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EP3033320A1 - Glycidyléthers de dérivés de divinylbenzène et oligomères desdits glycidyléthers de dérivés de divinylbenzène en tant que résine époxy durcissable - Google Patents

Glycidyléthers de dérivés de divinylbenzène et oligomères desdits glycidyléthers de dérivés de divinylbenzène en tant que résine époxy durcissable

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Publication number
EP3033320A1
EP3033320A1 EP14747946.3A EP14747946A EP3033320A1 EP 3033320 A1 EP3033320 A1 EP 3033320A1 EP 14747946 A EP14747946 A EP 14747946A EP 3033320 A1 EP3033320 A1 EP 3033320A1
Authority
EP
European Patent Office
Prior art keywords
glycidyl ether
glycidyl
group
atom
formula
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Withdrawn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
EP14747946.3A
Other languages
German (de)
English (en)
Inventor
Ulrich Karl
Monika CHARRAK
Hans-Josef Thomas
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 SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP14747946.3A priority Critical patent/EP3033320A1/fr
Publication of EP3033320A1 publication Critical patent/EP3033320A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/26—Polyhydroxylic alcohols containing only six-membered aromatic rings as cyclic part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/164—Unsaturated ethers containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • 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
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/50—Amines
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to glycidyl ethers of the formula I, which are glycidyl ethers of divinylbenzene derivatives of the formula II having two or more glycidyl groups.
  • the invention further relates to oligomers of the glycidyl ethers of the formula I.
  • the invention also relates to processes for the preparation of these monomeric and oligomeric glycidyl ethers, and their use for the production of adhesives, composites, moldings or coatings.
  • the present invention further relates to a curable epoxy resin composition
  • a curable epoxy resin composition comprising a hardener component and a resin component containing as polyepoxide compound at least one glycidyl ether of the formula I, an oligomer of a glycidyl ether of the formula I or an oligomer based on a glycidyl ether of the formula I.
  • the invention further relates to a process for curing these curable epoxy resin compositions and cured epoxy resins obtainable or obtained by curing this curable epoxy resin composition.
  • the invention also provides the divinylbenzene derivatives of the formula II used as an intermediate for the preparation of the glycidyl ethers according to the invention.
  • epoxy resins are usually called oligomeric compounds having on average more than one epoxide group per molecule, which are converted by reaction with suitable curing agents or by polymerization of the epoxy groups in thermosets or cured epoxy resins.
  • Cured epoxy resins because of their excellent mechanical and chemical properties, such as high impact strength, high abrasion resistance, good heat and chemical resistance, in particular a high resistance to alkalis, acids, oils and organic solvents, high weather resistance, excellent adhesion to many materials and high electrical insulation capacity , widespread. They serve as a matrix for composites and are often the main component in electro laminates, structural adhesives, casting resins, coatings and powder coatings.
  • Epoxy resins derived from epichlorohydrin are referred to as glycidyl based resins.
  • glycidyl based resins As a rule, bisphenol A or bisphenol F diglycidyl ethers or the corresponding oligomers are used as epoxy resins.
  • the coating should withstand strongly acidic or salt-containing foods (eg tomatoes) or drinks, so that no corrosion of the metal occurs, which in turn could lead to contamination of the contents.
  • the coating must not affect the taste or appearance of the food. Since coated containers are often further formed during the manufacture of the containers, the coating must be flexible. Many filling goods, eg food, are only in the Can pasteurized; therefore, the coating must survive heating to 121 ° C for at least 2 hours undamaged and without migration of ingredients.
  • WO 2012/089657 discloses a BPA-free preparation of a film-forming resin and an adhesion promoter.
  • an epoxidized resin is prepared, for example, from the diglycidyl ethers of NPG, ethylene glycol, propylene or dipropylene glycol, 1,4-butanediol or 1,6-hexanediol.
  • NPG diglycidyl ethers
  • ethylene glycol propylene or dipropylene glycol
  • 1,4-butanediol 1,6-hexanediol
  • WO 2010/100122 proposes a coating system obtainable by reacting an epoxidized vegetable oil with hydroxy-functional compounds, e.g. Propylene glycol, propane-1,3-diol, ethylene glycol, NPG, trimethylolpropane, diethylene glycol, and the like.
  • hydroxy-functional compounds e.g. Propylene glycol, propane-1,3-diol, ethylene glycol, NPG, trimethylolpropane, diethylene glycol, and the like.
  • WO 2012/091701 proposes various diols or their diglycidyl ethers as substitutes for BPA or BADGE for epoxy resins, inter alia derivatives of BPA and ring-hydrogenated BPA, alicyclic diols based on cydobutane and diols with a furan ring as the basic structure.
  • the present invention has for its object to provide monomeric or oligomeric glycidyl ether compounds for use in epoxy resin systems, in particular as at least partial replacement of BADGE in corresponding epoxy resin systems, especially for use for coating containers. Accordingly, the present invention relates to glycidyl ethers of the formula I.
