EP1261671A1 - Procede de preparation de polymeres postreticules par voie radicalaire, par utilisation d'elements structurels - Google Patents

Procede de preparation de polymeres postreticules par voie radicalaire, par utilisation d'elements structurels

Info

Publication number
EP1261671A1
EP1261671A1 EP01946880A EP01946880A EP1261671A1 EP 1261671 A1 EP1261671 A1 EP 1261671A1 EP 01946880 A EP01946880 A EP 01946880A EP 01946880 A EP01946880 A EP 01946880A EP 1261671 A1 EP1261671 A1 EP 1261671A1
Authority
EP
European Patent Office
Prior art keywords
compounds
stage
post
radical
polyurethanes
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Withdrawn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
EP01946880A
Other languages
German (de)
English (en)
Inventor
Horst Sulzbach
Rainer HÖFER
Ralf Bemmann
Michael Skwiercz
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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 Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1261671A1 publication Critical patent/EP1261671A1/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Withdrawn legal-status Critical Current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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a process for producing free-radically post-crosslinked polymers.
  • first stage one or more special acrylic or methacrylic acid derivatives based on naturally occurring oils are reacted with aromatic and / or aliphatic isocyanates, and in the second stage the polyurethanes (a *) obtained in this way are subjected to radical post-crosslinking in the presence of a radical initiator (b) subjected.
  • a radical initiator (b) subjected a radical initiator (b) subjected.
  • the requirement here is that a combination of the compounds (a *) with one or more compounds (c) is used in the second stage, the compounds (c) being selected from the group of acrolein, acrylamide, vinyl acetate and styrene.
  • the compounds (c) are also referred to as structural components.
  • US-A-3,979,270 describes a method for curing amine derivatives of reaction products of acrylated epoxidized soybean oil, the curing being carried out by high-energy radiation.
  • the object of the present invention was to provide a process for the preparation of polymers with excellent properties, in particular with regard to impact resistance, also hydrophobicity, chemical stability and water or water vapor resistance.
  • these polymers should be suitable as matrix materials for composite materials due to their special application properties.
  • the present invention relates to a process for the preparation of free-radically post-crosslinked polymers, the first stage being one or more compounds (a), the reaction products of epoxidized fatty acid esters and / or epoxidized triglycerides with acrylic acid and / or methacrylic acid, by reaction with aliphatic and / or aromatic isocyanates are converted into the corresponding polyurethanes (a *) and the polyurethanes (a *) thus prepared are then radically crosslinked in a second stage in the presence of at least one radical initiator (b), with the additional proviso that in the second stage uses a combination of the compounds (a *) with one or more compounds (c), the compounds (c) being selected from the group of acrolein, acrylamide, vinyl acetate and styrene.
  • the first stage being one or more compounds (a)
  • the term “subsequently” merely means that the second stage of the method according to the invention follows the first stage. There is no restriction in terms of time with this term.
  • the second stage of the method according to the invention can therefore be used immediately afterwards to the first stage of the process, but it can also - depending on the desired application - take place after storage of the intermediate product (of a polyurethane) obtained in the first stage of the process, there being no fundamental restrictions with regard to the storage time.
  • esters of olefinically unsaturated fatty acids or triglycerides which contain olefinically unsaturated fatty acids as fatty acid building blocks are subjected to epoxidation, one or more double bonds per molecule being converted into oxirane groups.
  • Preferred fatty acid building blocks of the fatty acid esters to be epoxidized are carboxylic acids having 12 to 24 carbon atoms and containing at least one olefinic double bond in the molecule.
  • those triglycerides are preferred in which at least one fatty acid building block contains at least one olefinic double bond per triglyceride molecule.
