EP2736940A1 - Structures de papier imprégnées de polyurée et procédé pour leur fabrication - Google Patents

Structures de papier imprégnées de polyurée et procédé pour leur fabrication

Info

Publication number
EP2736940A1
EP2736940A1 EP12738470.9A EP12738470A EP2736940A1 EP 2736940 A1 EP2736940 A1 EP 2736940A1 EP 12738470 A EP12738470 A EP 12738470A EP 2736940 A1 EP2736940 A1 EP 2736940A1
Authority
EP
European Patent Office
Prior art keywords
weight
nco
water
optionally
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12738470.9A
Other languages
German (de)
English (en)
Inventor
Rolf Albach
Hans-Detlef Arntz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer Intellectual Property GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Intellectual Property GmbH filed Critical Bayer Intellectual Property GmbH
Publication of EP2736940A1 publication Critical patent/EP2736940A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible

Definitions

  • the invention relates to pressure-resistant and rigid paper structures impregnated with urethane-modified polyurea, and to a process for their preparation.
  • US-A-5292391 and US-A-5332458 also use the inexpensive, unmodified, polymeric diphenylmethane diisocyanate (MDI).
  • MDI polymeric diphenylmethane diisocyanate
  • the polymeric MDI used in US Pat. No. 5,580,243 has a content of 40-60% of monomeric 4,4'-diphenylmethane diisocyanate and has a wide range of functionalities and viscosities.
  • the sandwich elements described in DE-A 102006016943, DE-A 102008033559 and DE-A 102008051436 are produced from a core material of isocyanate-finished paper honeycombs having improved compressive strength.
  • the object of the present invention was therefore to provide a paper structure which a) contains no solvent or can be prepared without the use of solvents and thus can be used indoors, b) can be produced without difficulty and within a short time to form a supporting element and c) for curing with moisture, a sufficiently hydrophilic synthetic resin is used.
  • the paper structure thus obtained should have a significantly improved bending or compressive rigidity.
  • the object could be achieved by a polyurea-impregnated paper structure, wherein the isocyanate used for the impregnation was chemically modified with long-chain ethylene oxide-containing polyethers.
  • the hardness of the paper structure could be increased, although the content of isocyanate groups in the isocyanate used, which is essential for the crosslinking of the paper structure and the polyurea, is significantly reduced by the modification with the polyethers per unit mass.
  • the invention relates to a process for the production of pressure-resistant and rigid paper structures by impregnation with isocyanate and subsequent reaction with water, water vapor and / or atmospheric moisture, characterized in that i) the paper structure having at least one or more urethane groups
  • NCO prepolymers having an NCO content of 18 to 27 wt .-%, wherein the prepolymer is a reaction product of
  • diphenylmethane diisocyanate isomers and optionally higher homologs thereof and optionally modified diphenylmethane diisocyanates having at least 50 wt .-%, preferably 60 to 90 wt .-%, monomeric diphenyl methane diisocyanate and
  • polymeric polyalkylene oxides having from 1.8 to 8, preferably 2 to 6, particularly preferably 3 to 6, isocyanate-reactive groups per molecule (number-average functionality) and having at least 5 to 100 wt .-%, preferably at least 13 to 90 wt.
  • the polyalkylene oxides preferably have molecular weights of from 1,000 to 15,000, more preferably from 3,000 to 13,000, and may be partially or wholly replaced by polycarbonate polyols having molecular weights of from 1,000 to 15,000.
  • the prepolymer catalysts in an amount of 0.05 to 1 wt.%, Based on the sum of components A) and B) added.
  • metal-containing catalysts are used.
  • catalysts are added to the water, as are normally used in polyurethane chemistry. These include e.g. Carboxylates, phenates, amine oxides and particularly preferably tertiary amine catalysts in an amount of
  • amine catalysts are: alkoxylated ethylenediamine having 3 to 8 molecules of propylene oxide per ethylenediamine, alkoxylated triethanolamine and other alkoxylated amines, optionally in admixture with triethylenediamine and / or pentamethyldiethylenetriamine, dimethylbenzylamine or other tertiary amines known from the prior art.
  • the weight ratio of 4,4'-diphenylmethane diisocyanate to 2,4'-diphenylmethane diisocyanate is preferably between 5 to 1 and 1 to 2.
  • modified diphenylmethane diisocyanates such as uretonimines, carbodiimides or isocyanurates can be used as isocyanate component for the preparation of NCO prepolymers.
  • 4-flame retardant e.g., organic and / or inorganic phosphates or phosphites, expandable graphite.
  • Another object of the invention are pressure-resistant and rigid paper structures, which are impregnated with at least one urethane polyurea, said urethane polyurea having the urethane groups is obtainable from a) one or more urethane containing NCO prepolymers having an NCO content of 18 to 27 wt. -% available