  • A is a glycidyl group ) or an H atom
  • B is an H atom or a C 1 -C 10 -alkyl group, preferably an H atom or a C 1 -C 4 -alkyl group, in particular an H atom, and
  • R 9 and R 10 are each, independently of one another, an H atom or a C 1 -C 4 -alkyl group, preferably an H atom,
  • At least 2, but preferably all A radicals are each a glycidyl group.
  • glycidyl ethers of the formula I in this specification of the radicals are also referred to for the purposes of this invention as "glycidyl ether I”.
  • the present invention relates to glycidyl ethers of the formula I in variant A,
  • A is a glycidyl group
  • B is an H atom or a C 1 -C 10 -alkyl group, preferably an H atom or a C 1 -C 4 -alkyl group, in particular an H atom.
  • glycidyl ethers of the formula I in this specification of the radicals (variant A) are also referred to for the purposes of this invention as "glycidyl ether IA”.
  • the present invention relates to glycidyl ethers of the formula I in variant B,
  • B is an H atom or a C 1 -C 10 -alkyl group, preferably an H atom or a C 1 -C 4 -alkyl group, in particular an H atom, and
  • R1, R4, R5 or R8 is a CR9R10OA group
  • A is a glycidyl group or an H atom
  • R 9 and R 10 are each, independently of one another, an H atom or a C 1 -C 4 -alkyl group, preferably an H atom,
  • At least 2, but preferably all A radicals are each a glycidyl group.
  • glycidyl ethers of the formula I in this specification of the radicals (variant B) are also referred to in the context of this invention as "glycidyl ether IB" for short.
  • Glycidyl ethers IA and IB are subsets of glycidyl ether I.
  • the glycidyl ethers I, IA and IB expressly include all possible stereoisomers.
  • the glycidyl ethers I, IA and IB also explicitly include the constitutional isomers wherein the two substituents on the benzene ring are ortho, meta or para to each other.
  • a C 1 -C 10 -alkyl group is an aliphatic, saturated hydrocarbon chain having 1 to 10 C atoms, which may be linear, branched or cyclic and has no heteroatoms.
  • a Ci-C4-alkyl group is a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl group.
  • the term glycidyl ether I, IA or IB expressly also relates to individual specific compounds from the respective group as well as mixtures of several specific compounds of the respective group.
  • Another object of the invention are also oligomers of glycidyl ethers I, IA and IB, respectively, by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the glycidyl ethers I, IA and IB and their partial (1 glycidyl group having ) or non-glycidylated (having no glycidyl group) derivatives with formation of the oxirane ring, the hydroxyl group of the oligomer resulting from the ring opening of the oxirane ring in turn also being able to be present in glycidylated form.
  • the oligomers have 2 to 100, preferably 2 to 30 monomeric units (degree of oligomerization). They can be linear or branched, preferably they are linear. On average, they have at least 1, 3, preferably at least 1, 5, more preferably at least 2 glycidyl groups.
  • the term oligomer of the glycidyl ethers I, IA or IB also encompasses mixtures of different oligomers (for example oligomers with different degrees of oligomerization, with different branching structures or different monomers of the respective variant (glycidyl ethers I, IA or IB)). These oligomers are also referred to in the context of this invention as oligomeric glycidyl ethers I, IA and IB.
  • the invention thus provides a glycidyl ether selected from the group consisting of glycidyl ether I and oligomeric glycidyl ethers thereof (oligomeric glycidyl ether I), wherein the oligomeric glycidyl ether by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the formula I.
  • oligomeric glycidyl ether formed by the ring opening of the oxirane ring can again also be present in glycidylated form, and wherein the oligomeric glycidyl ether has a degree of oligomerization of from 2 to 100 and in the Agent has at least 1, 3 glycidyl groups.
  • the invention thus also provides a glycidyl ether selected from the group consisting of glycidyl ether IA and oligomeric glycidyl ethers thereof (oligomeric glycidyl ethers IA), the oligomeric glycidyl ether being obtained by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives to form the opening of the oxirane ring, the resulting by the ring opening of the oxirane ring hydroxyl group of the oligomeric glycidyl ether may in turn be present in glycidylierter form, and wherein the oligomeric glycidyl ether a degree of oligomerization of 2 to 100 and on average at least 1 , 3 glycidyl groups.
  • the invention thus also provides a glycidyl ether selected from the group consisting of glycidyl ether IB and oligomeric glycidyl ethers thereof (oligomeric glycidyl ether IB), wherein the oligomeric glycidyl ether by the intermolecular reaction of glycidylated residues with non-glycidylated, hydroxyl-containing residues of the monomeric glycidyl ether of the formula I and their partially or non-glycidylated derivatives to form the opening of the oxirane ring, wherein the resulting by the ring opening of the oxirane ring hydroxyl group of the oligomeric glycidyl ether may again be present in glycidylierter form, and wherein the oligomeric glycidyl ether a degree of oligomerization of 2 to 100 and on average having at least 1, 3 glycidyl groups.
  • One embodiment of the invention relates to mixtures of monomeric glycidyl ether I, IA or IB and the corresponding oligomeric glycidyl ether I, IA or IB.