  • epoxidized triglycerides are the epoxidation products of the following unsaturated oils: soybean oil, linseed oil, tall oil, cottonseed oil, peanut oil, palm oil, sunflower oil (old and new cultivation), rape oil and claw oil. They are produced in particular by reacting the unsaturated oils mentioned with performic or peracetic acid.
  • Preferred triglycerides are those which have an iodine number in the range from 50 to 200 and which, with extensive epoxidation of the olefinic double bonds, are converted into epoxides with a content of 3 to 10% by weight of epoxy oxygen.
  • epoxidized triglycerides are epoxidized soybean oil (e.g. commercial product "Edenol D 81" from Cognis Deutschland GmbH - formerly Henkel KGaA) and epoxidized linseed oil (e.g. commercial product "Edenol B 316" from Cognis Deutschland GmbH - formerly Henkel KGaA).
  • the ring-opening product of the epoxidized soybean oil with acrylic acid which has a hydroxyl number of about 158 mg KOH per g substance, is used as the acrylated oil (a).
  • This acrylate is first reacted with aromatic and / or aliphatic isocyanates, a catalyst, for example an organic tin compound, preferably being used in the aliphatic isocyanates.
  • one or more (meth) acrylated compounds (a) are subjected to a 2-stage treatment according to the process of the invention, namely
  • Diisocyanates, oligo- or polyisocyanates, and mixtures of these compounds are preferably used.
  • the polyisocyanates include, for example, adducts of diisocyanates with trimethylolpropane, biurets, uretdiones (cyclodimerized isocyanates), isocyanurates (cyclotrimerized isocyanates), allophanates, carbodiimide-based isocyanates and the like (merely by way of example with regard to this Knowledge of the person skilled in the art with regard to the di- and polyisocyanates is referred to: Ullmanns Encyklopadie der Technische Chemie, Volume 19, 4th edition, Weinheim 1980, pages 302-304 and to Kirk-Othmer, Encyclopedia of Chemical Technology, 4th edition, New York 1995, Volume 14, pages 902-934) and finally on Gerhard W.
  • Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thioglycol or dihydroxydihexyl sulfide.
  • Other important diisocyanates are trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,12-diisocyanatododecane and dimer fatty acid diisocyanate (commercial product "Sovermol DDI 1410" from Cognis Deutschland GmbH - formerly Henkel KgaA).
  • diisocyanates are: tetramethylene, hexamethylene, undecane, decamethylene, 2,2,4-trimethylhexane, 1,3-cyclohexane, 1,4-cyclohexane, 1,3- and 1, 4- tetramethylxylene, isophorone, 4,4-dicyclohexylmethane and lysine ester diisocyanate.
  • higher-functional isocyanates are used, which is understood to mean those isocyanates which have an average NCO functionality of at least 2.0.
  • polyisocyanates for example polymer MDI and the like and the polyisocyanates of the formulas 1 to 7 disclosed in EP-A-438 836) which have an NCO functionality above 2.0.
  • NCO functionality because the corresponding higher-functional isocyanates do not necessarily have to be in the form of chemically uniform individuals, such as cyclotrimerized isocyanates, but - particularly in the case of commercially available technical products - frequently represent mixtures of different chemical individuals, each of which defines a defined NCO Functionalities.
  • reaction ratios of the components (a) and the isocyanates are chosen so that the equivalent ratio of NCO: OH is in the range from 0 , 03: 1 to 1.2: 1. It is preferred to work in the range of about 0.4: 1.
  • the compounds (c) are selected from the group of acrolein, acrylamide, vinyl acetate and styrene.
  • the individual members of this group can be used either alone or in combination with each other.
  • the substances (c) are used in technical quality.
  • the compounds (c) are present in the second stage of the process. So that this criterion is met, the compounds (c) can be metered in specifically to the compounds (a *); however, it may also be desirable to mix the compounds (c) in the first stage with the Compounds (a) use, since they are practically not affected by the urethamization reaction. A combination of both possibilities of metering in the compounds (c) is also possible.
  • the postcrosslinking in the second step of the process according to the invention is carried out in the presence of at least one radical initiator (b).
  • This initiator is not critical in itself.