  • polymeric polyalkylene oxides having from 1.8 to 8, preferably 2 to 6, particularly preferably 3 to 6, isocyanate-reactive groups per molecule (number-average functionality) and having at least 5 to 100 wt .-%, preferably at least 13 to 90 wt. -%, particularly preferably at least 17 to 90 wt .-%, most preferably at least 25 to 85 wt .-%, based on polyalkylene oxide, ethylene oxide units and / or polymeric polycarbonate polyols having molecular weights of 1000 to 15000, a '), optionally in admixture with modified diphenylmethane diisocyanates, and b) water, water vapor and / or atmospheric moisture.
  • a further subject of the invention are sandwich elements, which are characterized in that they comprise i) a core of the paper structure according to the invention and ii) at least one layer of fiber-reinforced polyurea and / or polyurethane located on at least one of the two sides of the core.
  • the paper structure is impregnated, for example, by dipping the paper structure in the prepolymer or by applying the prepolymer to the paper structure or by spraying the paper structure with the prepolymer.
  • the height of the paper weight, the quality of the paper (defined according to the fiber structure) and the honeycomb size have mutual effects on the (pressure) strength of the honeycomb.
  • the coating material NCO prepolymer
  • this should preferably penetrate into the fibers of the paper structures. Therefore, paper grades are preferably used which, on the one hand, have good absorbent properties and, on the other hand, do not over-swell during impregnation and consequently lose their structure and strength.
  • Paper structures preferably excess coating material (NCO prepolymer) of the structures removed, for example by tapping, blotting or by means of dry compressed air or other dry compressed gases.
  • NCO prepolymer excess coating material
  • the NCO prepolymer reacts with elimination of carbon dioxide and forms a foam which can also fill the interior of the paper structure (for example the honeycombs).
  • the impregnation of the paper structures according to the invention makes them waterproof, resistant to chemicals and considerably stiffer than untreated paper structures. They are also suitable for outdoor use.
  • the reinforced paper structures can be used as spacers for the production of
  • Isocyanate A is a NCO prepolymer based on diphenylmethane diisocyanate having an NCO content of 23 wt .-% and a viscosity of 405 mPa ⁇ s at 25 ° C. It contains 25% by weight of polymeric polyalkylene oxide based on glycerol having a weight-average molecular weight of 4500 and an ethylene oxide content of 73% by weight.
  • the MDI used consists of 83% by weight of monomeric MDI with a weight ratio of 4,4'-MDI to 2,4'-MDI of 2.9: 1 and 6% by weight of uretonimine.
  • Isocyanate B is a NCO prepolymer based on diphenylmethane diisocyanate having an NCO content of 21.3 wt .-% and a viscosity of 680 mPa ⁇ s at 25 ° C. It contains 31% by weight of polymeric polyalkylene oxide based on propylene glycol and glycerol with a weight average
  • Isocyanate C is an NCO prepolymer based on diphenylmethane diisocyanate with an NCO-
  • the MDI used consists of 60% by weight of monomeric MDI with a weight ratio of 4,4'-MDI to 2,4'-MDI of 2.9: 1.
  • Isocyanate D is an NCO prepolymer based on diphenylmethane diisocyanate having an NCO content of 23.5% by weight and a viscosity of 534 mPa ⁇ s at 25 ° C. It contains 24.7% by weight of polymeric polyalkylene oxide having a weight-average molecular weight of 6000 based on glycerol and an ethylene oxide content of 17% by weight.
  • the MDI used consists of 53% by weight of monomeric MDI with a weight ratio of 4,4 '-MDI to 2,4' -MDI of 2.4: 1 and a uretonimine content of about 2% by weight.
  • Isocyanate E is a propylene carbonate diluted, unmodified, polymeric
  • Diphenylmethane diisocyanate having a viscosity of 63 mPa ⁇ s at 25 ° C and an NCO content of about 24 wt .-%.
  • the paper honeycomb used has a honeycomb diameter of 5 mm, a height of 6.5 mm and a basis weight of 430 g / m 2 .
  • the paper was dipped in the corresponding isocyanate at room temperature, and after
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example ⁇
  • the flexural strength was determined at a constant span of 80 mm.
  • the table shows that the use of the NCO prepolymers A, B, C and D compared to the use of polymeric MDI (isocyanate E) paper structures with improved flexural and / or 5 provides compressive strength.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des structures de papier résistantes à la pression et rigides en flexion qui sont imprégnées de polyurée modifiée par de l'uréthane, ainsi qu'un procédé pour leur fabrication
EP12738470.9A 2011-07-29 2012-07-25 Structures de papier imprégnées de polyurée et procédé pour leur fabrication Withdrawn EP2736940A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011080090 2011-07-29
PCT/EP2012/064624 WO2013017508A1 (fr) 2011-07-29 2012-07-25 Structures de papier imprégnées de polyurée et procédé pour leur fabrication