  • the present invention further relates to a process for the preparation of monomeric and oligomeric glycidyl ethers I, IA or IB comprising the reaction of the corresponding divinylbenzene derivatives II, IIA or IIB with epichlorohydrin.
  • the divinylbenzene derivatives II are divinylbenzene derivatives of the formula II
  • B is an H atom or a C 1 -C 10 -alkyl group, preferably an H atom or a C 1 -C 4 -alkyl group, in particular an H atom, and
  • R9 and R10 are each independently an H atom or a Ci-C4-alkyl group, preferably an H atom.
  • the divinylbenzene derivatives IIA are divinylbenzene derivatives of the formula II in variant A with the following specification of the radicals:
  • B is an H atom or a C 1 -C 10 -alkyl group, preferably an H atom or a C 1 -C 4 -alkyl group, in particular an H atom.
  • the divinylbenzene derivatives IIA are diols.
  • the divinylbenzene derivatives IIB are divinylbenzene derivatives of the formula II in variant B with the following specification of the radicals:
  • B is an H atom or a C 1 -C 10 -alkyl group, preferably an H atom or a C 1 -C 4 -alkyl group, in particular an H atom, and
  • At least one of the radicals R1, R4, R5 or R8 is a CR9R10OH group, and R9 and R10 are each independently an H atom or a Ci-C4-alkyl group, preferably an H atom.
  • the divinylbenzene derivatives IIB are trihydric and tetrahydric alcohols (polyols).
  • the glycidylation reaction generally produces a mixture of monomeric and oligomeric glycidyl ether.
  • the monomeric glycidyl ethers can be separated from the oligomeric glycidyl ethers by means of separation methods known to those skilled in the art, such as, for example, chromatographic, extractive or distillative processes.
  • the reaction according to the invention of the divinylbenzene derivatives is carried out to the corresponding with 1 to 20, preferably with 1 to 10 equivalents of epichlorohydrin at a temperature in a range from 20 to 180 ° C, preferably from 70 to 150 ° C in the presence of a Lewis acid as a catalyst, preferably in the presence of stannic chloride.
  • the reaction mixture is mixed with a base (for example dilute sodium hydroxide solution) and heated for a further period of time (for example 1 to 5 h) (for example under reflux). Thereafter, the product can be isolated by means of phase separation and washing steps with water.
  • 1 to 20 equivalents, preferably 2 to 10 equivalents of epichlorohydrin are used for the preparation of the glycidyl ethers according to the invention.
  • the reaction is usually carried out in a temperature range from -10 ° C to 120 ° C, preferably 20 ° C to 60 ° C.
  • bases such as aqueous or alcoholic solutions or dispersions of inorganic salts, such as LiOH, NaOH, KOH, Ca (OH) 2 or Ba (OH) 2 may be added.
  • suitable catalysts such as tertiary amines can be used.
  • the divinylbenzene derivatives IIA and IIB can be prepared according to the following reaction scheme from divinylbenzene derivatives of the formula III
  • R 19 and R 20 are each independently an H atom or a C 1 -C 10 -alkyl group, preferably an H atom or a C 1 -C 4 -alkyl group, in particular an H atom, and the two substituents on the benzene ring in ortho, meta - or para position can stand.
  • the divinylbenzene derivative of the formula III is converted by means of hydroformylation (HF) with carbon monoxide (CO) and hydrogen (H 2) into the corresponding dicarbonyl compounds. This can then either directly to the diols (divinylbenzene derivatives IIA), or after an aldol reaction (AD) with, for example.
  • Formaldehyde (H2CO) to the polyols (divinylbenzene derivatives IIB) be hydrogenated (Hyd), for example. With hydrogen (H2).
  • H2CO Formaldehyde
  • the aldol reaction is only possible if a hydrogen atom is bonded to the carbon atom alpha-permanent carbon atom.
  • the divinylbenzene derivatives II correspond to the entirety of the group of divinylbenzene derivatives IIA and IIB.
  • the reaction of the divinylbenzene derivative of the formula III to the corresponding dialdehydes is usually carried out by means of hydroformylation.
  • the divinylbenzene derivative of the formula III is reacted with a mixture of carbon monoxide and hydrogen (synthesis gas) in the presence of a hydroformylation catalyst (for example organometallic cobalt or rhodium compounds) at elevated pressure (for example 10 to 100 bar overpressure) and at Temperatures in the range of, for example. 40 to 200 ° C converted to the corresponding dialdehydes.
  • a hydroformylation catalyst for example organometallic cobalt or rhodium compounds
  • dialdehyde derivatives of the divinylbenzene derivative of the formula III can be hydrogenated directly to the corresponding diols (divinylbenzene derivatives IIA). Such hydrogenation can be carried out, for example, by means of hydrogen under elevated pressure in the presence of a hydrogenation catalyst.
  • dialdehyde derivatives of the divinylbenzene derivative of formula III can also be converted to the corresponding polyols (divinylbenzene derivatives IIB).