  • an organic peroxide is preferably used as the radical initiator. Such organic peroxides are commercially available in large numbers.
  • the postcrosslinking is carried out in the presence of 0.1 to 10% by weight, based on the polyurethane (a *) used, of one or more radical initiators (b).
  • the postcrosslinking can be carried out per se according to all relevant methods known to the person skilled in the art.
  • Transition metal compounds (d) are preferably used as catalysts.
  • the amount of the transition metal compound - metal content of the transition metal compound based on the polyurethane obtained in the first stage of the process according to the invention - is from 0.01 to 1000 ppm.
  • the type of transition metal compound there is no particular restriction per se. Accordingly, within the framework of the teaching of the present invention In principle, all transition metal compounds known to the person skilled in the art are used.
  • transition metal salts are used as transition metal compounds, preferably salts based on organic acids with 6-22 C atoms.
  • those transition metal compounds are used whose metals are selected from the group consisting of cobalt, zirconium, iron, lead, manganese, nickel, chromium, vanadium, cerium, titanium and tin.
  • Cobalt-II-octoate which is used in particular in the form of a solution, for example in phthalate, is particularly preferred as the catalyst.
  • the postcrosslinking is carried out in the absence of a catalyst at temperatures in the range from 60 to 160 ° C. and in particular 120 to 160 ° C.
  • This special type of post-crosslinking can be referred to as hot curing. Short-term heating to temperatures of around 150 ° C is particularly advantageous; response times in the range of just a few minutes are typically required.
  • a particular advantage of heat curing is that post-crosslinkable resins which contain components (a *), (b) and (c) are considerably more stable in storage than systems which additionally also contain component (d).
  • the process according to the invention is carried out in the first and / or second stage in the presence of up to 20% by weight of conventional plastic auxiliaries, by weight% of the total of all plastic auxiliaries, based on the total amount of the compounds (a) used.
  • plastic auxiliaries are, for example, thickeners, leveling agents, defoamers, lubricants, fillers, UV stabilizers.
  • auxiliaries are sufficiently known to the person skilled in the art from coating or coating technology. Care must be taken to ensure that the plastic auxiliaries used have essentially no free hydroxyl groups, provided that they are used in the first stage of the process according to the invention, so that they do not react with the isocyanates used in this stage.
  • a mixture of the polyurethanes (a *) obtained in the first stage of the process according to the invention is drawn up in a mixture with the desired compounds (b) and (c) and, if appropriate, additionally the desired compounds (d) in the desired layer thickness a solid substrate and then - immediately or after storage - carries out the post-crosslinking.
  • Wood, paper, plastic surfaces, mineral building materials such as shaped cement blocks or cement fiber boards, and also metals or coated metals are particularly suitable as solid substrates.
  • the post-crosslinking process which can also be referred to as curing, can, if desired, be repeated one or more times.
  • the polyurethanes (a *) are applied to the solid substrate in a mixture with the desired compounds (b) and (c) and, if appropriate, additionally with the desired compounds (d), for example by spraying, filling, knife coating, brushing, rolling or pouring.
  • the coating thickness is generally in the range from 3 to 500 g / m and in particular 10 to 200 g / m or wet film thicknesses of approximately 3 to 500 ⁇ m and in particular 50 to 200 ⁇ m.
  • the application can take place both at room temperature and at elevated temperature, but in particular not above 100 ° C.
  • the second process step is carried out by impregnating synthetic and / or natural fibers with a mixture of components (a *), (b) and (c) and, if desired, plastic auxiliaries and then the radical Networking.
  • This procedure is based on the so-called prepreg technology.
  • Prepreg is understood to mean a semi-finished product pre-impregnated with thermoplastic or thermoset material, which is further processed into the finished part in a further processing step.
