform. The fact that the solid dissolves almost completely is a clear indication that almost complete dewetting in stage 2
• Fig.l the synthesis of the exemplary crosslinker of Example 3 is shown for better clarity.
• the designations level 1 to 3 correspond to the example.
• the numbers shown in brackets can also be found in the example. In addition, find yourself
• PhS0 2 Na sodium phenylsulfinate
• Pr 4 NBr Tetrapropylammonium bromide
• CH 3 CN acetonitrile
• Crosslinker (5) from Example 3 shown. The letters are used to assign the signals to the respective protons of the crosslinker (5).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Sealing Material Composition (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Paints Or Removers (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

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• 2010
  • 2010-02-16 DE DE102010001987A patent/DE102010001987A1/de not_active Withdrawn
• 2011
  • 2011-01-04 ES ES11700157.8T patent/ES2635083T3/es active Active
  • 2011-01-04 US US13/577,932 patent/US8916635B2/en not_active Expired - Fee Related
  • 2011-01-04 CA CA2789841A patent/CA2789841C/en not_active Expired - Fee Related
  • 2011-01-04 CN CN201180007005.1A patent/CN102844391B/zh not_active Expired - Fee Related
  • 2011-01-04 EP EP11700157.8A patent/EP2536797B1/de not_active Not-in-force
  • 2011-01-04 AU AU2011217504A patent/AU2011217504A1/en not_active Abandoned
  • 2011-01-04 BR BR112012020564A patent/BR112012020564A2/pt not_active Application Discontinuation
  • 2011-01-04 JP JP2012553236A patent/JP5855021B2/ja not_active Expired - Fee Related
  • 2011-01-04 WO PCT/EP2011/050043 patent/WO2011101176A1/de not_active Ceased
  • 2011-01-04 PL PL11700157T patent/PL2536797T3/pl unknown
  • 2011-01-04 DK DK11700157.8T patent/DK2536797T3/en active
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