  • the invention thus provides a process for the preparation of glycidyl ether IA which comprises (i) the hydroformylation of divinylbenzene derivatives of the formula III with a mixture of carbon monoxide and hydrogen in the presence of a hydroformylation catalyst at elevated pressure to give the corresponding dialdehydes, and (ii ) the catalytic hydrogenation of the dialdehydes from the hydroformylation to the corresponding diols, and (iii) the reaction of the diols from the catalytic hydrogenation with epichlorohydrin to the corresponding glycidyl ethers IA, wherein in the divinylbenzene derivatives of the formula III the radicals R19 and R20 each independently of one another are an H atom or a C 1 -C 10 -alkyl group, preferably an H atom or a C 1 -C 4 -alkyl group, in particular an H atom.
  • the invention also provides the divinylbenzene derivatives II, IIA and IIB which serve as an intermediate in the preparation of the glycidyl ethers I, IA or IB according to the invention.
  • the present invention further relates to processes for the preparation of oligomers based on glycidyl ether I, IA or IB, by reacting monomeric glycidyl ether I, IA, and IB with diols (chain extension).
  • oligomeric glycidyl ether I, IA, or IB preferably has a low degree of oligomerization, in particular a degree of oligomerization of from 5 to 10. Preference is given to 0.01 to 0.95, more preferably 0.05 to 0.8, in particular 0.1 to 0.4 equivalents of the diol based on the glycidyl ether or used used.
  • the resulting oligomer based on glycidyl ethers I, IA or IB has an average of more than 1, preferably more than 1.5, more preferably more than 1, 9 epoxide groups per molecule.
  • the reaction is usually carried out in a temperature range from 50 ° C to 200 ° C, preferably from 60 ° C to 160 ° C.
  • Suitable diols are typically aromatic, cycloaliphatic or aliphatic dihydroxy compounds, for example furandimethanol, ring-hydrogenated bisphenol A, ring-hydrogenated bisphenol F, neopentyl glycol, bisphenol A, bisphenol F or bisphenol S, preferably furandimethanol, ring-hydrogenated bisphenol A or ring-hydrogenated bisphenol F.
  • the subject of the present invention are also oligomers based on glycidyl ethers I, IA, and IB, which are available or obtained by reacting a monomeric glycidyl ether I, IA, or IB or the corresponding oligomeric glycidyl ether or a Mixture of monomeric glycidyl ether I, IA, or IB and the corresponding oligomeric glycidyl ether with one or more diols.
  • the oligomeric glycidyl ether I, IA or IB preferably has a low degree of oligomerization, in particular a degree of oligomerization of from 5 to 10.
  • the one or more diols used are not identical to the divinylbenzene derivatives IIA, whereby mixed oligomers based on glycidyl ethers I, IA, and IB, respectively, are obtainable.
  • the one or more diols used are identical to the divinylbenzene derivatives IIA, whereby oligomers based on glycidyl ethers I, IA, and IB, respectively, are obtainable.
  • relatively high molecular weight oligomeric glycidyl ethers I, IA or IB can also be prepared starting from oligomeric glycidyl ethers I, IA or IB with a lower degree of oligomerization.
  • the present invention also relates to curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I, IA or IB, oligomeric glycidyl ether I, IA or IB and oligomer based on glycidyl ethers I, IA and IB, respectively.
  • the present invention also relates to curable epoxy resin compositions
  • curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I, IA or IB, oligomeric glycidyl ether I, IA or IB and Mischoligo- mer, which is based on glycidyl ethers I, IA and IB.
  • the present invention relates to curable epoxy resin compositions
  • curable epoxy resin compositions comprising a hardener component containing at least one curing agent and a resin component containing at least one polyepoxide compound selected from the group consisting of monomeric glycidyl ether I and oligomeric glycidyl ether I.
  • the present invention relates to Invention curable epoxy resin compositions
  • the present invention relates to curable epoxy resin compositions
  • EW epoxy equivalent
  • the curable epoxy resin composition according to the invention preferably comprises less than 40% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight, in particular less than 1% by weight, of bisphenol A or F based compounds on the entire resin component.
  • the curable epoxy resin composition of the invention is free of bisphenol A or F based compounds.
  • Bisphenol A or F based compounds in the context of the present invention are bisphenol A and F themselves, their diglycidyl ethers, and oligomers or polymers based thereon.
  • the polyepoxide compounds according to the invention overall make up a proportion of at least 40% by weight, preferably at least 60% by weight, in particular at least 80% by weight, based on the total resin component.
  • the total resin component makes up at least 10% by weight, in particular at least 25% by weight, based on the total curable epoxy resin composition.
  • Epo For the purposes of the present invention, all epoxy compounds and only the epoxide compounds of the curable epoxy resin composition of the resin component are attributable.
  • Epo For the purposes of the present invention, xid compounds are compounds having at least one epoxide group, that is to say corresponding reactive diluents, for example.
  • the epoxy compounds of the resin component preferably have on average at least 1.1, preferably at least 1.5, in particular at least 1.9 epoxide groups per molecule.
  • Hardeners in the context of the invention are compounds which are suitable for effecting crosslinking of the polyepoxide compounds according to the invention.