Publications (1)

Publication Number Publication Date
EP2736940A1 true EP2736940A1 (fr) 2014-06-04

Family

ID=46579038

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12738470.9A Withdrawn EP2736940A1 (fr) 2011-07-29 2012-07-25 Structures de papier imprégnées de polyurée et procédé pour leur fabrication

Country Status (3)

Country Link
EP (1) EP2736940A1 (fr)
CN (1) CN103703046A (fr)
WO (1) WO2013017508A1 (fr)

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2744042A (en) 1951-06-21 1956-05-01 Goodyear Tire & Rubber Laminated panels
SE357222B (fr) * 1968-08-27 1973-06-18 Takeda Chemical Industries Ltd
US5008359A (en) 1988-11-25 1991-04-16 Weyerhaeuser Company Isocyanate modified cellulose products and method for their manufacture
US5140086A (en) 1988-11-25 1992-08-18 Weyerhaeuser Company Isocyanate modified cellulose products and method for their manufacture
US5332458A (en) 1991-04-29 1994-07-26 Weyerhaeuser Co Corrugated paperboard strength enhancing process
US5280097A (en) * 1990-11-27 1994-01-18 Weyerhaeuser Company Laminated composites of polyurea-cellulose and methods for their manufacture
US5292391A (en) 1991-04-29 1994-03-08 Wyerhaeuser Company Corrugated paperboard strength enhancing process
WO1993005232A1 (fr) * 1991-08-30 1993-03-18 Weyerhaeuser Company Composites en cellulose-polycarbamide et procede de fabrication
AU2765392A (en) * 1991-10-02 1993-05-03 Weyerhaeuser Company Polyurea-reinforced fiber-based materials
US5580243A (en) 1995-06-01 1996-12-03 Bloore; John A. Removable orthodontic aligner with eyelet arm springs
US5580922A (en) 1995-06-06 1996-12-03 Weyerhaeuser Company Cellulose products treated with isocyanate compositions
US6372322B1 (en) 1998-05-28 2002-04-16 Pactiv Corporation Shaped honeycomb structures and method and apparatus for making shaped honeycomb structures
DE202006020073U1 (de) 2006-04-11 2008-09-04 Gundelsheimer, Herbert Bauteil aus beschichteter Papierwabe mit tragender Funktion für Sandwichmaterialien
DE102008033559A1 (de) 2008-09-09 2010-03-11 Herbert Gundelsheimer Bauteil aus Sandwichmaterial für höchste Festigkeiten, bestehend aus glasfaserverstärkten Deckschichten und einem Papierwabenkern aus beschichteten Papierwaben
DE102008051436A1 (de) 2008-10-15 2010-04-22 Herbert Gundelsheimer Sandwichmaterial aus einem Kernmaterial von veredelten Papierwaben und Deckschichten aus Holz

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013017508A1 *

Also Published As

Publication number Publication date
CN103703046A (zh) 2014-04-02
WO2013017508A1 (fr) 2013-02-07

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