US20070055032A1 - Solvent-free production method for producing acrylate pressure-sensitive adhesive substances - Google Patents
Solvent-free production method for producing acrylate pressure-sensitive adhesive substances Download PDFInfo
- Publication number
- US20070055032A1 US20070055032A1 US10/555,173 US55517304A US2007055032A1 US 20070055032 A1 US20070055032 A1 US 20070055032A1 US 55517304 A US55517304 A US 55517304A US 2007055032 A1 US2007055032 A1 US 2007055032A1
- Authority
- US
- United States
- Prior art keywords
- polymerization
- extruder
- regulators
- initiators
- group
- 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.)
- Abandoned
Links
- 0 *SC(*)=S Chemical compound *SC(*)=S 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N C=C(C)C(=O)OC Chemical compound C=C(C)C(=O)OC VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AOBUORDMCSYPBW-UHFFFAOYSA-N CC(C)C(c1ccccc1)N(O)C(C)(C)C.CC(ON(C(c1ccccc1)C(C)C)C(C)(C)C)c1ccccc1 Chemical compound CC(C)C(c1ccccc1)N(O)C(C)(C)C.CC(ON(C(c1ccccc1)C(C)C)C(C)(C)C)c1ccccc1 AOBUORDMCSYPBW-UHFFFAOYSA-N 0.000 description 1
- QAIFTEKXRFATOA-UHFFFAOYSA-N CC(SC(=S)SC(C)c1ccccc1)c1ccccc1.S=C(Sc1ccccc1)c1ccccc1 Chemical compound CC(SC(=S)SC(C)c1ccccc1)c1ccccc1.S=C(Sc1ccccc1)c1ccccc1 QAIFTEKXRFATOA-UHFFFAOYSA-N 0.000 description 1
- UDSHZVOXWOEDHA-UHFFFAOYSA-N CC1=NC(C)(C)N(C)N1 Chemical compound CC1=NC(C)(C)N(C)N1 UDSHZVOXWOEDHA-UHFFFAOYSA-N 0.000 description 1
- PPXBKVQRNKMXQL-UHFFFAOYSA-N CN(C)C.CN(C)C.CN(C)C Chemical compound CN(C)C.CN(C)C.CN(C)C PPXBKVQRNKMXQL-UHFFFAOYSA-N 0.000 description 1
- XVGWZRZBQVIHKF-UHFFFAOYSA-N CN=C(SC)SC.CSC(=O)SC Chemical compound CN=C(SC)SC.CSC(=O)SC XVGWZRZBQVIHKF-UHFFFAOYSA-N 0.000 description 1
- ZWETVMKPIYRRAX-UHFFFAOYSA-N CSC(=S)SC.CSC(C)=S Chemical compound CSC(=S)SC.CSC(C)=S ZWETVMKPIYRRAX-UHFFFAOYSA-N 0.000 description 1
- ZQWUFEJHELSQJN-UHFFFAOYSA-N c1ccc(C2=NC(c3ccccc3)(c3ccccc3)N(c3ccccc3)N2)cc1.c1ccc(C2=NC3(c4ccccc4-c4ccccc43)N(c3ccccc3)N2)cc1 Chemical compound c1ccc(C2=NC(c3ccccc3)(c3ccccc3)N(c3ccccc3)N2)cc1.c1ccc(C2=NC3(c4ccccc4-c4ccccc43)N(c3ccccc3)N2)cc1 ZQWUFEJHELSQJN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1818—Tubular reactors in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/435—Sub-screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/435—Sub-screws
- B29C48/44—Planetary screws
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
-
- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
-
- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00132—Controlling the temperature using electric heating or cooling elements
- B01J2219/00135—Electric resistance heaters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00186—Controlling or regulating processes controlling the composition of the reactive mixture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/918—Polymerization reactors for addition polymer preparation
Definitions
- the present invention relates to an improved process for the continuous preparation of acrylate pressure-sensitive adhesives by solvent-free polymerization.
- polyacrylate pressure-sensitive adhesives For industrial pressure-sensitive adhesive tape applications it is very common to use polyacrylate pressure-sensitive adhesives.
- Polyacrylates possess a variety of advantages over other elastomers. They are highly stable toward UV light, oxygen, and ozone. Synthetic and natural rubber adhesives generally contain double bonds, which makes these adhesives unstable to the aforementioned environmental influences.
- Another advantage of polyacrylates is their transparency and their usefulness across a relatively wide temperature range.
- Polyacrylate pressure-sensitive adhesives are generally prepared in solution by a free-radical polymerization.
- the polyacrylates are generally coated onto the corresponding backing material from solution, using a coating bar, and then dried. In order to increase the cohesion the polymer is crosslinked. Curing proceeds thermally or by UV crosslinking or by EB curing (EB: electron beams).
- EB electron beams
- PSA pressure-sensitive adhesive
- This new technology has its limitations. Prior to coating, the solvent is removed from the PSA, which is still prepared in solution, in a drying extruder. This concentration procedure, as it is known, in the drying extruder removes the solvent from the polymer solution down to a residual level of ⁇ 2%. Since polymerization therefore continues to take place in solution, the high consumption of organic solvents represents a problem both environmentally and economically. A further factor is that possible solvent residues in the adhesive can lead to odor nuisance in the course of subsequent use.
- a solvent-free polymerization of the acrylate PSA therefore, would result in a considerable improvement of the process as a whole. This, however, is very difficult, since polymerizations are associated with considerable heat production and an increase in viscosity. The high viscosities can lead to problems of mixing and hence also of heat removal and reaction regime.
- the free-radical polymerization of vinyl monomers is known and extensively described (Ullmann's Encyclopedia of Industrial Chemistry, 2nd Edt. Vol. A21, 1992, 305ff, VCH Weinheim).
- EP 016 03 94 describes the solvent-free preparation of polyacrylates in a twin-screw extruder.
- the acrylate hotmelt PSAs prepared by that process have a gel fraction which is in some cases considerably high, of up to 55%, thereby severely impairing the further processing of the PSAs.
- the high gel fraction means that the adhesive can no longer be coated.
- a variety of polymerization methods are suitable for preparing low-molecular-weight PSAs.
- State of the art is the use of regulators, such as of alcohols or thiols (MakromolekOle, Hans-Georg Elias, 5th edition, 1990, Hüthig & Wepf Verlag Basle). These regulators reduce the molecular weight but broaden the molecular weight distribution.
- a further controlled polymerization method employed is that of atom transfer radical polymerization, ATRP, where the initiators used are preferably, monofunctional or difunctional, secondary or tertiary halides and the halide(s) is(are) abstracted using complexes of Cu, of Ni, of Fe, of Pd, of Pt, of Ru, of Os, of Rh, of Co, of Ir, of Cu, of Ag or of Au [EP 0 824 111; EP 0 826 698; EP 0 824 110; EP 0 841 346; EP 0 850 957].
- ATRP atom transfer radical polymerization
- metal catalysts are used, a side effect of which is to affect adversely the aging of the PSAs (gelling, transesterification). Furthermore, the majority of metal catalysts are toxic, discolor the adhesive, and are removable from the polymer only by means of costly and inconvenient precipitation procedures.
- U.S. Pat. No. 4,581,429 discloses a controlled free-radical polymerization process.
- the process employs as its initiator a compound of the formula R′R′′N—O—X, in which X represents a free radical species able to polymerize unsaturated monomers.
- X represents a free radical species able to polymerize unsaturated monomers.
- the reactions exhibit low conversion rates.
- a particular problem is the polymerization of acrylates, which proceeds only to very low yields and molecular weights.
- WO 98/13392 describes open-chain alkoxyamine compounds which have a symmetrical substitution pattern.
- EP 0 735 052 A1 discloses a process for preparing thermoplastic polymers having narrow polydispersities.
- WO 96/24620 describes a polymerization process for which very special radical compounds are described, such as phosphorus-containing nitroxides, for example.
- WO 98/30601 discloses specific nitroxyls based on imidazolidine.
- WO 98/4408 discloses specific nitroxyls based on morpholines, piperazinones, and piperazinediones.
- solvent-free polymerization in a planetary roller extruder produces polymers having a narrow molecular weight distribution.
- the fraction of low-molecular-weight and of high-molecular-weight molecules in the polymer is sharply reduced.
- the flow viscosity is lower. This leads to improved mixing in the planetary roller extruder and hence also to an improvement in heat input and heat removal.
- the invention accordingly provides a process for continuous polymerization of acrylic monomers to polyacrylates in the presence of polymerization regulators, at least one polymerization step being carried out within at least one reaction extruder.
- the reaction extruder is a planetary roller extruder, in particular a hydraulically filled planetary roller extruder.
- the polymerization regulators are selected advantageously from the group of nitroxide regulators and/or RAFT regulators, particularly the alkoxyamines, triazolinyl compounds, thioesters and/or thiocarbonates.
- Regulators which have proven particularly suitable for solvent-free polymerization in a planetary roller extruder are asymmetric alkoxyamines of type (II) in conjunction with their free nitroxyl precursors and with an azo or peroxo initiator which exhibits slow thermal decomposition.
- a combination of the compounds (Ia) and (IIa) is used as initiator system.
- free-radical sources are peroxides, hydroperoxides, and azo compounds; as a number of nonexclusive examples of typical free-radical initiators, mention may be made here of potassium peroxodisulfate, dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-tert-butyl peroxide, azodiisobutyronitrile, cyclohexylsulfonyl acetyl peroxide, diisopropyl percarbonate, tert-butyl peroctoate, and benzpinacol.
- the free-radical initiator used is 1,1′-azobis-(cyclohexanecarbonitrile) (Vazo 88TM from DuPont).
- the compounds of the formula (II) are present preferably in an amount of 0.0001 mol % to 1 mol %, more preferably in an amount of 0.0008 to 0.0002 mol %, based on the monomers.
- the compounds of the formula (I) is present preferably in an amount of 1 mol % to 10 mol %, more preferably in an amount of 3 to 7 mol %, based on compound (II).
- the thermally decomposing initiator from c) is present with particular preference in an amount of 1 to 10 mol %, more preferably in an amount of 3 to 7 mol %, based on compound of the formula (II).
- the reaction is initiated by scission of the X—O bond of the initiator component of the formula (II).
- the scission of the bond is brought about preferably by ultrasound treatment, heating or exposure to electromagnetic radiation in the wavelength range of y radiation, or by microwaves. More preferably the scission of the C—O bond is brought about by heating and takes place at a temperature between 70 and 160° C.
- the initiator system used is at least one triazolinyl compound of the general formula where R # , R ⁇ , R ### , and R #### are chosen independently of one another or are identical and are
- Control reagents (triazolinyl compounds in the sense of the initiator system depicted above) of type (I) are composed, in a more-preferred version, of the following, further-restricted compounds:
- Halogens here are preferably F, Cl, Br or I, more preferably Cl and Br.
- alkyl, alkenyl, and alkynyl radicals in the various substituents both linear chains and branched chains are outstandingly suitable.
- alkyl radicals containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isobutyl, butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
- alkenyl radicals having 3 to 18 carbon atoms are propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl and oleyl.
- alkynyl having 3 to 18 carbon atoms examples include propynyl, 2-butynyl, 3-butynyl, n-2-octynyl and n-2-octadecynyl.
- hydroxy-substituted alkyl radicals are hydroxypropyl, hydroxybutyl or hydroxyhexyl.
- halogen-substituted alkyl radicals are dichlorobutyl, monobromobutyl or trichlorohexyl.
- a suitable C 2 -C 18 heteroaryl radical having at least one oxygen atom in the carbon chain is, for example, —CH 2 —CH 2 —O—CH 2 —CH 3 .
- C 3 -C 12 cycloalkyl radicals include cyclopropyl, cyclopentyl, cyclohexyl or trimethylcyclohexyl.
- C 6 -C 10 aryl radicals include phenyl, naphthyl, benzyl, or further substituted phenyl radicals, such as, for example, ethylbenzene, propylbenzene, p-tert-butylbenzyl, etc., toluene, xylene, mesitylene, isopropylbenzene, dichlorobenzene or bromotoluene.
- the triazolinyl compounds are selected such that R ### and R #### are joined to one another in the form of a spiro compound.