  • polyepoxide compounds By reaction with hardeners, polyepoxide compounds can be converted into non-fusible, three-dimensionally "crosslinked", duroplastic materials.
  • the curing agent has at least two functional groups which can react with the oxirane and / or hydroxyl groups of the polyepoxide compounds to form covalent bonds (polyaddition reaction). Curing then results in the formation of a polymeric network of covalently linked units derived from the polyepoxide compounds and units derived from the hardener molecules, whereby the degree of crosslinking can be controlled via the relative amounts of the functional groups in the curing agent and in the polyepoxide compound.
  • a compound is used which causes the homopolymerization of Polyepoxidnaps each other. Such compounds are often referred to as initiator or catalyst.
  • Homopolymerization-inducing catalysts are Lewis bases (anionic homopolymerization, anionic curing catalysts) or Lewis acids (cationic homopolymerization, cationic curing catalysts). They cause the formation of ether bridges between the epoxide compounds. It is believed that the catalyst reacts with a first epoxide group to form a reactive hydroxy group, which in turn reacts with another epoxide group to form an ether bridge, resulting in a new reactive hydroxy group. Due to this reaction mechanism, the sub-stoichiometric use of such catalysts for curing is sufficient. Imidazole is an example of a catalyst that induces anionic homopolymerization of epoxide compounds.
  • Boron trifluoride is an example of a catalyst that initiates cationic homopolymerization. It is also possible to use mixtures of various polyaddition reaction hardeners and mixtures of homopolymerization-inducing hardeners, as well as mixtures of polyaddition reaction-inducing and homopolymerization-inducing hardeners for curing polyepoxide compounds.
  • Suitable functional groups which can undergo a polyaddition reaction with the oxirane groups of polyepoxide compounds are, for example, amino groups, hydroxy groups, thioalcohols or derivatives thereof, isocyanates and carboxyl groups or derivatives thereof, such as anhydrides.
  • epoxy resins polyepoxide compounds
  • aliphatic, cycloaliphatic and aromatic polyamines carboxylic anhydrides
  • polyesters are usually used as hardeners for epoxy resins. aliphatic, cycloaliphatic and aromatic polyamines, carboxylic anhydrides.
  • lyamidoamine, aminoplasts such as formaldehyde condensation products of melamine, urea, benzoguanamine or phenoplasts such as novolacs used.
  • acrylate-based oligomeric or polymeric curing agents having hydroxy or glycidyl functions in the side chain as well as epoxy vinylester resins are used.
  • the skilled worker knows for which applications a fast or slow-acting hardener is used.
  • a hardener which acts very slowly (or only at a higher temperature).
  • a hardener which is released as an active form only under conditions of use, for example ketimines or aldimines.
  • Known hardeners have a linear or at most weakly crosslinked structure. They are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, Wiley-VCH, Chapter "Epoxy Resins", which is hereby incorporated by reference in its entirety.
  • Suitable hardeners for the curable epoxy resin composition according to the invention are, for example, polyphenols, polycarboxylic acids, polymercaptans, polyamines, primary monoamines, sulfonamides, aminophenols, aminocarboxylic acids, carboxylic anhydrides, phenolic hydroxy-containing carboxylic acids, sulfanilamides, and mixtures thereof.
  • the respective poly compounds for example polyamine
  • di compounds for example diamine
  • Preferred hardeners for the curable epoxy resin composition of the present invention are amino hardeners and phenolic resins.
  • the curable epoxy resin composition of the invention includes an amino hardener as a curing agent.
  • Amino hardeners suitable for the polyaddition reaction are compounds which have at least two secondary or at least one primary amino group. Linkage of the amino groups of the amino hardener with the epoxide groups of the polyepoxide compound forms polymers whose units derive from the amino hardeners and the polyepoxide compounds. Amino hardeners are therefore usually used in a stoichiometric ratio to the epoxy compounds. If, for example, the amino hardener has two primary amino groups, ie can couple with up to four epoxide groups, crosslinked structures can be formed.
  • the amino hardeners of the curable epoxy resin composition of the present invention have at least one primary amino group or two secondary amino groups.
  • Starting from polyepoxide compounds having at least two epoxide groups hardening by a polyaddition reaction (chain extension) can take place with an amino compound having at least two amino functions.
  • the functionality of an amino compound corresponds to their number of NH bonds.
  • a primary amino group thus has a functionality of 2 while a secondary amino group has a functionality of 1.
  • amino hardeners are used with a functionality of at least 3 (for example, at least 3 secondary amino groups or at least one primary and one secondary amino group), especially those having two primary amino groups (functionality of 4).
  • Preferred amino hardeners are dimethyldicykan (DMDC), dicyandiamide (DICY), isophoronediamine (IPDA), diethylenetriamine (DETA), triethylenetetramine (TETA), bis (p-aminocyclohexyl) methane (PACM), methylenedianiline (for example 4,4'-methylenedianiline)
  • Polyetheramines for example polyetheramine D230, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), 2,4-toluenediamine, 2,6-toluenediamine, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2,4-diamino-3
  • DICY isophorone diamine
  • IPDA isophorone diamine
  • methylenedianiline for example 4,4'-methylenedianiline
  • aminoplasts such as condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde or benzaldehyde with melamine, urea or benzoguanamine.
