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WO2001072868A1 - Resine epoxy exempte d'halogenes a masse moleculaire definie - Google Patents

Resine epoxy exempte d'halogenes a masse moleculaire definie Download PDF

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Publication number
WO2001072868A1
WO2001072868A1 PCT/DE2001/000933 DE0100933W WO0172868A1 WO 2001072868 A1 WO2001072868 A1 WO 2001072868A1 DE 0100933 W DE0100933 W DE 0100933W WO 0172868 A1 WO0172868 A1 WO 0172868A1
Authority
WO
WIPO (PCT)
Prior art keywords
halogen
epoxy resin
free epoxy
free
component
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/DE2001/000933
Other languages
German (de)
English (en)
Inventor
Peter GRÖPPEL
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of WO2001072868A1 publication Critical patent/WO2001072868A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O

Definitions

  • Halogen-free epoxy resin with a defined molecular weight
  • the invention relates to a halogen-free epoxy resin with a defined molecular weight.
  • Halogen-free epoxy resin compositions in which the viscosity of the resulting resin is adjusted by the molar ratio of the educts, are shown in accordance with
  • epoxy resins are used, among other things, as masking and potting compounds.
  • An important property concerns the molar mass distribution.
  • the resin components are often said to contain high molecular weight products in order to make the flow and shrinkage behavior of the formulations derived from them inexpensive.
  • Epoxy resins with a high proportion of low molecular weight, highly functional compounds interfere because they can initiate a little flexible network with high voltages. Too high a molar mass can in turn lead to incompatibilities with other components in the resin mixture. A targeted adjustment of the molecular weight would therefore be a great advantage with regard to the possible uses of an epoxy resin.
  • the object of the invention is to provide a halogen-free epoxy resin with a defined molecular weight.
  • the invention relates to the use of a halogen-free epoxy resin with a defined molecular weight as
  • 4-methyl-1-cyclohexene-1,2-epoxy, limonene oxide, 5-methyl-2-norbonenoxide, 1,3-butadiene monoxide, 1,5-hexadiene monoxide, dicyclopentadiene monoxide is preferably used as the epoxy component.
  • 4-Vmyl-1-cyclohexene-1,2-epoxy is particularly preferably used.
  • Typical phenolic hardeners such as bisphenols, for example bisphenol-A or naphthalene, are preferred as the phenolic component.
  • Talindiol used.
  • phenols such as p-nonylphenol or polyphenols such as Hostanox 03 (Fa. Hoechst AG) can also be used.
  • Polyphenols such as phenol novolaks, cresol novolaks or trihydroxyanthracene may also be used.
  • phenolic components which are used are those with substituents which carry aliphatically bound hydroxyl groups, such as, for example: 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4-hydroxy-3-methoxybenzyl alcohol and ethylene glycol monosalicylate.
  • substituents which carry aliphatically bound hydroxyl groups such as, for example: 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 4-hydroxy-3-methoxybenzyl alcohol and ethylene glycol monosalicylate.
  • R " simple derivatives and homologs with an R ", such as can be prepared by lengthening alkyl chains, replacing a proton by an alkyl radical, etc.
  • All halogen-free bases can be used as catalysts.
  • An onium hydroxide is preferably used as the catalyst.
  • the stoichiometry of the reaction depends on the functionality of the phenol component.
  • the components are used in an equivalent ratio of phenol component to epoxy component of 1: 2.
  • the equivalent ratio for monofunctional phenols is 1: 1.
  • the reaction can be carried out either in a solvent or without using a solvent.
  • the end of the reaction can be recognized from the fact that the epoxy value is ⁇ 1% of the initial value.
  • the process for producing the halogen-free epoxy resin with a defined molecular weight is carried out in two stages:
  • the first step is based on compounds that are Characterize that they have both at least one epoxy group and at least one carbon-carbon double bond. Their general formula looks like this:
  • Ri represents a linear and / or branched acylene chain with 2 to 15 carbon atoms or a cycloaliphatic ring system with 4 to 15 carbon atoms. Ri can also contain a polyoxyalkylene group R ⁇ > or a polyester group with R ⁇ >.
  • the double bond is preferably a vinyl, but alkylene radicals other than hydrogen can also be bonded to the double bond as long as they do not prevent epoxidation.
  • R 2 stands for the residue formed from the phenol component, for example a p, p '-diphenylmethane or p, p' -diphenylpropane etc.
  • the reaction product obtained is epoxidized. Since in the case of the difunctional epoxy components used, the more reactive grouping has already been reacted by reaction with a phenolic grouping, the epoxidation of the double bond poses a low safety risk.
  • halogen compounds such as hypochlorite or bromine acid, m-chloroperbenzoic acid or N-bromosuccinimide
  • hypochlorite or bromine acid m-chloroperbenzoic acid or N-bromosuccinimide
  • Epoxidations can also be base-catalyzed or carried out in the presence of metal catalysts.
  • Halogen-free means, for example, that the halogen content of the finished compound is less than 100 ppm, in particular less than 50 ppm and preferably less than 20 ppm.
  • the associated manufacturing instructions are as follows: 112 g (0.5 mol) of bisphenol-A (Merck, synthesis quality) in 124 g (1 mol) of 4-vinyl-1-cyclohexene are placed in a 500 ml three-necked flask with a KPG stirrer, internal thermometer and reflux condenser. 1, 2-epoxy dissolved. 3.36 g (1%) of tetraethylammonium hydroxide (20% solution in water, Aldrich) are added. The reaction vessel is heated to 100 ° C. with stirring and then kept at 100 ° C. for a further 48 hours. To remove the accelerator, the reaction mixture is stirred in an oil pump vacuum at 0.6 mbar and an oil bath temperature of 130 ° C. until only a small amount of bubbles can be observed.
  • the epoxy value is less than 0.1 mol / lOOg.
  • the great advantage of a defined molecular mass can be seen in the small melting interval between the glassy solidified state at room temperature and a relatively thin substance.
  • the typical melting range spans approx. 10 ° C.
  • a defined glass transition ( ⁇ relaxation) can be determined with the hardened epoxy resin. This results in a stable modulus of elasticity in the temperature range below T g , which enables technical use as molding materials for adhesive applications.
  • a halogen-free epoxy resin with a defined molecular weight was used in the following composition as a screen printing formulation for a molding material:
  • Epoxy resin 100 parts by mass
  • Adhesion promoter 0.5 parts by mass
  • a molding material with a smooth surface and sharp edges is obtained from the screen printing compound after curing.
  • the molding material is therefore suitable as a damping compound for surface wave filters.
  • the reaction of a monofunctional epoxy compound with a phenol component and subsequent epoxidation gives a resin component with a defined molar mass distribution. This is not possible with the one-step reaction used to date.
  • the reactivity of the starting materials and the two-stage reaction procedure make it possible to produce a halogen-free epoxy resin with a defined molecular weight.

