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WO2002074827A1 - Ethers monoglycidyliques de polyalkylene glycol relies a un isocyanate - Google Patents

Ethers monoglycidyliques de polyalkylene glycol relies a un isocyanate Download PDF

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Publication number
WO2002074827A1
WO2002074827A1 PCT/EP2002/002416 EP0202416W WO02074827A1 WO 2002074827 A1 WO2002074827 A1 WO 2002074827A1 EP 0202416 W EP0202416 W EP 0202416W WO 02074827 A1 WO02074827 A1 WO 02074827A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
component
polyalkylene glycol
ether
epoxide
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.)
Ceased
Application number
PCT/EP2002/002416
Other languages
English (en)
Inventor
Wolfgang Scherzer
Jörg Volle
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.)
Huntsman Advanced Materials Deutschland GmbH
Original Assignee
Vantico 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 Vantico GmbH and Co KG filed Critical Vantico GmbH and Co KG
Publication of WO2002074827A1 publication Critical patent/WO2002074827A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/2845—Monohydroxy epoxy compounds
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring

Definitions

  • the invention relates to novel glycidyl ethers obtainable by linking a polyalkylene monoglycidyl ether to a difunctional or polyfunctional isocyanate, to curable compositions comprising these glycidyl ethers, and to the use of these curable compositions for the coating, hardening and adhesive bonding of metallic and mineral surfaces and for the production of mouldings having improved adhesion and comparatively low chlorine contents as well as good elastifying properties.
  • Curable compositions based on glycidyl compounds and various curing agents are widely used in industry for the coating, hardening and adhesive bonding of metallic and mineral surfaces and for the production of mouldings.
  • the epoxy resin component used here is essentially an epoxy base resin based on difunctional or polyfunctional phenols, such as, for example, bisphenol A, bisphenol F or novolaks.
  • the viscosity of these low-molecular-weight epoxy resins is frequently too high for processing at room temperature.
  • the viscosity of, for example, bisphenol A diglycidyl ether at 25°C is about 10,000 mPa-s.
  • epoxide group-containing compounds in particular mono- and polyglycidyl ethers.
  • reactive flexibilizers Through the reactive flexibilizers, a certain degree of internal plasticiza- tion of the epoxy resin moulded material is achieved, depending on the type and amount of the added compound, while other, unreactive diluents merely cause external plasticization with the known disadvantages.
  • One way is flexibilization through the addition of monofunctional compounds.
  • compounds having short alkyl chains such as, for example, allyl glycidyl ether, phenyl glycidyl ether or butyl glycidyl ether, are unsuitable owing to their high toxicity and/or their high volatility.
  • the relatively long monofunctional glycidyl ethers also make the formation of relatively long resin molecule chains more difficult as a consequence of chain degradation. With increasing content of these compounds, a significant drop in strength therefore occurs as a consequence of incomplete crosslinking.
  • modifiers containing two or more epoxide groups per molecule are frequently used. These are able to react with the curing agent at at least two points during curing and are thus incorporated into the molecular network instead of resin molecules at a number of points on corresponding metering of the components. The widening of the structure due to side chains that occurs in the case of monofunctional epoxide compounds is thus avoided, and in principle greater mechanical strength, in particular at elevated temperatures, and better heat distortion resistances can be expected.
  • modifiers of this type enable a certain degree of flexibility of the moulded material to be achieved, depending on the length and structure of the network chain lying between the epoxide groups and on the type of curing agent employed.
  • polyalkylene glycol diglycidyl ethers having a relatively low degree of polymerization (molecular weight of from 300 to 3000), since they facilitate curing both by means of acid anhydrides and by means of aliphatic and aromatic amines. Addition of a small amount of such compounds (10-40%) provides the moulded material with good and in some cases increased impact strength, flexural strength, com- pressive strength and thermal shock resistance. Addition of a greater amount of flexibilizer further lowers the softening range, giving moulded materials which are soft, flexible or rubber-like even at room temperature. A disadvantage of these polyalkylene glycol diglycidyl ethers is their poor adhesion to various substrates.
  • the object of the present invention was to eliminate the above-mentioned disadvantages and to provide flexibilizing reactive modifiers which have adequate adhesion to the substrate and whose non-hydrolysable chlorine contents are low.