- the compounds of the initiator system are present preferably in an amount of 0.001 mol % to 10 mol %, preferably in an amount of 0.01 to 1 mol %, based on the monomer mixture.
- the solvent-free polymerization was carried out by virtue of the presence of at least one free-radical initiator with at least one thioester as polymerization regulator.
- the thioesters used are compounds of the following general structural formula where R ⁇ and R ⁇ are selected independently of one another and Rs is a radical from one of groups i) to iv) and R ⁇ is a radical from one of groups i) to iii):
- Regulators used are preferably dithioesters and trithiocarbonates.
- the thioester is used with a weight fraction of 0.001% -5%, in particular of 0.025% to 0.25%.
- the molar ratio of free-radical initiator to thioester is in the range from 50:1 and 1:1, in particular between 10:1 and 2:1.
- Polymerization regulators which can be used with great advantage in this case for the inventive purpose are trithiocarbonates or dithioesters.
- control reagent of the general formula: in which
- Control reagents of type (I) are composed, in a more-preferred version, of the following compounds:
- Halogens here are preferably F, Cl, Br or I, more preferably Cl and Br.
- alkyl, alkenyl, and alkynyl radicals in the various substituents both linear chains and branched chains are outstandingly suitable.
- alkyl radicals containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isobutyl, butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
- alkenyl radicals having 3 to 18 carbon atoms are propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl and oleyl.
- alkynyl having 3 to 18 carbon atoms examples include propynyl, 2-butynyl, 3-butynyl, n-2-octynyl and n-2-octadecynyl.
- hydroxy-substituted alkyl radicals are hydroxypropyl, hydroxybutyl or hydroxyhexyl.
- halogen-substituted alkyl radicals are dichlorobutyl, monobromobutyl or trichlorohexyl.
- a suitable C 2 -C 18 heteroaryl radical having at least one oxygen atom in the carbon chain is, for example, —CH 2 —CH 2 —O—CH 2 —CH 3 .
- C 3 -C 12 cycloalkyl radicals include cyclopropyl, cyclopentyl, cyclohexyl or trimethylcyclohexyl.
- C 6 -C 10 aryl radicals include phenyl, naphthyl, benzyl, 4-tert-butylbenzyl or further substituted phenyl, such as, for example, ethyl, toluene, xylene, mesitylene, isopropylbenzene, dichlorobenzene or bromotoluene.
- R $$$ can comprise the aforementioned radicals R $ or R $$ , independently of their selection.
- compounds (la) and (lha) are used as control reagents.
- initiator systems which additionally comprise further free-radical initiators for the polymerization, especially thermally decomposing, free-radical-forming azo or peroxo initiators.
- thermally decomposing, free-radical-forming azo or peroxo initiators for the polymerization, especially thermally decomposing, free-radical-forming azo or peroxo initiators.
- suitability is possessed in principle by all customary initiators that are known for acrylates.
- the production of C-centered radicals is described in Houben Weyl, Methoden der Organischen Chemie, Vol. E 19a, pp. 60-147. These methods are preferentially employed analogously.
- further free-radical initiators for the polymerization are present, especially thermally decomposing initiators, particularly free-radical-forming azo or peroxo initiators.
- thermally decomposing initiators particularly free-radical-forming azo or peroxo initiators.
- the invention further provides a process for preparing acrylate pressure-sensitive adhesives, in which a monomer mixture composed of ethylenically unsaturated compounds, particularly of (meth)acrylic acid and/or derivatives thereof, is subjected to free-radical polymerization using the inventive initiator system described.
- the monomer mixture it is preferred to use a mixture composed of acrylic monomers of the general formula
- monomers used include, additionally, vinyl compounds having a fraction of up to 30% by weight, in particular one or more vinyl compounds selected from the following group:
- vinyl esters vinyl halides, vinylidene halides, nitrites of ethylenically unsaturated hydrocarbons.
- vinyl compounds of this kind examples include vinyl acetate, N-vinylformamide, vinylpyridines, acrylamides, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethyl vinyl ether, vinyl chloride, vinylidene chloride, acrylonitrile, maleic anhydride, styrene, without wishing by dint of this enumeration to impose any unnecessary restriction. Furthermore it is possible to use all additional vinyl compounds which fall within the group set out above, and also all other vinyl compounds which do not fall within the classes of compound specified above.
- the monomers are selected such that the resulting polymers can be used as industrially useful PSAs, particularly such that the resulting polymers possess PSA properties in accordance with the “Handbook of Pressure Sensitive Adhesive Technology” by Donatas Satas (van Nostrand, New York 1989).
- the static glass transition temperature of the resulting polymer is advantageously below 25° C.
- the polymers prepared preferably have an average molecular weight of 50 000 to 600 000 g/mol, more preferably between 100 000 and 500 000 g/mol.
- the average molecular weight is determined by size exclusion chromatography (SEC) or by matrix-assisted laser desorption/ionization—mass spectrometry (MALDI-MS).
- SEC size exclusion chromatography
- MALDI-MS matrix-assisted laser desorption/ionization—mass spectrometry
- the acrylate PSAs prepared by this process possess a polydispersity M w /M n of ⁇ 4.5.
- the planetary roller extruder has proven suitable for a process of this kind.
- Polymerization in the planetary roller extruder has the advantage that the tendency to form gel is substantially lower than in the case, for example, of a twin-screw extruder, and particularly when regulators and copolymerizable photoinitiators are used the observed tendency to form gel is particularly low. This produces, as a result, narrow-distribution polyacrylate hotmelt PSAs with very good properties for further processing, which, furthermore, can be crosslinked very efficiently.
- the low polydispersity leads to advantages in the case of polymerization in the planetary roller extruder, thereby reinforcing the outstanding mixing properties which mark out a planetary roller extruder.
- polymers of low polydispersity are produced, which has advantageous consequences for solvent-free polymerization.
- the viscosity which plays a decisive part particularly in the case of solvent-free polymerization, is brought, as a result of the low polydispersity, into a range which is favorable for solvent-free polymerization. With greater polydispersity the viscosity is likewise increased, thereby reducing the heat removal options and also the mixing action in the reactor. These properties are of critical importance to the reliable implementation of solvent-free polymerizations.
- the positive influence of polydispersity on the viscosity enables a higher conversion and also, as a result, reduces the tendency to form gel, which is in turn important for the use of the adhesive as a hotmelt PSA.
- the planetary roller extruder is suitable for this solvent-free polymerization in particular by virtue of its outstanding thermal characteristics and also of the extremely diverse possibilities of temperature control.
- the extruder used is preferably operated continuously. Partial recycling of the product stream, referred to as loop operation, may also be advantageous. The most advantageous is to prepare a solvent-free polyacrylate PSA in a hydraulically filled planetary roller extruder. Hydraulic filling simplifies compliance with oxygen-free conditions and also the best-possible utilization of the screw length. Moreover, phase boundaries are avoided; such boundaries can have a disruptive effect on the polymerization process.
- the monomers can be metered to the polymerization reactor either individually or as a mixture. Preliminary mixing, especially of the copolymerizable photoinitiator, ensures a uniform distribution of the reaction mixture. In principle, however, mixing in the reactor or by combining different reactant streams in an upstream continuous mixer, which is dynamically operated or which may be a static mixer or a micromixer, is also possible.
- the polymer following polymerization in a planetary roller extruder, is removed from residual volatile constituents such as unreacted monomers in a devolatilizing extruder. After determination of their composition, these constituents can be recycled to the reactant stream.
- the polymer following polymerization and, where necessary, devolatilization and the optional addition of one or more of the additives, the addition being able to take place in the polymerization extruder and/or in a downstream compounding extruder, is advantageously coated from the melt without gel onto a backing (“without gel” denotes compliance with the requirements for coatability of the compositions using the coating apparatus which is commonly used and is familiar to the skilled worker for these purposes, particularly for a coatability distinguished by a uniform (homogeneous) coating pattern without inhomogeneities or streaks when coating takes place through the coating nozzles that are commonly used or through a roller applicator).
- the polyacrylates prepared by the inventive process are optimized by optional blending with at least one resin.
- Tackifying resins for addition include, without exception, all existing tackifier resins which are described in the literature. Representatives that may be mentioned include the pinene resins, indene resins, and rosins, their disproportionated, hydrogenated, polymerized, and esterified derivatives and salts, the aliphatic and aromatic hydrocarbon resins, terpene resins and terpene-phenolic resins, and also C5, C9, and other hydrocarbon resins. Any desired combinations of these and further resins may be used in order to adjust the properties of the resulting adhesive in accordance with requirements.
- any resins that are compatible (soluble) with the corresponding polyacrylate in particular, reference may be made to all aliphatic, aromatic, and alkylaromatic hydrocarbon resins, hydrocarbon resins based on single monomers, hydrogenated hydrocarbon resins, functional hydrocarbon resins, and natural resins. Express reference is made to the depiction of the state of knowledge in the “Handbook of Pressure Sensitive Adhesive Technology”, by Donatas Satas (van Nostrand, 1989).
- one or more plasticizers are metered into the PSA, such as low-molecular-weight polyacrylates, phthalates, whale oil plasticizers or plasticizing resins, for example.
- the acrylate hotmelts may further be blended with one or more additives such as aging inhibitors, light stabilizers, ozone protectants, fatty acids, resins, nucleators, expandants, compounding agents and/or accelerants.
- additives such as aging inhibitors, light stabilizers, ozone protectants, fatty acids, resins, nucleators, expandants, compounding agents and/or accelerants.
- fillers such as fibers, carbon black, zinc oxide, titanium dioxide, solid or hollow glass (micro)beads, microbeads of other materials, silica, silicates, and chalk, the addition of blocking-free isocyanates being a further possibility.
- the polyacrylate is applied as a layer preferably from the melt to a backing or to a backing material.
- the polyacrylate material is applied as a hotmelt composition in the form of a layer to a backing or to a backing material.
- Backing materials used for the PSA are the materials that are customary and familiar to the skilled worker, such as films (polyesters, PET, PE, PP, BOPP, PVC), nonwovens, foams, wovens, and woven sheets, and also release paper (glassine, HDPE, LDPE). This enumeration is not exhaustive.
- crosslinking may be induced, advantageously, by thermal means or by means of high-energy radiation, in the latter case in particular by electron beams (EB) or, following the addition of appropriate photoinitiators, by means of ultraviolet radiation.
- EB electron beams
- Examples of preferred substances which crosslink under irradiation in accordance with the inventive process are difunctional or polyfunctional acrylates or difunctional or polyfunctional urethane acrylates, difunctional or polyfunctional isocyanates or difunctional or polyfunctional epoxides. Use may also be made here, however, of all further difunctional or polyfunctional compounds which are familiar to the skilled worker and are capable of crosslinking polyacrylates.
- Suitable photoinitiators are preferably Norrish type I and type II cleaving compounds, some possible examples of both classes being benzophenone derivatives, acetophenone derivatives, benzil derivatives, benzoin derivatives, hydroxyalkyphenone derivatives, phenyl cyclohexyl ketone derivatives, anthraquinone derivatives, thioxanthone derivatives, triazine derivatives, or fluorenone derivatives, this enumeration making no claim to completeness.
- polyacrylate PSA prepared as described for an adhesive tape, in which case the polyacrylate PSA may have been applied to one or both sides of a backing.
- the polymerization was implemented using a planetary roller extruder consisting of three roller barrels in series, as the reactor.
- the temperature-control medium used was pressurized water.
- the reactor is operated continuously. Before commencement of metering the reactor is flushed with nitrogen for one hour. A mixture is produced from monomers and initiator. Nitrogen is passed through this initial charge in order to render it inert.
- the reaction mixture is conveyed through a static mixer, which is equipped with further feed devices, and then through a heat exchanger into the reactor. The reaction mixture is added to the reactor continuously via a bore on the periphery of the first roller barrel. At the exit from the reactor there is a valve which is used to ensure the hydraulic filling of the reactor.
- the heat exchanger for feed preheating, central spindle, and roller barrels are controlled to the particular desired temperatures.
- the central spindle a temperature of 80° C. was set; the medium for feed preheating to 90° C.
- Roller barrels 1 and 3 were controlled to 100° C., roller barrel 2 to 95° C.