  • polyepoxide compound and amino hardener are preferably used in an approximately stoichiometric ratio in relation to the epoxide or amino functionality. Particularly suitable ratios of epoxide groups to amino functionality are, for example, 1: 0.8 to 0.8: 1.
  • the curable epoxy resin composition of the present invention includes a phenolic resin as a curing agent.
  • Phenol resins suitable for the polyaddition reaction have at least two hydroxyl groups.
  • Phenolic resins can typically be used in both stoichiometric and substoichiometric proportions to the epoxy compounds.
  • the use of suitable catalysts promotes the reaction of the secondary hydroxyl groups of the already formed epoxy resin with epoxide groups.
  • Suitable phenolic resins are novolaks, phenolic resoles, generally condensation products of aldehydes (preferably formaldehyde and acetaldehyde) with phenols.
  • Preferred phenols are phenol, cresol, xylenols, p-phenylphenol, p-tert.-butyl-phenol, p-tert.amyl-phenol, cyclopentylphenol, p-nonyl and p-octylphenol.
  • the curable epoxy resin composition of the invention may also comprise an accelerator for curing.
  • curing accelerators examples include imidazole or imidazole derivatives or urea derivatives (urones), for example 1,1-dimethyl-3-phenylurea (fenuron).
  • urones 1,1-dimethyl-3-phenylurea
  • tertiary amines such as Triethanolamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and tetramethyl guanidine as curing accelerator is described (US 4,948,700).
  • tertiary amines such as Triethanolamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol and tetramethyl guanidine
  • the curing of epoxy resins with DICY can be accelerated by the addition of fenuron.
  • the curable epoxy resin composition of the present invention may also include a diluent.
  • Diluents for the purposes of this invention are conventional diluents or reactive diluents.
  • the addition of diluent to a curable epoxy resin composition usually lowers its viscosity.
  • Conventional diluents are typically organic solvents or mixtures thereof, for example ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), diethyl ketone or cyclohexanone, esters of aliphatic carboxylic acids such as ethyl acetate, propyl acetate, methoxypropyl acetate or butyl acetate, glycols such as ethylene glycol, diethylene glycol, triethylene glycol or propylene glycol, etc.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), diethyl ketone or cyclohexanone
  • esters of aliphatic carboxylic acids such as ethyl acetate, propyl acetate, methoxypropyl acetate or butyl acetate
  • glycols such as ethylene glycol,
  • Glycol derivatives such as ethoxyethanol, ethoxyethanol acetate, ethylene or propylene glycol mono- or dimethyl ethers, aromatic hydrocarbons such as toluene or xylenes, aliphatic hydrocarbons such as heptane, and alkanols such as methanol, ethanol, n- or isopropanol or butanols.
  • Reactive diluents are low molecular weight substances which, in contrast to conventional solvents, have functional groups, generally oxirane groups, which can react with the hydroxy groups of the resin and / or the functional groups of the hardener to form covalent bonds.
  • Reactive diluents for the purposes of the present invention are aliphatic or cycloaliphatic compounds. They do not evaporate during curing, but are covalently bonded into the forming resin matrix during curing.
  • Suitable reactive diluents are, for example, mono- or polyfunctional oxiranes. Examples of monofunctional reactive diluents are glycidyl ethers of aliphatic and cycloaliphatic monohydroxy compounds having generally 2 to 20 carbon atoms, such as.
  • polyfunctional reactive diluents are, in particular, glycidyl ethers of polyfunctional alcohols having generally 2 to 20 C atoms which typically have on average 1.5 to 4 glycidyl groups, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether or the glycidyl ethers of Trimethylolpropane or pentaerythritol.
  • the reactive diluents described so far improve the viscosity properties of the epoxy resin compositions, they often worsen the hardness of the cured resin and lead to lower solvent resistance. Furthermore, it is known that the reactive diluents the Reactivity of the formulated epoxy resin compositions reduce, resulting in longer curing times.
  • the curable epoxy resin composition of the invention may also include fillers, for example pigments.
  • suitable fillers are metal oxides such as titanium dioxide, zinc oxide and iron oxide or hydroxides, sulfates, carbonates, silicates of these or other metals, for example calcium carbonate, aluminum oxide, aluminum silicates.
  • Further suitable fillers are, for example, silicon dioxide, pyrogenic or precipitated silica and also carbon black, talc, barite or other nontoxic pigments. It is also possible to use mixtures of the fillers.
  • the proportion by weight of the fillers in the coating, their particle size, hardness and their aspect ratio will be selected by a person skilled in the art according to the application requirements.
  • the curable epoxy resin composition according to the invention may contain further additives as required, for example defoamers, dispersants, wetting agents, emulsifiers, thickeners, biocides, co-solvents, bases, corrosion inhibitors, flame retardants, release agents and / or waxes.
  • further additives for example defoamers, dispersants, wetting agents, emulsifiers, thickeners, biocides, co-solvents, bases, corrosion inhibitors, flame retardants, release agents and / or waxes.