  • glycidyl ethers obtainable by linking 1 ), a polyalkylene glycol monoglycidyl ether of the general formula (I)
  • reaction ratio of polyalkylene glycol monoglycidyl ether to isocyanate compound is chosen to be stoichiometric, i.e. one isocyanate group of the difunctional or polyfunctional isocyanate is employed for reaction per hydroxyl group of the polyalkylene glycol monoglycidyl ether.
  • the hydroxyl-containing polyalkylene glycol monoglycidyl ethers can be prepared by reaction of polyalkylene glycols with epichlorohydrin, followed by treatment with sodium hydroxide solution, where the molar ratio between polyalkylene glycol and epichlorohydrin is preferably 1 :1.
  • An excess of epichlorohydrin results in reduced formation of diglycidyl ethers, while a sub-stoichiometric amount of epichlorohydrin results in larger amounts of reactive, unreacted polyalkylene glycols remaining the product. It is possible to use ethylene glycols and propylene glycols, starting from the monomers, i.e.
  • ethylene glycol and propylene glycol up to the polymers thereof having a mean molecular weight of about 3000.
  • the reaction of the polyalkylene glycol monoglycidyl ether with the polyisocyanate is carried out by addition of the polyisocyanate to the initially introduced, dewatered, hydroxyl- containing polyalkylene glycol monoglycidyl ether at about 60°C in the presence of a catalyst (for example dibutyltin laurate), and then stirring the mixture for one hour.
  • a catalyst for example dibutyltin laurate
  • the choice of the alkylene glycol and the polyisocyanate enables properties such as, for example, elasticity or chlorine content, to be adjusted.
  • the chlorine content is comparatively low, since an excess of hydroxyl groups is present in the polyalkylene monoglycidyl ether prepared in the first step during reaction with epichlorohydrin, and the formation of non- hydrolysable chlorohydhn ethers through the addition of epichlorohydrin onto the secondary hydroxyl group of a chlorohydhn ether already formed is thus reduced.
  • the glycidyl ethers according to the invention in spite of the higher molecular weights compared with the polyalkylene glycol diglycidyl ethers usually used, exhibit no reduction in the tensile shear strengths. On the contrary, they even have significantly greater tensile shear strengths by comparison. Such an improvement in the tensile shear strengths could not have been foreseen.
  • the chlorine contents of the glycidyl ethers according to the invention are comparatively low.
  • the isocyanates used in accordance with the invention for linking of the polyalkylene glycol monoglycidyl ethers are commercially available aliphatic, araliphatic, cycloaliphatic or aromatic difunctional or polyfunctional isocyanates and trimerization products thereof. Examples which may be mentioned are: tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylenedi(phenyl isocyanate) and tetramethylene diisocyanate. This list is not exhaustive, but it goes without saying that in principle any at least difunctional isocyanates can be used for linking the polyalkylene glycol monoglycidyl ethers.
  • Preferred isocyanates are tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
  • the invention furthermore relates to a curable composition
  • a curable composition comprising a), as the only epoxy resin component, a glycidyl ether according to the invention or a composition comprising a plurality of glycidyl ethers according to the invention which are different from one another, and c) a curing agent for epoxy resins.
  • the curing agent c) is employed in the usual advantageous amounts, according to which from 0.5 to 2.0, preferably from 0.75 to 1.25, functional groups of the curing agent are present per epoxide group in the respective composition.
  • the invention furthermore relates to a primarily described curable composition additionally comprising a component b) in the form of an epoxide compound which is different from a).
  • the epoxy resin component b) has on average more than one epoxide group in the molecule.
  • the proportion advantageously to be employed of component b) in the compositions according to the invention can vary within broad limits depending on the area of application and is well known to the person skilled in the art. Based on the total amount of a) and b), the proportion of component a) should, however, be at least 5% by weight, preferably at least 30% by weight, particularly preferably at least 50% by weight.
  • the epoxide compounds b) to be used concomitantly in accordance with the invention are commercially available products containing more than one epoxide group per molecule . which are derived from polyhyd c or polycyclic phenols, in particular bisphenols or novolaks. An extensive list of these diphenols or polyphenols is given, for example, in the handbook “Epoxiditatien und Epoxidharze” [Epoxide Compounds and Epoxy Resins] by A.M. Paquin, Springer Verlag Berlin, 1958, Chapter IV, and in Lee & Neville "Handbook of Epoxy Resins", 1967, Chapter 2.