- the rotary speed of the central spindle was 50 revolutions per minute.
- the hydrodynamic residence time was 15 minutes. Following emergence from the reactor, a sample is taken for determination of the conversion. Subsequently, remaining volatile constituents are removed in a devolatilizing extruder.
- the adhesive is coated at 50 g/m 2 onto a Saran-primed PET film 23 ⁇ m thick, using a hotmelt coater with two heatable rollers.
- the 2,2′-bisphenylethyl thiocarbonate is synthesized starting from 2-phenylethyl bromide with carbon disulfide and sodium hydroxide in accordance with a set of instructions in Synth. Communications 18(13), pp. 1531-6, 1988. Yield after distillation: 72%. Characterization: 1 H NMR (CDCl 3 ) ⁇ (ppm): 7.20-7.40 (m, 10 H), 1.53, 1.59 (2 ⁇ d, 6 H), 3.71, 381 (2 ⁇ m, 2 H).
- the conversion was determined gravimetrically and is expressed as a percentage in relation to the amount by weight of the monomers used.
- the polymer is isolated by being dried in a vacuum oven. The weight of the polymer is taken and divided by the initial weight of the monomers employed. The calculated figure corresponds to the percentage conversion.
- the average molecular weight M w and the polydispersity PD were determined via gel permeation chromatography.
- the eluent used was THF with 0.1% by volume trifluoroacetic acid. Measurement took place at 25° C.
- the precolumn used was PSS-SDV, 5 ⁇ , 10 3 A, ID 8.0 mm ⁇ 50 mm. Separation was carried out using the columns PSS-SDV, 5 ⁇ , 10 3 and also 10 5 and 10 6 each with ID 8.0 mm ⁇ 300 mm.
- the sample concentration was 4 g/l, the flow rate 1.0 ml per minute. Measurement was carried out against PMMA standards.
- a polymer was prepared by method A.
- Components used were 5% acrylic acid, 95% n-butyl acrylate and 0.015% azoisobutyronitrile (AIBN, Vazo 64TM, DuPont).
- AIBN azoisobutyronitrile
- the average molecular weight and the polydispersity were determined by means of test B, the conversion by test A, and the gel value by test C. Subsequently a swatch specimen was produced in accordance with method B.
- a polymer was prepared by method A.
- Components used were 5% acrylic acid, 95% n-butyl acrylate and also 0.124% 2,2,-bisphenylethyl thiocarbonate and 0.015% azoisobutyronitrile (AIBN, Vazo 64TM, DuPont).
- AIBN 1,2,-bisphenylethyl thiocarbonate
- 0.015% azoisobutyronitrile AIBN, Vazo 64TM, DuPont.
- the average molecular weight and the polydispersity were determined by means of test B, the conversion by test A, and the gel value by test C. Subsequently a swatch specimen was produced in accordance with method B.
- a polymer was prepared by method A.
- Components used were 1 % acrylic acid, 49.5% n-butyl acrylate, 49.5% 2-ethylhexyl acrylate and also 0.124% 2,2,-bisphenylethyl thiocarbonate and 0.015% azoisobutyronitrile (AIBN, Vazo 64TM, DuPont).
- AIBN 1,2,-bisphenylethyl thiocarbonate
- the average molecular weight and the polydispersity were determined by means of test B, the conversion by test A, and the gel value by test C. Subsequently a swatch specimen was produced in accordance with method B.
- Example 1 serves as the reference example.
- examples 2 to 3 are added.
- examples 2 to 3 acrylate PSAs with a low molar mass were prepared. Through the use of a regulator, polymers having a narrow molecular weight distribution were obtained.
- Example 1 has a very high molecular mass and cannot be coated.
- the molecular weight is lowered to such an extent that coating, which is necessary for use in an adhesive tape, is possible.
- example 2 with a M w of 557 000 g/mol
- example 3 with a lower M w of 431 000 g/mol are coatable at 120° C. and at just 110° C.
- the adhesive tapes can be produced entirely without solvent.
Abstract
Method for the continuous polymerization of acrylic monomers to polyacrylates in an extruder and in the presence of polymerization regulators
Description
- The present invention relates to an improved process for the continuous preparation of acrylate pressure-sensitive adhesives by solvent-free polymerization.
- For industrial pressure-sensitive adhesive tape applications it is very common to use polyacrylate pressure-sensitive adhesives. Polyacrylates possess a variety of advantages over other elastomers. They are highly stable toward UV light, oxygen, and ozone. Synthetic and natural rubber adhesives generally contain double bonds, which makes these adhesives unstable to the aforementioned environmental influences. Another advantage of polyacrylates is their transparency and their usefulness across a relatively wide temperature range.
- Polyacrylate pressure-sensitive adhesives are generally prepared in solution by a free-radical polymerization. The polyacrylates are generally coated onto the corresponding backing material from solution, using a coating bar, and then dried. In order to increase the cohesion the polymer is crosslinked. Curing proceeds thermally or by UV crosslinking or by EB curing (EB: electron beams). The operation described is relatively costly and environmentally objectionable, since as a general rule the solvent is not recycled and the high consumption of organic solvents represents a high environmental burden.
- It is very difficult, moreover, to produce pressure-sensitive adhesive tapes at high coatweight without bubbles.
- One remedy for these disadvantages is the hotmelt process. In this process the pressure-sensitive adhesive (PSA) is applied from the melt to the backing material. This new technology, however, has its limitations. Prior to coating, the solvent is removed from the PSA, which is still prepared in solution, in a drying extruder. This concentration procedure, as it is known, in the drying extruder removes the solvent from the polymer solution down to a residual level of <2%. Since polymerization therefore continues to take place in solution, the high consumption of organic solvents represents a problem both environmentally and economically. A further factor is that possible solvent residues in the adhesive can lead to odor nuisance in the course of subsequent use.
- A solvent-free polymerization of the acrylate PSA, therefore, would result in a considerable improvement of the process as a whole. This, however, is very difficult, since polymerizations are associated with considerable heat production and an increase in viscosity. The high viscosities can lead to problems of mixing and hence also of heat removal and reaction regime. The free-radical polymerization of vinyl monomers is known and extensively described (Ullmann's Encyclopedia of Industrial Chemistry, 2nd Edt. Vol. A21, 1992, 305ff, VCH Weinheim).
- EP 016 03 94 describes the solvent-free preparation of polyacrylates in a twin-screw extruder. The acrylate hotmelt PSAs prepared by that process, however, have a gel fraction which is in some cases considerably high, of up to 55%, thereby severely impairing the further processing of the PSAs. The high gel fraction means that the adhesive can no longer be coated.
- One solution for reducing this disadvantage is offered by polyacrylate adhesives with a low average molecular weight and narrow molecular weight distribution. Reducing the low-molecular-weight fraction lowers the number of oligomers which reduce the shear strength of the PSA.
- A variety of polymerization methods are suitable for preparing low-molecular-weight PSAs. State of the art is the use of regulators, such as of alcohols or thiols (MakromolekOle, Hans-Georg Elias, 5th edition, 1990, Hüthig & Wepf Verlag Basle). These regulators reduce the molecular weight but broaden the molecular weight distribution.
- A further controlled polymerization method employed is that of atom transfer radical polymerization, ATRP, where the initiators used are preferably, monofunctional or difunctional, secondary or tertiary halides and the halide(s) is(are) abstracted using complexes of Cu, of Ni, of Fe, of Pd, of Pt, of Ru, of Os, of Rh, of Co, of Ir, of Cu, of Ag or of Au [EP 0 824 111; EP 0 826 698; EP 0 824 110; EP 0 841 346; EP 0 850 957]. The various possibilities of ATRP are further described in U.S. Pat. No. 5,945,491, U.S. Pat. No. 5,854,364, and U.S. Pat. No. 5,789,487. Generally speaking, metal catalysts are used, a side effect of which is to affect adversely the aging of the PSAs (gelling, transesterification). Furthermore, the majority of metal catalysts are toxic, discolor the adhesive, and are removable from the polymer only by means of costly and inconvenient precipitation procedures.
- Another version is the RAFT process (reversible addition-fragmentation chain transfer). The process is described exhaustively in WO 98/01478 and WO 99/31144, but in the manner depicted there is unsuitable for preparing PSAs, since the conversions achieved are very low and the average molecular weight of the polymers prepared is too low for acrylate PSAs. The polymers described cannot, therefore, be used as acrylate PSAs. An improvement was achieved with the process described by BDF in DE 100 30 217.
- U.S. Pat. No. 4,581,429 discloses a controlled free-radical polymerization process. The process employs as its initiator a compound of the formula R′R″N—O—X, in which X represents a free radical species able to polymerize unsaturated monomers. In general, however, the reactions exhibit low conversion rates. A particular problem is the polymerization of acrylates, which proceeds only to very low yields and molecular weights.
- WO 98/13392 describes open-chain alkoxyamine compounds which have a symmetrical substitution pattern. EP 0 735 052 A1 discloses a process for preparing thermoplastic polymers having narrow polydispersities.
- WO 96/24620 describes a polymerization process for which very special radical compounds are described, such as phosphorus-containing nitroxides, for example.
- WO 98/30601 discloses specific nitroxyls based on imidazolidine.
- WO 98/4408 discloses specific nitroxyls based on morpholines, piperazinones, and piperazinediones.
- DE 199 49 352 A1 discloses heterocyclic alkoxyamines as regulators in controlled free-radical polymerizations.
- Corresponding developments of the alkoxyamines or of the corresponding free nitroxides improved the efficiency for the preparation of polyacrylates [Hawker, C. J., paper, National Meeting of the American Chemical Society, San Francisco, Spring 1997; Husemann, M., IUPAC World Polymer Meeting 1998, Gold Coast, Australia, paper on “Novel Approaches to Polymeric Brushes using ‘Living’ Free Radical Polymerizations” (July 1998)].
- The aforementioned patents and papers attempted to improve the control of free-radical polymerization reactions. Nevertheless, there exists a need for a polymerization process which is highly reactive and with which high conversions can be realized in conjunction with high molecular weight and low polydispersity. This is so in particular for the copolymerization of acrylate PSAs, since, here, high molecular weights are essential for PSA applications. These requirements were met in DE 100 36 801 A1, where the polymerization takes place in organic solvent or water as solvent, so giving rise, here again, to the problem of the high solvent consumption and/or solvent removal.
- It is an object of the invention, therefore, to provide a process for solvent-free preparation of acrylate hotmelt PSAs which exhibits the disadvantages of the cited prior art either not at all or only to a reduced extent.
- Surprisingly, it has been found that the use of regulating substances which produce a narrow molecular weight distribution of the polyacrylates is particularly advantageous in its effects on the solvent-free polymerization process in a reaction extruder, in particular a planetary roller extruder.
- As a result of the use of substances which regulate the polymerization process and are described in more detail below, solvent-free polymerization in a planetary roller extruder produces polymers having a narrow molecular weight distribution. The fraction of low-molecular-weight and of high-molecular-weight molecules in the polymer is sharply reduced. As a result of the drop in the high molecular weight fractions, the flow viscosity is lower. This leads to improved mixing in the planetary roller extruder and hence also to an improvement in heat input and heat removal. With the use of the regulating substances which result in the polymerization in the planetary roller extruder producing polymers having a narrow molecular weight distribution it has surprisingly been found that, as a result, the process of solvent-free polymerization is considerably less sensitive to operational fluctuations. The tendency to form gel in the case of operational fluctuations in, for example, the temperature or rotational speed, for instance, is considerably and unpredictably reduced. It has been found, moreover, that the polymers thus prepared exhibit a higher crosslinking efficiency, which is advantageous for the adhesive technology properties.
- The invention accordingly provides a process for continuous polymerization of acrylic monomers to polyacrylates in the presence of polymerization regulators, at least one polymerization step being carried out within at least one reaction extruder. Very advantageously the reaction extruder is a planetary roller extruder, in particular a hydraulically filled planetary roller extruder.
- The polymerization regulators are selected advantageously from the group of nitroxide regulators and/or RAFT regulators, particularly the alkoxyamines, triazolinyl compounds, thioesters and/or thiocarbonates.