  • the curable epoxy resin composition of the present invention may also contain reinforcing fibers such as glass fibers or carbon fibers. These can be present for example as short fiber pieces of a few mm to cm in length, and as continuous fibers, wound or tissue.
  • the present invention further relates to a process for producing a cured epoxy resin comprising curing the curable epoxy resin composition.
  • the curing can be carried out at atmospheric pressure and at temperatures below 250 ° C., in particular at temperatures below 235 ° C., preferably at temperatures below 220 ° C., in particular in a temperature range from 40 ° C. to 220 ° C.
  • the curing of the curable epoxy resin composition to moldings is usually carried out in a tool until dimensional stability is achieved and the workpiece can be removed from the tool.
  • the subsequent process for reducing residual stresses of the workpiece and / or completing the crosslinking of the cured epoxy resin is called tempering.
  • the tempering process usually takes place at temperatures at the limit of the stiffness of the mold (Menges et al., "Werkstoff ambience Kunststoffe” (2002), Hanser-Verlag, 5th edition, page 136.) Usually at temperatures of 120 ° C. to 220 ° C. ° C, preferably tempered at temperatures of 150 ° C. to 220 ° C. Usually, the hardened workpiece is exposed to the annealing conditions for a period of 30 to 240 minutes Depending on the dimensions of the workpiece, longer annealing times may also be appropriate.
  • the substrate to be coated is first exposed to the curable epoxy resin composition, and then the curable epoxy resin composition is cured on the substrate.
  • the curable epoxy resin composition can be applied before or after the desired article is formed by dipping, spraying, rolling, brushing, knife coating or the like in liquid formulations or by applying a powder coating.
  • the application can be carried out on individual pieces (for example can parts) or on basically endless substrates, for example on steel strip rolls in coil coating. Suitable substrates are usually steel, tinplate (tinned steel) or aluminum (e.g., for beverage cans).
  • the curing of the curable epoxy resin composition after application to the substrate usually takes place in the temperature range from 20 ° C to 250 ° C, preferably from 50 ° C to 220 ° C, more preferably from 100 ° C to 220 ° C instead.
  • the time is usually 0.1 to 60 minutes, preferably 0.5 to 20 minutes, particularly preferably 1 to 10 minutes.
  • the present invention further relates to the cured epoxy resins obtainable or obtained by curing the curable epoxy resin composition according to the invention, in particular in the form of coatings on metallic substrates.
  • the present invention further relates to the use of monomeric or oligomeric glycidyl ethers I, IA or IB according to the invention or of oligomers based on glycidyl ether I, IA or IB or of the curable epoxy resin composition according to the invention for the production of adhesives, composites, moldings and coatings , in particular of coatings, preferably of containers, in particular of containers for the storage of foodstuffs.
  • Divinylbenzene (650 g, Aldrich) was added with isopropanol (650 g) and Rh (CO) 2-acetoacetate (65 mg).
  • the reaction mixture was in an autoclave CO / H2 (1: 1) with a cold pressure of 20 bar pressed. Subsequently, the reaction was carried out at 90 ° C and a reaction pressure of 280 bar (by stepwise pressing on of further synthesis gas (CO / H2 (1: 1))) for 5 h with stirring. After depressurizing to atmospheric pressure, 1200 g of the reaction mixture containing the corresponding dialdehydes with distilled water (120 g) and Raney nickel (40 g) added.
  • the reaction mixture was pressed in an autoclave of hydrogen at a cold pressure of 60 bar. Subsequently, the reaction was carried out at 120 ° C and a reaction pressure of 100 bar (by further pressurizing with hydrogen) for 15 hours with stirring. After relaxing to atmospheric pressure, the Raney nickel was separated from the reaction mixture via a frit with diatomaceous earth. 1200 g of the remaining reaction mixture containing the corresponding diols were then purified by distillation. For this purpose, the isopropanol was first stripped off in a rotary evaporator at 80 ° C. and 100 to 10 mbar. The remaining diol-containing fraction was then fractionally distilled at temperatures of 15 to 185 ° C to obtain the Divinybenzol derivative IIA, which is a mixture of the different diols.
  • reaction mixture With a molar excess of aqueous formaldehyde (36.5% tig), whereupon this reaction mixture is then slowly added to a catalytic amount of triethanolamine, and it is then neutralized after the aldol reaction with formic acid (98% tig).
  • the reaction mixture thus prepared can, if appropriate after distillative purification, be subjected to a hydrogenation as described in Example 1, so that divinylbenzene derivative IIB, which is a mixture of the different polyols, can be obtained.
  • the divinylbenzene derivative IIA (0.7 mol, 136 g), which is a mixture of the various diols resulting from the hydroformylation and subsequent hydrogenation of divinylbenzene, was heated to 90 ° C and treated with stannic chloride (7, 6 mmol, 2 g).
  • Epichlorohydrin (1.4 mol, 129.5 g) was subsequently added dropwise in portions, during which the temperature did not rise above 140.degree. C. and should not fall below 85.degree. After the end of the addition, stirring was continued at 90 ° C. until no epoxide content could be measured.