  • the curing agents used concomitantly in accordance with the invention may contain, for example, amino groups, anhydride groups, phenolic hydroxyl groups or acid groups. How- ever, it is also possible to use catalytic curing agents which cause self-polymerization of the epoxy resin. An extensive list of curing agents of this type is given, for example, in the handbook “Epoxidharze” [Epoxy Resins] by Dr. H. Jahn, Leipzig, 1969, pp. 33-67. Preferred curing agents are curing agents containing amino groups.
  • auxiliaries and additives which are customary in epoxy resin technology can be employed as component d) in the epoxy resin compositions according to the invention, such as, for example: inorganic and/or organic additives, such as finely divided sands, talc, silica, alumina, metals or metal compounds in the form of turnings and powders, flame-inhibiting substances, fibrous materials, such as, for example, thixotropic agents, pigments, flow-control and deaeration agents, solvents, water, dyes, plasticizers, bitumen, mineral oils and the reactive and non-reactive diluents or flexibilizers known from the prior art.
  • inorganic and/or organic additives such as finely divided sands, talc, silica, alumina, metals or metal compounds in the form of turnings and powders, flame-inhibiting substances, fibrous materials, such as, for example, thixotropic agents, pigments, flow-control and deaeration agents, solvents, water
  • the invention furthermore relates to a product obtainable by curing a curable composition according to the invention.
  • the curing can be carried out cold, i.e. supply of heat is not necessary, in particular if an aminic curing agent is used.
  • curable compositions according to the invention are particularly suitable for the coating, hardening and adhesive bonding of metallic and mineral surfaces and for the production of mouldings having improved adhesion and comparatively low chlorine contents as well as good elastifying properties.
  • a polypropylene glycol diglycidyl ether having the following characteristic data is obtained from 620 g of polypropylene glycol 620 (1 mol) and 185 g of epichlorohydrin (2.0 mol) by a generally known process - addition of epichlorohydrin onto the polyalkylene glycol in the presence of tetrafluoroboric acid and ring closure in the presence of aqueous sodium hydroxide solution: epoxide value: 0.21 mol of epoxide per 100 g; chlorine: T: 2.66%; H:
  • a polypropylene glycol monoglycidyl ether based on PPG 620 is prepared by the process from Example 1. Amounts used: 620 g of polypropylene glycol 620 (1 mol) and 92.5 g of epichlorohydrin (1 mol). The product has a hydroxyl number of 80. 222 g (1 mol) of isophorone diisocyanate are metered into 1400 g of the polypropylene glycol monoglycidyl ether ( ⁇ 2 hydroxyl equivalents) by a known process in the presence of 0.1 g of dibutyltin laurate.
  • a polypropylene glycol diglycidyl ether containing urethane groups and having the following characteristic data is formed: epoxide value: 0.12 mol of epoxide/100 g; chlorine: T: 0.13%; H: 0.05%.
  • a polypropylene glycol monoglycidyl ether based on PPG 400 is prepared by the process from Example 1. Amounts used: 400 g of polypropylene glycol 400 (1 mol) and 92.5 g of epichlorohydrin (1 mol). The product has a hydroxyl number of 117. 958 g of the polypropylene glycol monoglycidyl ether ( ⁇ 2 hydroxyl equivalents) are reacted with 174 g (1 mol) of tolylene 2,4-diisocyanate as described in Example 2. The product has the following characteristic data: epoxide value: 0.17 mol of epoxide per 100 g; chlorine: T: 0.11%; H: 0.03%.
  • a polypropylene glycol monoglycidyl ether based on PPG 1900 is prepared by the process from Example 1. Amounts used: 1900 g of polypropylene glycol 1900 (1 mol) and 92.5 g of epichlorohydrin (1 mol). The product has a hydroxyl number of 28.
  • a polyethylene glycol monoglycidyl ether based on PEG 400 is prepared by the process from
  • Example 1 Amounts used: 400 g of polyethylene glycol 400 (1 mol) and 92.5 g of epichlorohydrin (1 mol). The product has a hydroxyl number of 115.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Cette invention concerne des éthers glycidyliques que l'on obtient en reliant 1) un éther monoglycidylique de polyalkylène glycol représenté par la formule générale (I) [dans laquelle R est un radical -H ou -CH3, et n vaut de1 à 50] à 2) un isocyanate difonctionnel ou polyfonctionnel (polyisocyanate). L'invention concerne également des compositions durcissables comprenant, comme seul composant de résine époxy, ces éthers glycidyliques et un agent durcisseur, ainsi que des compositions durcissables comprenant en outre un composant de résine époxy qui est différent de ces éthers glycidyliques. Enfin, l'invention concerne l'utilisation de ces compositions durcissables pour le revêtement, le durcissement et le collage de surfaces métalliques et minérales ainsi que pour la fabrication de moules caractérisés par une adhérence améliorée, des teneurs en chlore relativement faibles et un bon pouvoir élastifiant.
PCT/EP2002/002416 2001-03-15 2002-03-06 Ethers monoglycidyliques de polyalkylene glycol relies a un isocyanate Ceased WO2002074827A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10112556.9 2001-03-15
DE10112556 2001-03-15