- Regulators which have proven particularly suitable for solvent-free polymerization in a planetary roller extruder are asymmetric alkoxyamines of type (II) in conjunction with their free nitroxyl precursors and with an azo or peroxo initiator which exhibits slow thermal decomposition.
-
-
- R′, R″, R″′ and R″″ are selected independently of one another and are
- a) branched and unbranched C1 to C18 alkyl radicals; C3 to C18 alkenyl radicals; C3 to C18 alkynyl radicals;
- b) C3 to C18 alkynyl radicals; C3 to C18 alkenyl radicals; C1 to C18 alkyl radicals substituted by at least one OH group or halogen atom or silyl ether;
- c) C2-C18 heteroalkyl radicals having at least one oxygen atom and/or NR group in the carbon chain; R being selected from one of the groups a), b) or d) to g),
- d) C3-C18 alkynyl radicals, C3-C18 alkenyl radicals, Cl-C,8 alkyl radicals substituted by at least one ester group, amine group, carbonate group and/or epoxide group and/or by sulfur and/or by sulfur compounds, especially thioethers or dithio compounds;
- e) C3-C12 cycloalkyl radicals;
- f) C6-C10 aryl radicals;
- g) hydrogen;
- is a group having at least one carbon atom and is such that the free radical X- derived from X is able to initiate polymerization of ethylenically unsaturated monomers.
- R′, R″, R″′ and R″″ are selected independently of one another and are
- Halogens here are preferably F, Cl, Br or I, more preferably Cl and Br. As alkyl, alkenyl, and alkynyl radicals in the various substituents, both linear chains and branched chains are outstandingly suitable.
- Examples of alkyl radicals containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isobutyl, butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
- Examples of alkenyl radicals having 3 to 18 carbon atoms are propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl and oleyl.
- Examples of alkynyl having 3 to 18 carbon atoms are propynyl, 2-butynyl, 3-butynyl, n-2-octynyl and n-2-octadecynyl.
- Examples of hydroxy-substituted alkyl radicals are hydroxypropyl, hydroxybutyl or hydroxyhexyl.
- Examples of halogen-substituted alkyl radicals are dichlorobutyl, monobromobutyl or trichlorohexyl.
- A suitable C2-C18 heteroaryl radical having at least one oxygen atom in the carbon chain is, for example, —CH2—CH2—O—CH2—CH3.
- Examples of C3-C12 cycloalkyl radicals include cyclopropyl, cyclopentyl, cyclohexyl or trimethylcyclohexyl.
- Examples of C6-C10 aryl radicals include phenyl, naphthyl, benzyl, or further substituted phenyl radicals, such as, for example, ethyl, toluene, xylene, mesitylene, isopropylbenzene, dichlorobenzene or bromotoluene.
- The lists above serve only as examples of the respective groups of the compound, and do not possess any claim to completeness.
-
- In a very advantageous development of the inventive initiator system, additionally, further free-radical initiators for the polymerization are present, especially thermally decomposing, free-radical-forming azo or peroxo initiators. In principle, however, suitability for this purpose is possessed by all customary initiators known for acrylates. The production of C-centered radicals is described in Houben Weyl, Methoden der Organischen Chemie, Vol. E 19a, pp. 60-147. These methods are preferentially employed analogously.
- Examples of free-radical sources are peroxides, hydroperoxides, and azo compounds; as a number of nonexclusive examples of typical free-radical initiators, mention may be made here of potassium peroxodisulfate, dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-tert-butyl peroxide, azodiisobutyronitrile, cyclohexylsulfonyl acetyl peroxide, diisopropyl percarbonate, tert-butyl peroctoate, and benzpinacol. In one very preferred version the free-radical initiator used is 1,1′-azobis-(cyclohexanecarbonitrile) (Vazo 88™ from DuPont).
- The compounds of the formula (II) are present preferably in an amount of 0.0001 mol % to 1 mol %, more preferably in an amount of 0.0008 to 0.0002 mol %, based on the monomers. The compounds of the formula (I) is present preferably in an amount of 1 mol % to 10 mol %, more preferably in an amount of 3 to 7 mol %, based on compound (II). The thermally decomposing initiator from c) is present with particular preference in an amount of 1 to 10 mol %, more preferably in an amount of 3 to 7 mol %, based on compound of the formula (II).
- The reaction is initiated by scission of the X—O bond of the initiator component of the formula (II). The scission of the bond is brought about preferably by ultrasound treatment, heating or exposure to electromagnetic radiation in the wavelength range of y radiation, or by microwaves. More preferably the scission of the C—O bond is brought about by heating and takes place at a temperature between 70 and 160° C.
-
-
- branched and unbranched C1 to C18 alkyl radicals; C3 to C18 alkenyl radicals; C3 to C18 alkynyl radicals;
- C1 to C18 alkoxy radicals;
- C3 to C18 alkynyl radicals; C3 to C18 alkenyl radicals; C1 to C18 alkyl radicals substituted by at least one OH group or halogen atom or silyl ether;
- C2-C18 heteroalkyl radicals having at least one oxygen atom and/or R#### group in the carbon chain; R#### being able to be any desired organic radical, and, in particular, branched and unbranched C1 to C18 alkyl radicals; C3 to C18 alkenyl radicals; C3 to C18 alkynyl radicals,
- C3-C8 alkynyl radicals, C3-C18 alkenyl radicals, Cl-C,8 alkyl radicals substituted by at least one ester group, amine group, carbonate group, cyano group, isocyano group and/or epoxide group and/or by sulfur, especially thioethers or dithio compounds;
- C3-C12 cycloalkyl radicals;
- C6-C10 aryl radicals;
- hydrogen.
- Control reagents (triazolinyl compounds in the sense of the initiator system depicted above) of type (I) are composed, in a more-preferred version, of the following, further-restricted compounds:
- Halogens here are preferably F, Cl, Br or I, more preferably Cl and Br. As alkyl, alkenyl, and alkynyl radicals in the various substituents, both linear chains and branched chains are outstandingly suitable.
- Examples of alkyl radicals containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isobutyl, butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
- Examples of alkenyl radicals having 3 to 18 carbon atoms are propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl and oleyl.
- Examples of alkynyl having 3 to 18 carbon atoms are propynyl, 2-butynyl, 3-butynyl, n-2-octynyl and n-2-octadecynyl.
- Examples of hydroxy-substituted alkyl radicals are hydroxypropyl, hydroxybutyl or hydroxyhexyl.
- Examples of halogen-substituted alkyl radicals are dichlorobutyl, monobromobutyl or trichlorohexyl.
- A suitable C2-C18 heteroaryl radical having at least one oxygen atom in the carbon chain is, for example, —CH2—CH2—O—CH2—CH3.
- Examples of C3-C12 cycloalkyl radicals include cyclopropyl, cyclopentyl, cyclohexyl or trimethylcyclohexyl.
- Examples of C6-C10 aryl radicals include phenyl, naphthyl, benzyl, or further substituted phenyl radicals, such as, for example, ethylbenzene, propylbenzene, p-tert-butylbenzyl, etc., toluene, xylene, mesitylene, isopropylbenzene, dichlorobenzene or bromotoluene.
- The lists above serve only as examples of the respective groups of the compound, and do not possess any claim to completeness.
- In one particularly advantageous procedure the triazolinyl compounds are selected such that R### and R#### are joined to one another in the form of a spiro compound.
-
- The compounds of the initiator system are present preferably in an amount of 0.001 mol % to 10 mol %, preferably in an amount of 0.01 to 1 mol %, based on the monomer mixture.
- In a further development of the process the solvent-free polymerization was carried out by virtue of the presence of at least one free-radical initiator with at least one thioester as polymerization regulator.
-
-
- i) C1-C18 alkyl, C2-C18 alkenyl, C2-C8 alkynyl, each linear or branched; aryl, phenyl, benzyl, aliphatic and aromatic heterocycles,
- ii) —NH2, —NH—R1, —NR1R2, —NH—C(O)—R1, —NR1—C(O)—R2, —NH—C(S)—R1, —NR1—C(S)—R2,
- where R1 and R2 are radicals selected independently of one another from group i),
- iii) —S—R3, —S—C(S)—R3,
- where R3 is a radical selected from one of groups i) or ii),
- iv) —O—R3, —O—C(OR)—R3,
- where R3 is a radical selected from one of groups i) or ii).
- Regulators used, accordingly, are preferably dithioesters and trithiocarbonates. In a further advantageous version of the inventive process the thioester is used with a weight fraction of 0.001% -5%, in particular of 0.025% to 0.25%. Moreover, it is very favorable for the inventive purpose if the molar ratio of free-radical initiator to thioester is in the range from 50:1 and 1:1, in particular between 10:1 and 2:1.
- Polymerization regulators which can be used with great advantage in this case for the inventive purpose are trithiocarbonates or dithioesters.
-
-
- R$ and R$$ are selected independently of one another or are the same
- branched and unbranched C1 to C18 alkyl radicals; C3 to C18 alkenyl radicals; C3 to C18 alkynyl radicals;
- H or C1 to C18 alkoxy;
- C3 to C18 alkynyl radicals; C3 to C18 alkenyl radicals; C1 to C18 alkyl radicals substituted by at least one OH group or halogen atom or silyl ether;
- C2-C18 heteroalkyl radicals having at least one oxygen atom and/or NR* group in the carbon chain;
- C3-C18 alkynyl radicals, C3-C18 alkenyl radicals, Cl-Cl8 alkyl radicals substituted by at least one ester group, amine group, carbonate group, cyano group, isocyano group and/or epoxide group and/or by sulfur;
- C3-C12 cycloalkyl radicals;
- C6-C18 aryl or benzyl radicals;
- hydrogen;
- R$ and R$$ are selected independently of one another or are the same
- Control reagents of type (I) are composed, in a more-preferred version, of the following compounds:
- Halogens here are preferably F, Cl, Br or I, more preferably Cl and Br. As alkyl, alkenyl, and alkynyl radicals in the various substituents, both linear chains and branched chains are outstandingly suitable.
- Examples of alkyl radicals containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isobutyl, butyl, isobutyl, tert-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
- Examples of alkenyl radicals having 3 to 18 carbon atoms are propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, isododecenyl and oleyl.
- Examples of alkynyl having 3 to 18 carbon atoms are propynyl, 2-butynyl, 3-butynyl, n-2-octynyl and n-2-octadecynyl.
- Examples of hydroxy-substituted alkyl radicals are hydroxypropyl, hydroxybutyl or hydroxyhexyl.
- Examples of halogen-substituted alkyl radicals are dichlorobutyl, monobromobutyl or trichlorohexyl.
- A suitable C2-C18 heteroaryl radical having at least one oxygen atom in the carbon chain is, for example, —CH2—CH2—O—CH2—CH3.
- Examples of C3-C12 cycloalkyl radicals include cyclopropyl, cyclopentyl, cyclohexyl or trimethylcyclohexyl.
- Examples of C6-C10 aryl radicals include phenyl, naphthyl, benzyl, 4-tert-butylbenzyl or further substituted phenyl, such as, for example, ethyl, toluene, xylene, mesitylene, isopropylbenzene, dichlorobenzene or bromotoluene.
- The lists above serve only as examples of the respective groups of the compound, and do not possess any claim to completeness.
-
- where R$$$ can comprise the aforementioned radicals R$ or R$$, independently of their selection.
-
- In connection with the abovementioned polymerizations which proceed by a controlled-growth free-radical mechanism, it is preferred to use initiator systems which additionally comprise further free-radical initiators for the polymerization, especially thermally decomposing, free-radical-forming azo or peroxo initiators. For this purpose, however, suitability is possessed in principle by all customary initiators that are known for acrylates. The production of C-centered radicals is described in Houben Weyl, Methoden der Organischen Chemie, Vol. E 19a, pp. 60-147. These methods are preferentially employed analogously.
- In one very advantageous development of the inventive process, additionally, further free-radical initiators for the polymerization are present, especially thermally decomposing initiators, particularly free-radical-forming azo or peroxo initiators. These initiators are preferably added before or in the course of the polymerization, the addition of the further initiators taking place in at least two process stages.