  • fibers are usually impregnated with a resin matrix in suitable systems.
  • the prepregs can then either directly after their production or after a certain period of intermediate storage can be processed into the desired finished parts.
  • the stated embodiment of the invention therefore aims to provide fiber composite materials made of fibers and a matrix material, in which the matrix material is a free-radically post-crosslinked polymer accessible by the process according to the invention.
  • Another object of the present invention is the use of polymers obtainable by the process according to the invention as a matrix material for composites based on synthetic and / or natural fibers.
  • Another object of the present invention is a polymer-based material which can be obtained by, in the first stage, at least one or more compounds (a) which are reaction products of epoxidized fatty acid esters and / or epoxidized triglycerides with acrylic acid and / or methacrylic acid Reaction with aliphatic and / or aromatic isocyanates is converted into the corresponding polyurethanes (a *) and the polyurethanes (a *) thus prepared are then radically crosslinked in a second stage in the presence of at least one radical initiator (b), with the additional proviso that in the second stage uses a combination of the compounds (a *) with one or more compounds (c), the compounds (c) being selected from the group of acrolein, acrylamide, vinyl acetate and styrene.
  • compounds (a) which are reaction products of epoxidized fatty acid esters and / or epoxidized triglycerides with acrylic acid and / or methacrylic
  • the production of the polymer-based material is carried out in a second stage in the sense of the prepreg technology mentioned above in the presence of synthetic and / or natural fibers.
  • synthetic fibers such as glass fibers, carbon fibers, metal fibers and the like can be used, as well as natural fibers.
  • those fibers are preferred which at least partially, but preferably completely, contain natural fibers.
  • the natural fibers can be used in the form of short fibers, yarns, rovings or, preferably, textile fabrics in the form of nonwovens, needled nonwovens, tangled nonwovens, fabrics, scrims or knitted fabrics.
  • the natural fibers are preferably selected from flax, hemp, straw, wood wool, sisal, jute, coconut, ramie, bamboo, bast, cellulose, cotton or wool fibers, animal hair or fibers based on of chitin / chitosan or their combination. Those materials are preferred that contain all or part of flax fibers.
  • the proportion by weight of fiber material - based on the total amount of the compounds (a), (b) and (c) used - is between 10 and 70% by weight.
  • the fibers can be brought into contact with the matrix by all methods known per se to the person skilled in the art in order to obtain prepregs in this way.
  • the fibers are preferably immersed in the matrix, but spray processes are also possible.
  • Mixtures containing (a *), (b) and (c) which have a Brookfield viscosity in the range from 600 to 1400 mPas (measured with spindle 5 at 10 revolutions / min) are preferably used.
  • the viscosity values relate to the application temperature.
  • the matrix is preferably applied to the fibers at temperatures in the range from 40 ° to 80 ° C., it being particularly advantageous to select such matrices which have a Brookfield viscosity in the range from 600 to 1200 mPas at a temperature of 65 ° C.
  • the matrix is not yet fully cured, so that prepregs are obtained that can be shaped in almost any way, which facilitates their further processing. Add to that these prepregs at Room temperature and air access do not harden as quickly as the prepregs known from the prior art and thus have a significantly increased storage stability.
  • fiber composite materials The materials which can be obtained as just described and in which the production is carried out in a second stage in the presence of synthetic and / or natural fibers can be referred to as fiber composite materials. These fiber composite materials have a number of fields of application due to their excellent application properties. Accordingly, the present invention further relates to the use of these fiber composite materials for the production of components for vehicle construction, aircraft construction, the construction industry, window construction, the furniture industry, the electrical industry, sports equipment, toys, machine and apparatus construction, the packaging industry and agriculture or security technology.