  • the reaction mixture was cooled to room temperature, treated with 25% sodium hydroxide solution (1, 4 mol, 224 g) and heated once to boiling. After cooling, the phases were separated, the organic phase washed several times with water and dried in vacuo. The product was obtained with a yield of 95%.
  • the resulting epoxy resin had an EEW of 202, suggesting that in addition to monomeric diglycidyl ether, dimers, trimers, and higher molecular weight diglycidyl ethers are also present. were goods.
  • the monomeric diglycidyl ether can be separated by distillation from the oligomers.
  • the glycidyl ether IB can be prepared analogously to Example 3 by reaction with epichlorohydrin.
  • the molar amount of epichlorohydrin used is preferably adjusted based on the number of hydroxyl groups of the divinylbenzene derivative IIB in comparison with the divinylbenzene derivative IIA.
  • the monomeric glycidyl ether IB can be purified by distillation from the oligomers.
  • Glycidyl ether IA from Example 3 (EEW 202 g / eq) was mixed immediately after the preparation and without further purification with a stoichiometric amount of an amine hardener.
  • the hardener used was isophoronediamine (IPDA).
  • IPDA isophoronediamine
  • a corresponding stoichiometric mixture of bisphenol A-based epoxy resin (BADGE, Epilox A19-03 from LEUNA resins, EEW 182 g / eq) and IPDA was prepared. The mixtures were incubated at 23 ° C and 75 ° C for rheological characterization.
  • the rheological measurements for investigating the reactivity profile were carried out on a shear stress controlled plate-plate rheometer (MCR 301 from Anton Paar) with a plate diameter of, for example, 15 mm and a gap distance of, for example, 0.25 mm at the different temperatures.
  • MCR 301 shear stress controlled plate-plate rheometer
  • the measurement of the gelling time was carried out in a rotationally oscillating manner on the abovementioned rheometer at, for example, 23 ° C. and 75 ° C.
  • the intersection of loss modulus (G ") and storage modulus (G ') provides the gelation time
  • the average viscosity for 2 to 5 minutes after preparation of the mixture was considered to be initial viscosity (AV).
  • Tg glass transition temperature

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Abstract

L'invention concerne des glycidyléthers de dérivés de divinylbenzène. Les résines époxy durcies sont largement répandues en raison de leurs propriétés mécaniques et chimiques exceptionnelles. On utilise habituellement des résines époxy à base de diglycidyléthers de bisphénol A ou bisphénol F, qui posent toutefois des problèmes dans de nombreux domaines en raison de leur effet endocrinien. La présente invention concerne des glycidyléthers de diols et/ou polyols à base de divinylbenzène et des compositions de résine époxy durcissable à base de ces derniers en lieu et place de diglycidyléthers de bisphénol A ou bisphénol F ou de compositions de résine époxy à base de ces derniers.
EP14747946.3A 2013-08-14 2014-08-07 Glycidyléthers de dérivés de divinylbenzène et oligomères desdits glycidyléthers de dérivés de divinylbenzène en tant que résine époxy durcissable Withdrawn EP3033320A1 (fr)

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EP14747946.3A EP3033320A1 (fr) 2013-08-14 2014-08-07 Glycidyléthers de dérivés de divinylbenzène et oligomères desdits glycidyléthers de dérivés de divinylbenzène en tant que résine époxy durcissable
PCT/EP2014/066952 WO2015022253A1 (fr) 2013-08-14 2014-08-07 Glycidyléthers de dérivés de divinylbenzène et oligomères desdits glycidyléthers de dérivés de divinylbenzène en tant que résine époxy durcissable

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Non-Patent Citations (4)

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SERGIO?A. CALDARELLI ET AL: "Synthesis and Evaluation of Bis-Thiazolium Salts as Potential Antimalarial Drugs", CHEMMEDCHEM, vol. 5, no. 7, 5 July 2010 (2010-07-05), pages 1102 - 1109, XP055450162, ISSN: 1860-7179, DOI: 10.1002/cmdc.201000097 *
TETSUO TAKEMURA ET AL: "Separation and characterization of all configurational isomers by enzymatic discrimination of each chiral function", TETRAHEDRON LETTERS, 1 January 1992 (1992-01-01), pages 6335 - 6338, XP055450129, Retrieved from the Internet <URL:http://www.sciencedirect.com/science/article/pii/S004040390060967X/pdf?md5=58b4f89def60394136d22aa518cceb7e&pid=1-s2.0-S004040390060967X-main.pdf> DOI: 10.1016/S0040-4039(00)60967-X *
YAJUN GAO ET AL: "2,2'-( p -Phenylenedimethylene)bis(propane-1,3-diol)", ACTA CRYSTALLOGRAPHICA SECTION C. CRYSTAL STRUCTURE COMMUNICATIONS, vol. 65, no. 1, 15 January 2009 (2009-01-15), DK, pages o170 - o170, XP055450173, ISSN: 0108-2701, DOI: 10.1107/S1600536808041688 *

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