- The invention further provides a process for preparing acrylate pressure-sensitive adhesives, in which a monomer mixture composed of ethylenically unsaturated compounds, particularly of (meth)acrylic acid and/or derivatives thereof, is subjected to free-radical polymerization using the inventive initiator system described.
-
- where R&=H or CH3 and R&&=H or an alkyl chain having 1-20 carbon atoms.
- In one advantageous embodiment of the inventive process monomers used include, additionally, vinyl compounds having a fraction of up to 30% by weight, in particular one or more vinyl compounds selected from the following group:
- vinyl esters, vinyl halides, vinylidene halides, nitrites of ethylenically unsaturated hydrocarbons.
- Examples of vinyl compounds of this kind that may be mentioned here include vinyl acetate, N-vinylformamide, vinylpyridines, acrylamides, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethyl vinyl ether, vinyl chloride, vinylidene chloride, acrylonitrile, maleic anhydride, styrene, without wishing by dint of this enumeration to impose any unnecessary restriction. Furthermore it is possible to use all additional vinyl compounds which fall within the group set out above, and also all other vinyl compounds which do not fall within the classes of compound specified above.
- For the polymerization the monomers are selected such that the resulting polymers can be used as industrially useful PSAs, particularly such that the resulting polymers possess PSA properties in accordance with the “Handbook of Pressure Sensitive Adhesive Technology” by Donatas Satas (van Nostrand, New York 1989). For these applications the static glass transition temperature of the resulting polymer is advantageously below 25° C.
- The polymers prepared preferably have an average molecular weight of 50 000 to 600 000 g/mol, more preferably between 100 000 and 500 000 g/mol. The average molecular weight is determined by size exclusion chromatography (SEC) or by matrix-assisted laser desorption/ionization—mass spectrometry (MALDI-MS). Depending on reaction regime, the acrylate PSAs prepared by this process possess a polydispersity Mw/Mn of <4.5.
- It has been found that the solvent-free preparation of a polyacrylate hotmelt PSA is possible with advantage in an extruder. The planetary roller extruder, in particular, has proven suitable for a process of this kind. Polymerization in the planetary roller extruder has the advantage that the tendency to form gel is substantially lower than in the case, for example, of a twin-screw extruder, and particularly when regulators and copolymerizable photoinitiators are used the observed tendency to form gel is particularly low. This produces, as a result, narrow-distribution polyacrylate hotmelt PSAs with very good properties for further processing, which, furthermore, can be crosslinked very efficiently.
- Owing to the usually short residence time in the case of polymerizations in a planetary roller extruder, it could not have been foreseen that, when using polymerization regulators during the polymerization in the planetary roller extruder, polyacrylate hotmelt PSAs having good crosslinkability would be prepared.
- The low polydispersity leads to advantages in the case of polymerization in the planetary roller extruder, thereby reinforcing the outstanding mixing properties which mark out a planetary roller extruder. Through the use of regulators, polymers of low polydispersity are produced, which has advantageous consequences for solvent-free polymerization. The viscosity, which plays a decisive part particularly in the case of solvent-free polymerization, is brought, as a result of the low polydispersity, into a range which is favorable for solvent-free polymerization. With greater polydispersity the viscosity is likewise increased, thereby reducing the heat removal options and also the mixing action in the reactor. These properties are of critical importance to the reliable implementation of solvent-free polymerizations. Likewise, the positive influence of polydispersity on the viscosity enables a higher conversion and also, as a result, reduces the tendency to form gel, which is in turn important for the use of the adhesive as a hotmelt PSA.
- The planetary roller extruder is suitable for this solvent-free polymerization in particular by virtue of its outstanding thermal characteristics and also of the extremely diverse possibilities of temperature control.
- The extruder used is preferably operated continuously. Partial recycling of the product stream, referred to as loop operation, may also be advantageous. The most advantageous is to prepare a solvent-free polyacrylate PSA in a hydraulically filled planetary roller extruder. Hydraulic filling simplifies compliance with oxygen-free conditions and also the best-possible utilization of the screw length. Moreover, phase boundaries are avoided; such boundaries can have a disruptive effect on the polymerization process.
- The monomers can be metered to the polymerization reactor either individually or as a mixture. Preliminary mixing, especially of the copolymerizable photoinitiator, ensures a uniform distribution of the reaction mixture. In principle, however, mixing in the reactor or by combining different reactant streams in an upstream continuous mixer, which is dynamically operated or which may be a static mixer or a micromixer, is also possible.
- The addition of further substances such as, for example, initiators, polymerization regulators, and further monomers to the reactant stream along the screw section of the reactor may be advisable. When using a planetary roller extruder composed of a plurality of roller barrels in series, such additions may take place via bores in the connecting flanges of the roller barrels.
- With afterdosing of suitable initiators or initiator mixtures it is possible to achieve high conversions without at the same time, as a result of a high concentration of primary radicals, inducing low molecular weights or instances of polymer gelling.
- In one development of the process the polymer, following polymerization in a planetary roller extruder, is removed from residual volatile constituents such as unreacted monomers in a devolatilizing extruder. After determination of their composition, these constituents can be recycled to the reactant stream.
- In another development of the process, the polymer, following polymerization and, where necessary, devolatilization and the optional addition of one or more of the additives, the addition being able to take place in the polymerization extruder and/or in a downstream compounding extruder, is advantageously coated from the melt without gel onto a backing (“without gel” denotes compliance with the requirements for coatability of the compositions using the coating apparatus which is commonly used and is familiar to the skilled worker for these purposes, particularly for a coatability distinguished by a uniform (homogeneous) coating pattern without inhomogeneities or streaks when coating takes place through the coating nozzles that are commonly used or through a roller applicator).
- Then it is advantageous to crosslink the polymer by means of high-energy radiation and/or thermally; this takes place in particular after the operation of coating onto the backing.
- In summary it is possible to construct the following scheme for an advantageous procedure:
-
- polymerization process of a monomer mixture comprising not only (meth)acrylic acid-based monomers but also polymerization regulators,
- the polymerization taking place in a solvent-free process,
- which is made possible by the use of a planetary roller extruder.
- Through the use of the control reagent, polydispersities of 1.2 to 4.5, in particular up to less than 4, are obtained.
- The polymerization process may be followed by a devolatilizing operation.
- The polymer can be further processed directly. Solvent recycling is unnecessary.
- The polymer is coated from the melt without gel, and
- after coating, it is crosslinked using high-energy radiation and/or thermally.
- For the use of the polyacrylates prepared by the inventive process as pressure-sensitive adhesives (PSAs), the polyacrylates are optimized by optional blending with at least one resin. Tackifying resins for addition which can be used include, without exception, all existing tackifier resins which are described in the literature. Representatives that may be mentioned include the pinene resins, indene resins, and rosins, their disproportionated, hydrogenated, polymerized, and esterified derivatives and salts, the aliphatic and aromatic hydrocarbon resins, terpene resins and terpene-phenolic resins, and also C5, C9, and other hydrocarbon resins. Any desired combinations of these and further resins may be used in order to adjust the properties of the resulting adhesive in accordance with requirements. Generally speaking it is possible to use any resins that are compatible (soluble) with the corresponding polyacrylate; in particular, reference may be made to all aliphatic, aromatic, and alkylaromatic hydrocarbon resins, hydrocarbon resins based on single monomers, hydrogenated hydrocarbon resins, functional hydrocarbon resins, and natural resins. Express reference is made to the depiction of the state of knowledge in the “Handbook of Pressure Sensitive Adhesive Technology”, by Donatas Satas (van Nostrand, 1989).
- In a further advantageous development, one or more plasticizers are metered into the PSA, such as low-molecular-weight polyacrylates, phthalates, whale oil plasticizers or plasticizing resins, for example.
- The acrylate hotmelts may further be blended with one or more additives such as aging inhibitors, light stabilizers, ozone protectants, fatty acids, resins, nucleators, expandants, compounding agents and/or accelerants.
- Additionally they may be admixed with one or more fillers such as fibers, carbon black, zinc oxide, titanium dioxide, solid or hollow glass (micro)beads, microbeads of other materials, silica, silicates, and chalk, the addition of blocking-free isocyanates being a further possibility.
- Particularly for PSA use it is of advantage to the inventive process if the polyacrylate is applied as a layer preferably from the melt to a backing or to a backing material.
- Then, in one advantageous version of the process, the polyacrylate material is applied as a hotmelt composition in the form of a layer to a backing or to a backing material.
- Backing materials used for the PSA, for adhesive tapes for example, are the materials that are customary and familiar to the skilled worker, such as films (polyesters, PET, PE, PP, BOPP, PVC), nonwovens, foams, wovens, and woven sheets, and also release paper (glassine, HDPE, LDPE). This enumeration is not exhaustive.
- For the PSA utility it is particularly advantageous to crosslink the polyacrylates after they have been coated onto the backing or onto the backing material. To produce the PSA tapes the above-described polymers are for this purpose optionally blended with crosslinkers. Crosslinking may be induced, advantageously, by thermal means or by means of high-energy radiation, in the latter case in particular by electron beams (EB) or, following the addition of appropriate photoinitiators, by means of ultraviolet radiation.
- Examples of preferred substances which crosslink under irradiation in accordance with the inventive process are difunctional or polyfunctional acrylates or difunctional or polyfunctional urethane acrylates, difunctional or polyfunctional isocyanates or difunctional or polyfunctional epoxides. Use may also be made here, however, of all further difunctional or polyfunctional compounds which are familiar to the skilled worker and are capable of crosslinking polyacrylates.
- Suitable photoinitiators are preferably Norrish type I and type II cleaving compounds, some possible examples of both classes being benzophenone derivatives, acetophenone derivatives, benzil derivatives, benzoin derivatives, hydroxyalkyphenone derivatives, phenyl cyclohexyl ketone derivatives, anthraquinone derivatives, thioxanthone derivatives, triazine derivatives, or fluorenone derivatives, this enumeration making no claim to completeness.
- Also claimed is the use of the polyacrylate prepared by the inventive process as a pressure-sensitive adhesive.
- Of particular advantage is the use of the polyacrylate PSA prepared as described for an adhesive tape, in which case the polyacrylate PSA may have been applied to one or both sides of a backing.
- Practical Implementations
- Implementation of the Polymerization (Method A):
- The polymerization was implemented using a planetary roller extruder consisting of three roller barrels in series, as the reactor. The roller barrels used have a roller diameter of D=70 mm and were fitted with 7 planetary spindles. Not only the central spindle but also the roller barrels are equipped with temperature-control circuits that are separate from one another. The temperature-control medium used was pressurized water.
- For the polymerization the reactor is operated continuously. Before commencement of metering the reactor is flushed with nitrogen for one hour. A mixture is produced from monomers and initiator. Nitrogen is passed through this initial charge in order to render it inert. By means of a pump, the reaction mixture is conveyed through a static mixer, which is equipped with further feed devices, and then through a heat exchanger into the reactor. The reaction mixture is added to the reactor continuously via a bore on the periphery of the first roller barrel. At the exit from the reactor there is a valve which is used to ensure the hydraulic filling of the reactor.
- The heat exchanger for feed preheating, central spindle, and roller barrels are controlled to the particular desired temperatures. In the case of the central spindle a temperature of 80° C. was set; the medium for feed preheating to 90° C. Roller barrels 1 and 3 were controlled to 100° C., roller barrel 2 to 95° C.
- The rotary speed of the central spindle was 50 revolutions per minute. The hydrodynamic residence time was 15 minutes. Following emergence from the reactor, a sample is taken for determination of the conversion. Subsequently, remaining volatile constituents are removed in a devolatilizing extruder.
- Production of Swatch Specimens (Method B):
- The adhesive is coated at 50 g/m2 onto a Saran-primed PET film 23 μm thick, using a hotmelt coater with two heatable rollers.
- The 2,2′-bisphenylethyl thiocarbonate is synthesized starting from 2-phenylethyl bromide with carbon disulfide and sodium hydroxide in accordance with a set of instructions in Synth. Communications 18(13), pp. 1531-6, 1988. Yield after distillation: 72%. Characterization: 1H NMR (CDCl3) δ (ppm): 7.20-7.40 (m, 10 H), 1.53, 1.59 (2×d, 6 H), 3.71, 381 (2×m, 2 H).