Abstract

La présente invention concerne un procédé de préparation de polymères postréticulés par voie radicalaire. Dans une première étape du procédé, au moins un ou plusieurs composés (a) qui sont des produits réactionnels d'esters d'acides gras époxydés et/ou de triglycérides époxydés avec de l'acide acrylique et/ou de l'acide méthacrylique, sont transformés en polyuréthanes (a*) correspondants par réaction avec des isocyanates aliphatiques et/ou aromatiques, et, dans une seconde étape, les polyuréthanes (a*) ainsi obtenus sont finalement postréticulés par voie radicalaire en présence d'au moins un initiateur de radicaux (b), à la condition supplémentaire que l'on utilise dans la seconde étape, une combinaison des composés (a*) avec un ou plusieurs composés (c), les composés (c) étant choisis parmi le groupe comprenant acroléine, acrylamide, acétate de vinyle et styrol. Les polymères ainsi obtenus sont de très bons matériaux matriciels destinés à des matériaux composites.
EP01946880A 2000-01-29 2001-01-22 Procede de preparation de polymeres postreticules par voie radicalaire, par utilisation d'elements structurels Withdrawn EP1261671A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10003940A DE10003940A1 (de) 2000-01-29 2000-01-29 Verfahren zur Herstellung radikalisch nachverentzter Polymere unter Einsatz von Aufbaukomponenten
DE10003940 2000-01-29
PCT/EP2001/000647 WO2001055270A1 (fr) 2000-01-29 2001-01-22 Procede de preparation de polymeres postreticules par voie radicalaire, par utilisation d'elements structurels

Publications (1)

Publication Number Publication Date
EP1261671A1 true EP1261671A1 (fr) 2002-12-04

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP01946880A Withdrawn EP1261671A1 (fr) 2000-01-29 2001-01-22 Procede de preparation de polymeres postreticules par voie radicalaire, par utilisation d'elements structurels

Country Status (4)

Country Link
US (1) US20030139489A1 (fr)
EP (1) EP1261671A1 (fr)
DE (1) DE10003940A1 (fr)
WO (1) WO2001055270A1 (fr)

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CA2577882A1 (fr) * 2004-07-08 2006-02-09 Archer-Daniels-Midland Company Esters epoxydes d'acides gras d'huiles vegetales comme diluants reactifs
US20070181302A1 (en) * 2004-12-30 2007-08-09 Sun Drilling Products Corporation Method for the fracture stimulation of a subterranean formation having a wellbore by using thermoset polymer nanocomposite particles as proppants, where said particles are prepared by using formulations containing reactive ingredients obtained or derived from renewable feedstocks
DE102006041121A1 (de) * 2006-09-01 2008-03-13 Hobum Oleochemicals Gmbh Verfahren zur Herstellung von kaltgehärteten Biopolymeren
US8785547B2 (en) 2010-11-30 2014-07-22 The United States Of America As Represented By The Secretary Of The Army Toughening cross-linked thermosets
WO2013066461A2 (fr) 2011-08-10 2013-05-10 Palmese Giuseppe R Monomères (méth)acrylés biosourcés renouvelables servant d'agents de réticulation pour les esters de vinyle
WO2016040559A1 (fr) 2014-09-12 2016-03-17 Drexel University Durcissement de polymères époxy thermodurcissables durcis à l'anhydride au moyen de triglycérides greffés
US10428175B2 (en) 2014-09-12 2019-10-01 Drexel University Toughening of epoxy thermosets
WO2018098011A1 (fr) 2016-11-22 2018-05-31 Sadler Joshua Matthew Procédé permettant de produire des agents de réticulation de résine de (méth)acrylate/ester vinylique

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US3256225A (en) * 1962-01-24 1966-06-14 Staley Mfg Co A E Vicinal acryloxy hydroxy long chain fatty compounds and polymers thereof
US3979270A (en) * 1972-01-05 1976-09-07 Union Carbide Corporation Method for curing acrylated epoxidized soybean oil amine compositions
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Also Published As

Publication number Publication date
US20030139489A1 (en) 2003-07-24
DE10003940A1 (de) 2001-08-02
WO2001055270A1 (fr) 2001-08-02

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