Landscapes

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

Abstract

L'invention concerne une résine époxy exempte d'halogènes et présentant une masse moléculaire définie. Grâce à la réactivité des produits de départ et à la mise en oeuvre de la réaction en deux étapes, il est possible de fabriquer une résine époxy exempte d'halogènes présentant une masse moléculaire définie.
PCT/DE2001/000933 2000-03-24 2001-03-12 Resine epoxy exempte d'halogenes a masse moleculaire definie Ceased WO2001072868A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10014640.6 2000-03-24
DE2000114640 DE10014640A1 (de) 2000-03-24 2000-03-24 Halogenfreies Epoxidharz mit definierter Molekülmasse

Publications (1)

Publication Number Publication Date
WO2001072868A1 true WO2001072868A1 (fr) 2001-10-04

Family

ID=7636180

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2001/000933 Ceased WO2001072868A1 (fr) 2000-03-24 2001-03-12 Resine epoxy exempte d'halogenes a masse moleculaire definie

Country Status (2)

Country Link
DE (1) DE10014640A1 (fr)
WO (1) WO2001072868A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB904549A (en) * 1959-05-06 1962-08-29 British Celanese Preparation of epoxy ethers and formation of cured resinous products therefrom
EP0365428A2 (fr) * 1988-10-18 1990-04-25 Daicel Chemical Industries, Ltd. Une composition de revêtement sous forme de poudre
JPH03139521A (ja) * 1989-10-25 1991-06-13 Daicel Chem Ind Ltd ポリエーテル化合物およびエポキシ化合物
EP0859021A2 (fr) * 1991-10-31 1998-08-19 Daicel Chemical Industries, Ltd. Compositions époxydes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB904549A (en) * 1959-05-06 1962-08-29 British Celanese Preparation of epoxy ethers and formation of cured resinous products therefrom
EP0365428A2 (fr) * 1988-10-18 1990-04-25 Daicel Chemical Industries, Ltd. Une composition de revêtement sous forme de poudre
JPH03139521A (ja) * 1989-10-25 1991-06-13 Daicel Chem Ind Ltd ポリエーテル化合物およびエポキシ化合物
EP0859021A2 (fr) * 1991-10-31 1998-08-19 Daicel Chemical Industries, Ltd. Compositions époxydes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199130, Derwent World Patents Index; Class A21, AN 1991-218494, XP002171103 *

Also Published As

Publication number Publication date
DE10014640A1 (de) 2001-10-11

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