- Test Methods
- The following test methods were employed in order to evaluate the properties of the polymers and of the PSAs prepared.
- Determination of Conversion (Test A.)
- The conversion was determined gravimetrically and is expressed as a percentage in relation to the amount by weight of the monomers used. The polymer is isolated by being dried in a vacuum oven. The weight of the polymer is taken and divided by the initial weight of the monomers employed. The calculated figure corresponds to the percentage conversion.
- Gel Permeation Chromatography GPC (Test A)
- The average molecular weight Mw and the polydispersity PD were determined via gel permeation chromatography. The eluent used was THF with 0.1% by volume trifluoroacetic acid. Measurement took place at 25° C. The precolumn used was PSS-SDV, 5 μ, 103 A, ID 8.0 mm×50 mm. Separation was carried out using the columns PSS-SDV, 5 μ, 103 and also 105 and 106 each with ID 8.0 mm×300 mm. The sample concentration was 4 g/l, the flow rate 1.0 ml per minute. Measurement was carried out against PMMA standards.
- A polymer was prepared by method A. Components used were 5% acrylic acid, 95% n-butyl acrylate and 0.015% azoisobutyronitrile (AIBN, Vazo 64™, DuPont). The average molecular weight and the polydispersity were determined by means of test B, the conversion by test A, and the gel value by test C. Subsequently a swatch specimen was produced in accordance with method B.
- A polymer was prepared by method A. Components used were 5% acrylic acid, 95% n-butyl acrylate and also 0.124% 2,2,-bisphenylethyl thiocarbonate and 0.015% azoisobutyronitrile (AIBN, Vazo 64™, DuPont). The average molecular weight and the polydispersity were determined by means of test B, the conversion by test A, and the gel value by test C. Subsequently a swatch specimen was produced in accordance with method B.
- A polymer was prepared by method A. Components used were 1 % acrylic acid, 49.5% n-butyl acrylate, 49.5% 2-ethylhexyl acrylate and also 0.124% 2,2,-bisphenylethyl thiocarbonate and 0.015% azoisobutyronitrile (AIBN, Vazo 64™, DuPont). The average molecular weight and the polydispersity were determined by means of test B, the conversion by test A, and the gel value by test C. Subsequently a swatch specimen was produced in accordance with method B.
- Results
- Table 1 below initially collates the results of the polymerizations:
TABLE 1 Required roller Mw Polydispersity Conversion temperature for Example [g/mol] PD [%] coating [°] 1 2 380 000 6.1 72 Not coatable 2 557 000 3.5 65 120 3 431 000 3.4 63 110
Mw: average molecular weight from GPC
PD: Mw/Mn = polydispersity from GPC
- Example 1 serves as the reference example. For the inventive process, examples 2 to 3 are added. In examples 2 to 3, acrylate PSAs with a low molar mass were prepared. Through the use of a regulator, polymers having a narrow molecular weight distribution were obtained.
- The advantages of the process become clear when considering the coatability of the acrylate material. Example 1 has a very high molecular mass and cannot be coated. As a result of the use of the regulator in the case of examples 2 and 3, the molecular weight is lowered to such an extent that coating, which is necessary for use in an adhesive tape, is possible. Thus example 2, with a Mw of 557 000 g/mol, and example 3, with a lower Mw of 431 000 g/mol are coatable at 120° C. and at just 110° C. Through the process of the invention it is possible to process the prepared adhesive at a low coating temperature. Accordingly, the adhesive tapes can be produced entirely without solvent.
Claims (18)
1. A process for continuous polymerization of acrylic monomers to polyacrylates in the presence of polymerization regulators, wherin at least one polymerization step is carried out within at least one reaction extruder.
2. The process of claim 1 , wherein the polymerization regulators are selected from the group consisting of nitroxide regulators, RAFT regulators or both.
3. The process of claim 1 , wherein the polyacrylates have a polydispersity D=Mw/Mn of not more than 4.5.
4. The process of claim 1 , wherein the polyacrylates have weight-average molecular weights of 50 000 to 600 000 g/mol.
5. The process of claim 1 , wherein said at least one polymerization step is carried out as a bulk polymerization.
6. The process of claim 1 , wherein said reaction extruder is a planetary roller extruder.
7. The process of claim 1 , wherein downstream of the screw length of the reaction extruder further substances are added.
8. The process of claim 1 , wherin the polymerization process is followed by devolatilization.
9. The process of claim 1 , wherein, after the polymerization and any subsequent devolatilization, the polyacrylate is coated from the melt, without gel, onto a backing.
10. The process of claim 1 , wherein the polymer is crosslinked by means of high-energy radiation and/or thermally, after coating onto a backing.
11. The process of claim 1 , wherein before and/or during the polymerization thermally decomposing, free-radical-forming initiators are added.
12. A polyacrylate prepared by a the process of claim 1 .
13. A pressure-sensitive adhesive for a single-sided or double-sided adhesive tape comprising the polvacrylate of claim 12 .
14. The process of claim 2 , wherein said polymerization regulators are selected from the group consisting of alkoxyamines, triazolinyl compounds, thioesters and thiocarbonates.
15. The process of claim 4 , wherein said weight-average molecular weights are 100 000 to 500 000 g/mol.
16. The process of claim 6 , wherein said planetary extruder is a hydraulically filled planetary roller/extruder.
17. The process of claim 7 , wherein said further substances are selected from the group consisting of initiators, monomers, copolymerizable photoinitiators, and polymerization regulators,
18. The process of claim 11 , wherein said initiators are selected from the group consisting of azo initiators, peroxo initiators and combinations thereof.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10322830.6 | 2003-05-19 | ||
DE10322830A DE10322830A1 (en) | 2003-05-19 | 2003-05-19 | Process for the continuous production of polymers from vinyl compounds by bulk or solvent polymerization |
PCT/EP2004/005349 WO2004101627A1 (en) | 2003-05-19 | 2004-05-18 | Solvent-free production method for producing acrylate pressure-sensitive adhesive substances |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070055032A1 true US20070055032A1 (en) | 2007-03-08 |
Family
ID=33441050
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/555,173 Abandoned US20070055032A1 (en) | 2003-05-19 | 2004-05-18 | Solvent-free production method for producing acrylate pressure-sensitive adhesive substances |
US10/557,086 Abandoned US20070191503A1 (en) | 2003-05-19 | 2004-05-18 | Method for producing solvent-free uv-crosslinkable acrylate pressure-sensitive adhesives |
US10/555,472 Active US7279535B2 (en) | 2003-05-19 | 2004-05-18 | Method for the continuous production of polymers made of vinyl compounds by substance and/or solvent polymerization |
US12/733,000 Expired - Fee Related US8519076B2 (en) | 2003-05-19 | 2010-03-26 | Method for producing solvent-free UV-crosslinkable acrylate pressure-sensitive adhesives |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/557,086 Abandoned US20070191503A1 (en) | 2003-05-19 | 2004-05-18 | Method for producing solvent-free uv-crosslinkable acrylate pressure-sensitive adhesives |
US10/555,472 Active US7279535B2 (en) | 2003-05-19 | 2004-05-18 | Method for the continuous production of polymers made of vinyl compounds by substance and/or solvent polymerization |
US12/733,000 Expired - Fee Related US8519076B2 (en) | 2003-05-19 | 2010-03-26 | Method for producing solvent-free UV-crosslinkable acrylate pressure-sensitive adhesives |
Country Status (7)
Country | Link |
---|---|
US (4) | US20070055032A1 (en) |
EP (3) | EP1626994B1 (en) |
JP (3) | JP4839217B2 (en) |
DE (6) | DE10322830A1 (en) |
ES (3) | ES2282865T3 (en) |
TW (3) | TWI345572B (en) |
WO (3) | WO2004101626A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080058483A1 (en) * | 2006-08-30 | 2008-03-06 | Intertape Polymer Corp. | Recirculation loop reactor bulk polymerization process |
US20090048407A1 (en) * | 2006-08-30 | 2009-02-19 | Intertape Polymer Corp. | Recirculation loop reactor bulk polymerization process |
WO2015002749A1 (en) * | 2013-07-01 | 2015-01-08 | Mark Andy, Inc. | Method and apparatus for in-line solventless lamination |
US20160158971A1 (en) * | 2013-08-01 | 2016-06-09 | Tesa Se | Method for molding a body in a mold |
US9598518B2 (en) | 2006-01-24 | 2017-03-21 | Intertape Polymer Corp. | Continuous bulk polymerization of vinyl monomers |
WO2018176443A1 (en) | 2017-04-01 | 2018-10-04 | Dow Global Technologies Llc | Aqueous polymer dispersion and aqueous coating composition comprising the same |
US20210262233A1 (en) * | 2016-03-25 | 2021-08-26 | Firestone Building Products Company, Llc | Fully-adhered roof system adhered and seamed with a common adhesive |
US11446617B2 (en) | 2017-04-17 | 2022-09-20 | Entex Rust & Mitschke Gmbh | Extruder with planetary roller section for cooling melts |
US11485298B2 (en) | 2017-07-13 | 2022-11-01 | Entex Rust & Mitschke Gmbh | Feeder module in planetary roller extruder design |
US11613060B2 (en) | 2017-03-05 | 2023-03-28 | Entex Rust & Mitschke Gmbh | Planetary roller extruder with a degassing section |
Families Citing this family (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7671152B2 (en) * | 2005-12-22 | 2010-03-02 | The Goodyear Tire & Rubber Company | Surfactantless synthesis of amphiphilic cationic block copolymers |
BRPI0702850A (en) * | 2006-01-24 | 2008-05-20 | Intertape Polymer Corp | bulk polymerization process |
DE102007057189A1 (en) * | 2007-11-28 | 2009-06-04 | Automatik Plastics Machinery Gmbh | Process and apparatus for the production of polyamide |
KR101238782B1 (en) | 2009-07-03 | 2013-02-28 | 주식회사 엘지화학 | Reactor for photopolymerization and preparation method of super adsorbent polymer using the same |
EP2500367A1 (en) * | 2011-03-18 | 2012-09-19 | Henkel AG & Co. KGaA | Block-copolymer containing crosslinkable photoinitator groups |
DE102011112081A1 (en) | 2011-05-11 | 2015-08-20 | Entex Rust & Mitschke Gmbh | Process for processing elastics |
DE102011086502A1 (en) | 2011-11-16 | 2013-05-16 | Tesa Se | Process for the preparation of undyed polyacrylate adhesives having a narrow molecular weight distribution |
DE102011086503A1 (en) | 2011-11-16 | 2013-05-16 | Tesa Se | Process for the preparation of cohesive polyacrylate adhesives having a narrow molecular weight distribution |
DE102011089367A1 (en) * | 2011-12-21 | 2013-06-27 | Tesa Se | PSAs with high molecular weights and narrow molecular weight distribution and process for their preparation |
DE102012008170A1 (en) * | 2012-04-26 | 2013-10-31 | Entex Rust & Mitschke Gmbh | Planetary roller extruder with planetary spindles and thrust ring |