Publications (1)

Publication Number Publication Date
WO2002074827A1 true WO2002074827A1 (fr) 2002-09-26

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PCT/EP2002/002416 Ceased WO2002074827A1 (fr) 2001-03-15 2002-03-06 Ethers monoglycidyliques de polyalkylene glycol relies a un isocyanate

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004003048A1 (fr) * 2002-07-01 2004-01-08 Huntsman Advanced Materials (Switzerland) Gmbh Monoépoxydes polyéther uréthanne contenant de l'isocyanato
CN107118342A (zh) * 2017-06-02 2017-09-01 温州大学 一种用环氧氯丙烷合成含有缩醛键的聚乙二醇的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239580A (en) * 1962-03-19 1966-03-08 Dow Chemical Co Elastomeric epoxy resins
GB1170837A (en) * 1966-07-19 1969-11-19 Ciba Ltd New Urethane-Group-Containing Polyepoxides, process for their manufacture, and their use
US4891267A (en) * 1985-12-16 1990-01-02 Toho Rayon Co., Ltd. Carbon fiber cord for rubber reinforcement and process for producing the same
JPH03118117A (ja) * 1989-10-02 1991-05-20 Yokohama Rubber Co Ltd:The 型材および型取り方法
EP0553701A2 (fr) * 1992-01-27 1993-08-04 BASF Corporation Polyuréthane à fonction époxy et composition de revêtement durcissable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239580A (en) * 1962-03-19 1966-03-08 Dow Chemical Co Elastomeric epoxy resins
GB1170837A (en) * 1966-07-19 1969-11-19 Ciba Ltd New Urethane-Group-Containing Polyepoxides, process for their manufacture, and their use
US4891267A (en) * 1985-12-16 1990-01-02 Toho Rayon Co., Ltd. Carbon fiber cord for rubber reinforcement and process for producing the same
JPH03118117A (ja) * 1989-10-02 1991-05-20 Yokohama Rubber Co Ltd:The 型材および型取り方法
EP0553701A2 (fr) * 1992-01-27 1993-08-04 BASF Corporation Polyuréthane à fonction époxy et composition de revêtement durcissable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199126, Derwent World Patents Index; Class A32, AN 1991-190092, XP002203666 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004003048A1 (fr) * 2002-07-01 2004-01-08 Huntsman Advanced Materials (Switzerland) Gmbh Monoépoxydes polyéther uréthanne contenant de l'isocyanato
CN107118342A (zh) * 2017-06-02 2017-09-01 温州大学 一种用环氧氯丙烷合成含有缩醛键的聚乙二醇的方法

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