WO2014056553A1 (en) | 2012-10-11 | 2014-04-17 | Entex Gmbh Rust & Mitschke Gmbh | Extruder for processing plastics which are suitable for adhesion |
JP2014213572A (en) * | 2013-04-26 | 2014-11-17 | スリーエム イノベイティブプロパティズカンパニー | Method for producing laminate including cured pressure sensitive adhesive sheet |
CN104870569B (en) * | 2013-09-24 | 2018-06-29 | Lg化学株式会社 | Pressure-sensitive adhesive composition |
DE102013019611A1 (en) | 2013-11-25 | 2015-05-28 | Gneuss Gmbh | Apparatus for the production of polymers |
JP2016148459A (en) * | 2015-01-30 | 2016-08-18 | 秀之 春山 | Solution transfer cooling device and manufacturing method |
DE102015001167A1 (en) | 2015-02-02 | 2016-08-04 | Entex Rust & Mitschke Gmbh | Degassing during the extrusion of plastics |
DE102017001093A1 (en) | 2016-04-07 | 2017-10-26 | Entex Rust & Mitschke Gmbh | Degassing during the extrusion of plastics with sintered metal filter discs |
CN104721054A (en) * | 2015-04-09 | 2015-06-24 | 史祎 | Solvent-free online coating production equipment |
CN104758181A (en) * | 2015-04-09 | 2015-07-08 | 史祎 | Preparation technology of solvent-free sticking agent |
DE102016002143A1 (en) | 2016-02-25 | 2017-08-31 | Entex Rust & Mitschke Gmbh | Filling module in planetary roller extruder design |
DE102017105755A1 (en) | 2017-03-17 | 2018-09-20 | Lohmann Gmbh & Co. Kg | Functionalized acrylates (from the melt) |
DE102017005999A1 (en) | 2017-05-28 | 2018-11-29 | Entex Rust & Mitschke Gmbh | Production of edible sausage pelts from collagen or similar substances by extrusion |
DE102017005998A1 (en) | 2017-06-23 | 2018-12-27 | Entex Rust & Mitschke Gmbh | Chemical process control for flowable feedstock in a planetary roller extruder |
DE102018001412A1 (en) | 2017-12-11 | 2019-06-13 | Entex Rust & Mitschke Gmbh | Degassing during the extrusion of substances, preferably plastics |
JP7025554B2 (en) | 2018-01-11 | 2022-02-24 | エルジー・ケム・リミテッド | Method for manufacturing low molecular weight acrylic resin |
WO2019166125A1 (en) | 2018-02-28 | 2019-09-06 | Entex Rust & Mitschke Gmbh | Method for producing and processing polymers and polymer mixtures in a modular planetary roller extruder |
DE102018221589A1 (en) * | 2018-08-23 | 2020-02-27 | Tesa Se | Process for the production of an in particular thermally vulcanizable adhesive and an adhesive tape with the thermally vulcanizable adhesive |
DE102019207550A1 (en) * | 2019-05-23 | 2020-11-26 | Tesa Se | Process for the production of pressure-sensitive adhesive reactive adhesive tapes |
KR102611378B1 (en) * | 2019-09-26 | 2023-12-08 | 주식회사 엘지화학 | Esterification reaction epuipment and esterification reaction method |
DE102020007239A1 (en) | 2020-04-07 | 2021-10-07 | E N T E X Rust & Mitschke GmbH | Cooling when extruding melts |
EP3892441A1 (en) | 2020-04-07 | 2021-10-13 | Entex Rust & Mitschke GmbH | Retrofitting of an extruder system |
CN115197377B (en) * | 2022-07-20 | 2023-10-10 | 浙江卫星新材料科技有限公司 | Preparation method of continuous bulk polymerization high-absorptivity resin |
Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4581429A (en) * | 1983-07-11 | 1986-04-08 | Commonwealth Scientific And Industrial Research Organization | Polymerization process and polymers produced thereby |
US4619979A (en) * | 1984-03-28 | 1986-10-28 | Minnesota Mining And Manufacturing Company | Continuous free radial polymerization in a wiped-surface reactor |
US5608023A (en) * | 1995-03-30 | 1997-03-04 | Xerox Corporation | Rate enhanced polymerization processes |
US5767210A (en) * | 1996-08-12 | 1998-06-16 | Elf Atochem, S.A. | Process for controlled radical polymerization or copolymerization of (meth)acrylic and vinyl monomers and (co)polymers obtained |
US5789487A (en) * | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
US5811500A (en) * | 1996-11-07 | 1998-09-22 | Elf Atochem S.A. | Process for the controlled radical (CO) polymerization of (Meth) acrylic vinyl vinylidene and diene monomers in the presence of an Rh Co OR Ir |
US5854364A (en) * | 1996-12-26 | 1998-12-29 | Elf Atochem S.A. | Process for the controlled radical polymerization or copolymerization of (meth)acrylic, vinyl, vinylidene and diene monomers, and (co)polymers obtained |
US6114482A (en) * | 1996-08-12 | 2000-09-05 | Elf Atochem, S.A. | Process for the controlled radical polymerization or copolymerization of (meth) acrylic and vinyl monomers and (co) polymers obtained |
US6255448B1 (en) * | 1995-02-07 | 2001-07-03 | Atofina | Polymerization in the presence of a β-substituted nitroxide radical |
US6271340B1 (en) * | 1997-01-10 | 2001-08-07 | E. I. Du Pont De Nemours And Company | Method of controlling polymer molecular weight and structure |
US6281311B1 (en) * | 1997-03-31 | 2001-08-28 | Pmd Holdings Corp. | Controlled free radical polymerization process |
US6288162B2 (en) * | 1998-03-17 | 2001-09-11 | Ciba Specialty Chemicals Corp. | Continuous process for preparing polymer based pigment preparations |
US20010024699A1 (en) * | 2000-02-23 | 2001-09-27 | Basf Aktiengesellschaft | Stabilized UV-crosslinkable hot-melt pressure sensitive adhesives |
US6479608B1 (en) * | 1998-10-16 | 2002-11-12 | Ciba Specialty Chemicals Corporation | Heterocyclic alkoxyamines as regulators in controlled radical polymerization processes |
US20020193539A1 (en) * | 2000-06-20 | 2002-12-19 | Mare Husemann | Method for producing polyacrylates |
US6642318B1 (en) * | 1997-12-18 | 2003-11-04 | E. I. Du Pont De Nemours And Company | Polymerization process with living characteristics and polymers made therefrom |
US6705753B2 (en) * | 2000-02-24 | 2004-03-16 | Berstoff Gmbh | Extruder comprising blister mechanism |
US20040092685A1 (en) * | 2000-07-28 | 2004-05-13 | Marc Husemann | Acrylate contact adhesive materials having tight molecular weight distribution |
US20040171777A1 (en) * | 1996-07-10 | 2004-09-02 | Le Tam Phuong | Polymerization with living characteristics |
Family Cites Families (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2158246C3 (en) * | 1971-11-24 | 1979-06-28 | Eickhoff-Kleinewefers Kunststoffmaschinen Gmbh, 4630 Bochum | Device for the preparation and extrusion of thermoplastics |
DE2303366A1 (en) | 1973-01-24 | 1974-07-25 | Ludwig Wittrock | Extrudable thermoplastic or thermosetting resin mass - by preconsolidating in screw extruder, comminuting formed bodies, plasticising, and consolidating up to extrusion pressure |
DE2443414C2 (en) * | 1974-09-11 | 1983-05-19 | Beiersdorf Ag, 2000 Hamburg | Process for the manufacture of self-adhesive products |
JPS5456662A (en) * | 1977-10-13 | 1979-05-07 | Sumitomo Chem Co Ltd | Continuous production of methyl methacrylate resin plates |
DE3030541C2 (en) * | 1980-08-13 | 1988-09-08 | Rudolf P. 7000 Stuttgart Fritsch | Device for the continuous production of high molecular weight polymers |
JPS5853970A (en) * | 1981-09-28 | 1983-03-30 | Nitto Electric Ind Co Ltd | Pressure-sensitive adhesive composition |
DE3305727A1 (en) * | 1983-02-18 | 1984-08-23 | Nitto Electric Industrial Co., Ltd., Ibaraki, Osaka | Process for the free-radical polymerisation of acrylic monomers |
CS246370B1 (en) * | 1984-11-10 | 1986-10-16 | Miloslav Kolinsky | Method of vinyl polymers one-stage production and reactor for application of this method |
DE3621429A1 (en) | 1985-07-02 | 1987-01-08 | Milchem Inc | CONTINUOUS POLYMERIZATION PROCESS |
JPS6264822A (en) * | 1985-09-17 | 1987-03-23 | Teijin Ltd | Process and apparatus for producing polyester |
DE3605003A1 (en) * | 1986-02-18 | 1987-08-20 | Herberts Gmbh | Thermocurable adhesive film, process for the production thereof, and the use thereof |
JPS6429410A (en) * | 1987-07-25 | 1989-01-31 | Mitsubishi Petrochemical Co | Ultraviolet radiation-curing self-adhesive composition |
IL86605A (en) * | 1988-06-02 | 1992-02-16 | Bromine Compounds Ltd | Process for the polymerization of pentabromobenzylester monoacrylate |
DE3908415A1 (en) | 1989-03-15 | 1990-09-20 | Rust & Mitschke Entex | Processing of rubber mixtures |
DE3914374A1 (en) * | 1989-04-29 | 1990-10-31 | Basf Ag | THROUGH ULTRAVIOLET RADIATION UNDER AIR OXYGEN ATMOSPHERIC CROSSLINKABLE COPOLYMERS |
DE3940954A1 (en) * | 1989-12-12 | 1991-06-13 | Battenfeld Extrusionstech | Extruder screw for efficient mixing - has start and end parts with concentric circular core profiles but asymmetrical intermediate length which is pref. polygonal |
DE4001986C1 (en) * | 1990-01-24 | 1991-09-19 | Hermann Berstorff Maschinenbau Gmbh, 3000 Hannover, De | |
JPH06100605A (en) * | 1992-09-18 | 1994-04-12 | Sanyo Chem Ind Ltd | Production of acrylic resin |
DE4312249C1 (en) * | 1993-04-15 | 1994-03-17 | Inventa Ag | Planetary drive for multi-screw extruder and process - has housing with inner teeth, central shaft sun wheel, screws forming main planetary wheels and intermediate planetary wheels between them |
MX9701468A (en) * | 1994-09-09 | 1997-05-31 | Minnesota Mining & Mfg | Method of making a packaged hot melt adhesive. |
DE9421955U1 (en) | 1994-09-20 | 1997-05-07 | Rust & Mitschke Entex | Planetary roller extruder |
DE4433487C2 (en) | 1994-09-20 | 1998-07-02 | Rust & Mitschke Entex | Planetary roller extruder |
JP3375430B2 (en) * | 1994-10-03 | 2003-02-10 | 積水化学工業株式会社 | Method for producing acrylic polymer |
DE19518255C5 (en) | 1995-05-18 | 2004-07-08 | Entex Rust & Mitschke Gmbh | Planetary roller extruder |
DE19524182A1 (en) | 1995-07-03 | 1997-01-09 | Basf Ag | Process and device for the continuous production of polymers |
EP0755945B1 (en) * | 1995-07-26 | 1998-11-25 | Sulzer Chemtech AG | Process and device for carrying out a polymerisation in a tube reactor |
DE19534813C2 (en) | 1995-09-20 | 2001-12-13 | Rust & Mitschke Entex | Laboratory extruder |
DE19548136A1 (en) * | 1995-12-21 | 1997-06-26 | Gefinex Jackon Gmbh | Low cost, monomer processing to give semi-finished plastic products |
DE19631182A1 (en) | 1996-01-12 | 1997-07-17 | Rust & Mitschke Entex | Granulating extruder, especially for plastics and foodstuffs |
ES2149489T3 (en) * | 1996-03-13 | 2000-11-01 | Minnesota Mining & Mfg | METHODS TO MANUFACTURE VISCOELASTIC COMPOSITIONS. |
DE29724790U1 (en) * | 1997-05-17 | 2004-03-11 | Entex Rust & Mitschke Gmbh | Planetary gear extruder with simplified sensor connections - has running rings at the ends of each planetary gear extruder module with identical connectors in the rings for attaching a temperature and/or pressure sensor and/or an injector |
DE29710235U1 (en) | 1997-06-12 | 1997-08-14 | Battenfeld Extrusionstech | Device for plasticizing plastic material |
DE19806609A1 (en) * | 1998-02-18 | 1999-08-19 | Beiersdorf Ag | Process for the continuous, solvent and mastication free production of non-thermoplastic elastomers based self-adhesive compositions |
EP0943662B1 (en) * | 1998-03-17 | 2002-05-02 | Ciba SC Holding AG | Continuous process for preparing polymer based pigment preparations |
DE19915916A1 (en) | 1999-04-09 | 2000-10-12 | Basf Ag | Process for the continuous production of polymers |
DE19939073A1 (en) * | 1999-08-18 | 2001-02-22 | Beiersdorf Ag | Process for the continuous, solvent and mastication-free production of pressure-sensitive self-adhesive compositions based on non-thermoplastic elastomers and their coating for the production of self-adhesive articles |
DE19939077A1 (en) * | 1999-08-18 | 2001-02-22 | Beiersdorf Ag | Process for the continuous, solvent and mastication-free production of pressure-sensitive self-adhesive compositions based on non-thermoplastic elastomers and their coating for the production of self-adhesive articles |
JP4911811B2 (en) * | 2000-02-28 | 2012-04-04 | スリーエム イノベイティブ プロパティズ カンパニー | Thermally active adhesive and photocrosslinkable thermally active adhesive |
CN1216923C (en) * | 2000-06-23 | 2005-08-31 | 索罗蒂亚公司 | Process for forming solid pressure sensitive adhesive polymer microspheres |
GB0019074D0 (en) * | 2000-08-03 | 2000-09-27 | Ranier Ltd | Precision polyurethane manufacture |
DE10053563A1 (en) * | 2000-10-27 | 2002-05-02 | Tesa Ag | Process for the production of acrylic PSAs |
JP2002241410A (en) * | 2001-02-20 | 2002-08-28 | Nitto Denko Corp | Process for producing polymer |
CN1269860C (en) * | 2001-05-15 | 2006-08-16 | 西巴特殊化学品控股有限公司 | Method of grafting ethylenically unsaturated carboxylic acid derivatives onto thermoplastic polymers using hydroxylamine |
DE10149084A1 (en) * | 2001-10-05 | 2003-06-18 | Tesa Ag | UV crosslinkable acrylic hot melt pressure sensitive adhesive with narrow molecular weight distribution |
EP1336629A3 (en) * | 2002-02-16 | 2003-10-15 | Degussa AG | Process for the preparation of urethane (meth)acrylates |
DE10221047A1 (en) * | 2002-05-10 | 2003-11-27 | Degussa | Process for the solvent-free, continuous production of polyureas |
-
2003
- 2003-05-19 DE DE10322830A patent/DE10322830A1/en not_active Withdrawn
-
2004
- 2004-05-18 DE DE502004003348T patent/DE502004003348D1/en active Active
- 2004-05-18 EP EP04733535A patent/EP1626994B1/en not_active Expired - Fee Related
- 2004-05-18 TW TW093113950A patent/TWI345572B/en not_active IP Right Cessation
- 2004-05-18 ES ES04733562T patent/ES2282865T3/en active Active
- 2004-05-18 TW TW093113944A patent/TWI359157B/en not_active IP Right Cessation
- 2004-05-18 DE DE502004007146T patent/DE502004007146D1/en active Active
- 2004-05-18 DE DE112004000674T patent/DE112004000674D2/en not_active Expired - Fee Related
- 2004-05-18 TW TW093113946A patent/TWI359156B/en not_active IP Right Cessation
- 2004-05-18 WO PCT/EP2004/005339 patent/WO2004101626A1/en active IP Right Grant
- 2004-05-18 EP EP04733562A patent/EP1631599B1/en not_active Expired - Fee Related
- 2004-05-18 DE DE112004000673T patent/DE112004000673D2/en not_active Withdrawn - After Issue
- 2004-05-18 JP JP2006529863A patent/JP4839217B2/en not_active Expired - Fee Related
- 2004-05-18 US US10/555,173 patent/US20070055032A1/en not_active Abandoned
- 2004-05-18 WO PCT/EP2004/005349 patent/WO2004101627A1/en active Application Filing
- 2004-05-18 ES ES04733535T patent/ES2327739T3/en active Active
- 2004-05-18 EP EP04739242A patent/EP1627023B1/en not_active Expired - Fee Related
- 2004-05-18 JP JP2006529861A patent/JP4778901B2/en not_active Expired - Fee Related
- 2004-05-18 WO PCT/EP2004/005341 patent/WO2004101698A1/en active IP Right Grant
- 2004-05-18 DE DE502004009828T patent/DE502004009828D1/en active Active
- 2004-05-18 JP JP2006529864A patent/JP5002263B2/en not_active Expired - Fee Related
- 2004-05-18 ES ES04739242T patent/ES2305783T3/en active Active
- 2004-05-18 US US10/557,086 patent/US20070191503A1/en not_active Abandoned
- 2004-05-18 US US10/555,472 patent/US7279535B2/en active Active
-
2010
- 2010-03-26 US US12/733,000 patent/US8519076B2/en not_active Expired - Fee Related
Patent Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4581429A (en) * | 1983-07-11 | 1986-04-08 | Commonwealth Scientific And Industrial Research Organization | Polymerization process and polymers produced thereby |
US4619979A (en) * | 1984-03-28 | 1986-10-28 | Minnesota Mining And Manufacturing Company | Continuous free radial polymerization in a wiped-surface reactor |
US6255448B1 (en) * | 1995-02-07 | 2001-07-03 | Atofina | Polymerization in the presence of a β-substituted nitroxide radical |
US5608023A (en) * | 1995-03-30 | 1997-03-04 | Xerox Corporation | Rate enhanced polymerization processes |
US20040171777A1 (en) * | 1996-07-10 | 2004-09-02 | Le Tam Phuong | Polymerization with living characteristics |
US5789487A (en) * | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
US5945491A (en) * | 1996-07-10 | 1999-08-31 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
US5767210A (en) * | 1996-08-12 | 1998-06-16 | Elf Atochem, S.A. | Process for controlled radical polymerization or copolymerization of (meth)acrylic and vinyl monomers and (co)polymers obtained |
US6114482A (en) * | 1996-08-12 | 2000-09-05 | Elf Atochem, S.A. | Process for the controlled radical polymerization or copolymerization of (meth) acrylic and vinyl monomers and (co) polymers obtained |
US5811500A (en) * | 1996-11-07 | 1998-09-22 | Elf Atochem S.A. | Process for the controlled radical (CO) polymerization of (Meth) acrylic vinyl vinylidene and diene monomers in the presence of an Rh Co OR Ir |
US5854364A (en) * | 1996-12-26 | 1998-12-29 | Elf Atochem S.A. | Process for the controlled radical polymerization or copolymerization of (meth)acrylic, vinyl, vinylidene and diene monomers, and (co)polymers obtained |
US6271340B1 (en) * | 1997-01-10 | 2001-08-07 | E. I. Du Pont De Nemours And Company | Method of controlling polymer molecular weight and structure |
US6281311B1 (en) * | 1997-03-31 | 2001-08-28 | Pmd Holdings Corp. | Controlled free radical polymerization process |
US6642318B1 (en) * | 1997-12-18 | 2003-11-04 | E. I. Du Pont De Nemours And Company | Polymerization process with living characteristics and polymers made therefrom |
US6288162B2 (en) * | 1998-03-17 | 2001-09-11 | Ciba Specialty Chemicals Corp. | Continuous process for preparing polymer based pigment preparations |
US6479608B1 (en) * | 1998-10-16 | 2002-11-12 | Ciba Specialty Chemicals Corporation | Heterocyclic alkoxyamines as regulators in controlled radical polymerization processes |
US20010024699A1 (en) * | 2000-02-23 | 2001-09-27 | Basf Aktiengesellschaft | Stabilized UV-crosslinkable hot-melt pressure sensitive adhesives |
US6705753B2 (en) * | 2000-02-24 | 2004-03-16 | Berstoff Gmbh | Extruder comprising blister mechanism |
US20020193539A1 (en) * | 2000-06-20 | 2002-12-19 | Mare Husemann | Method for producing polyacrylates |
US6765078B2 (en) * | 2000-06-20 | 2004-07-20 | Tesa Ag | Method for producing polyacrylates |
US20040092685A1 (en) * | 2000-07-28 | 2004-05-13 | Marc Husemann | Acrylate contact adhesive materials having tight molecular weight distribution |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9598518B2 (en) | 2006-01-24 | 2017-03-21 | Intertape Polymer Corp. | Continuous bulk polymerization of vinyl monomers |
US20090048407A1 (en) * | 2006-08-30 | 2009-02-19 | Intertape Polymer Corp. | Recirculation loop reactor bulk polymerization process |
US7829640B2 (en) | 2006-08-30 | 2010-11-09 | Intertape Polymer Corp. | Recirculation loop reactor bulk polymerization process |
US7906598B2 (en) | 2006-08-30 | 2011-03-15 | Intertape Polymer Corp. | Recirculation loop reactor bulk polymerization process |
US20080058483A1 (en) * | 2006-08-30 | 2008-03-06 | Intertape Polymer Corp. | Recirculation loop reactor bulk polymerization process |
US10035338B2 (en) | 2013-07-01 | 2018-07-31 | Mark Andy, Inc. | Method and apparatus for in-line solventless lamination |
CN105451899A (en) * | 2013-07-01 | 2016-03-30 | 麦安迪股份有限公司 | Method and apparatus for in-line solventless lamination |
WO2015002749A1 (en) * | 2013-07-01 | 2015-01-08 | Mark Andy, Inc. | Method and apparatus for in-line solventless lamination |
US20160158971A1 (en) * | 2013-08-01 | 2016-06-09 | Tesa Se | Method for molding a body in a mold |
US20230235560A1 (en) * | 2016-03-25 | 2023-07-27 | Holcim Technology Ltd | Fully-adhered roof system adhered and seamed with a common adhesive |
US11624189B2 (en) * | 2016-03-25 | 2023-04-11 | Holcim Technology Ltd | Fully-adhered roof system adhered and seamed with a common adhesive |
US20210262233A1 (en) * | 2016-03-25 | 2021-08-26 | Firestone Building Products Company, Llc | Fully-adhered roof system adhered and seamed with a common adhesive |
US11613060B2 (en) | 2017-03-05 | 2023-03-28 | Entex Rust & Mitschke Gmbh | Planetary roller extruder with a degassing section |
WO2018176443A1 (en) | 2017-04-01 | 2018-10-04 | Dow Global Technologies Llc | Aqueous polymer dispersion and aqueous coating composition comprising the same |
US11186726B2 (en) | 2017-04-01 | 2021-11-30 | Dow Global Technologies Llc | Aqueous polymer dispersion and aqueous coating composition comprising the same |
AU2017407567B2 (en) * | 2017-04-01 | 2021-02-18 | Dow Global Technologies Llc | Aqueous polymer dispersion and aqueous coating composition comprising the same |
CN110546217A (en) * | 2017-04-01 | 2019-12-06 | 陶氏环球技术有限责任公司 | Aqueous polymer dispersion and aqueous coating composition comprising the same |
US11446617B2 (en) | 2017-04-17 | 2022-09-20 | Entex Rust & Mitschke Gmbh | Extruder with planetary roller section for cooling melts |
US11485298B2 (en) | 2017-07-13 | 2022-11-01 | Entex Rust & Mitschke Gmbh | Feeder module in planetary roller extruder design |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20070055032A1 (en) | Solvent-free production method for producing acrylate pressure-sensitive adhesive substances | |
US6720399B2 (en) | UV-crosslinkable acrylic hotmelt PSAs with narrow molecular weight distribution | |
US6974853B2 (en) | Acrylate contact adhesive materials having tight molecular weight distribution | |
US6765078B2 (en) | Method for producing polyacrylates | |
US7521487B2 (en) | Pressure-sensitive adhesive with dual crosslinking mechanism | |
TWI616500B (en) | Pressure-sensitive adhesives with high molar masses and narrow molar mass distribution and process for preparing them | |
US9540458B2 (en) | Method for producing non-colored polyacrylate adhesive compounds with a narrow molar mass distribution | |
US9683144B2 (en) | Pressure-sensitive adhesive mass for low energy or rough surfaces | |
US20140329971A1 (en) | Method for Producing Cohesive Polyacrylate Adhesive Compounds with a Narrow Molar Mass Distribution | |
TW201127854A (en) | Method for producing polyacrylate | |
US7514515B2 (en) | Method for the production of acrylate adhesive materials using metal-sulphur compounds | |
US20070106011A1 (en) | Method for producing copolymeric polyacrylate pressure-sensitive adhesive substances, and nitroxide-modified polyacrylates and comb block polymers obtained thereby | |
US7071269B2 (en) | Acrylic PSAs with narrow molecular weight distribution | |
US20070287807A1 (en) | Heat-Activable, Pressure-Sensitive Adhesive Mass |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: TESA AG, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LANGENBUCH, JESSICA;MASSOW, KLAUS;ZOLLNER, STEPHAN;REEL/FRAME:018450/0964;SIGNING DATES FROM 20060126 TO 20060131 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |