EP1877458A1 - Base de mannich a base de resorcine - Google Patents

Base de mannich a base de resorcine

Info

Publication number
EP1877458A1
EP1877458A1 EP06754919A EP06754919A EP1877458A1 EP 1877458 A1 EP1877458 A1 EP 1877458A1 EP 06754919 A EP06754919 A EP 06754919A EP 06754919 A EP06754919 A EP 06754919A EP 1877458 A1 EP1877458 A1 EP 1877458A1
Authority
EP
European Patent Office
Prior art keywords
amine
mannich base
component
formaldehyde
resorcinol
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Withdrawn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
EP06754919A
Other languages
German (de)
English (en)
Inventor
Ulrich Gerber
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
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 Sika Technology AG filed Critical Sika Technology AG
Priority to EP06754919A priority Critical patent/EP1877458A1/fr
Publication of EP1877458A1 publication Critical patent/EP1877458A1/fr
Withdrawn legal-status Critical Current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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/22—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
    • C07C215/28—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • C07C215/34—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings containing hydroxy groups and carbon atoms of six-membered aromatic rings bound to the same carbon atom of the carbon skeleton and at least one hydroxy group bound to another carbon atom of the carbon skeleton
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C08G59/623—Aminophenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to the field of preparation and use of Mannich bases.
  • Mannich bases The class of Mannich bases has been known for a long time and has already been used in hardener components of reactive systems. For the preparation of phenols are used. However, phenol (hydroxybenzene) as starting material has the great disadvantage that the Mannich bases prepared therefrom still contain portions of unreacted phenol. Due to the toxicity of phenol, phenol-based Mannich bases can not be used in many market sectors. Therefore, great efforts have been made to produce phenol-free Mannich bases. For example, Mannich bases based on nonylphenol or p-tert-butylphenol or cardanol have been developed and commercialized.
  • Mannich bases are mainly used as accelerators for epoxy resins or as hardeners for epoxy resins and polyurethanes.
  • WO 00/15687 describes a Mannich base accelerator which is prepared by transamination of a Mannich base with an amine.
  • EP-A-1 475 411 discloses a two-stage preparation process for the preparation of Mannich bases based on m-cresol or 3,5-xylenol and polyamines, in which a tertiary amine is preferably used.
  • EP-A-1 475 412 discloses a two-stage production process of Mannich bases, which are obtained from phenols such as m-cresol, 3,5-xylenol or resorcinol with polyamines, preferably using tertiary amines.
  • two-stage processes are associated with additional expense and increase the production of Mannich bases.
  • the object of the present invention is therefore to provide novel Mannich bases and the process for their preparation which are free of phenol and can be prepared by a simplified process.
  • Mannich bases according to claim 1 can be prepared by a specific selection of known in the art polyamine and phenolic compounds, which can solve this problem. These Mannich bases can be made from cheap, easily accessible raw materials through simple production. They are characterized by an excellent curing behavior, especially at low temperatures, with amine-reactive compounds.
  • the present invention relates to Mannich bases which can be prepared from resorcinol, formaldehyde and / or triethylenetetramine and / or tetraethylenepentamine.
  • Resorcinol (CAS No. [108-46-3]) is commercially available in a wide range of purities. Resorcinol is distinguished from the other dihydroxybenzene isomers catechol and hydroquinone, among other things by a lower toxicity (German water hazard class WGK 1 compared to 2 or 3 or Swiss poison class 3 compared to 2). It has particularly shown that resorcinol over these, as well as others Phenols such as phenol, the various isomers of cresol or xylenol surprisingly very well suited for the preparation of Mannich bases.
  • Formaldehyde can be used in forms commonly known to those skilled in the art directly or from formaldehyde-releasing compounds. Preferred is formaldehyde in the form of para-formaldehyde or as a formalin solution. Particularly preferred is formalin solution.
  • triethylenetetramine and / or tetraethylenepentamine is used for the preparation of the novel Mannich bases.
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • TETA and TEPA are commercially widely available and are very inexpensive. They are offered and used in particular in technical quality. Such technical quality is preferred. It is known to the person skilled in the art that TETA and TEPA in such technical quality are not a pure, uniform chemical substance.
  • TETA TETA
  • the predominantly formed substances and isomers are: N, N'-bis (2-aminoethyl) piperazine (BisAEP or DiAEP) (CAS No. [6531-38-0])
  • NTEA or NTE Tris (2-aminoethyl) amine (CAS No. [4097-89-6]) or, in the case of TEPA:
  • AETETA 4-Aminoethyltriethylenetetramine
  • AEPEEDA Aminoethyl piperazinoethylethylenediamine
  • PEDETA Piperazinoethyldiethylenetriamine
  • TETA and TEPA are examples of polyamines TETA and TEPA.
  • TETA and TEPA have a high N / C ratio, and accordingly, a lot of amino groups can be introduced by means of a small molecule, and hence a small amount.
  • Mannich base preferably has an amine number of between 800 and 1100 mg / g KOH, in particular in the range between 900 and 1000 mg / g KOH, preferably in the range between 950 and 1000 mg / g KOH.
  • Mannich bases can be prepared which no longer have measurable amounts of unreacted resorcinol, the amine number.
  • Another aspect of the present invention relates to the preparation of the described Mannich base.
  • resorcin, triethylenetetramine and / or tetraethylenepentamine with formaldehyde at a temperature below 25 0 C is reacted.
  • a premix of resorcinol and triethylenetetramine and / or tetraethylenepentamine formaldehyde under stirring and cooling to a temperature below 25 0 C, especially below 15 0 C is added.
  • the addition is preferably carried out in portions, in particular as a drop of.
  • the resorcinol / [TETA and / or TEPA] premix is preferably previously heated to a temperature of about 8O 0 C to dissolve the resorcinol and cooled again before the formaldehyde is added. It has been shown that it is advantageous if the premix further comprises a solvent, in particular an alcohol, preferably methanol, in order to better dissolve the resorcinol and lower the viscosity, and which is added before the reaction with formaldehyde. Particularly advantageously, the solvent is already used at the very beginning, ie in the preparation of the premix.
  • the reaction mixture is preferably raised to a temperature and in particular to about 95 0 C and at the same time a slight vacuum of typically 0.6 to 0.9 bar set.
  • a slight vacuum typically 0.6 to 0.9 bar set.
  • the solvent used is therefore advantageous to select so that it is easy to distill off at this temperature and pressure.
  • Mannich bases can also be prepared without the presence of additional tertiary amines which are not already present in technical triethylenetetramine and / or technical tetraethylenepentamine.
  • the molar ratios of resorcinol to formaldehyde to the sum of TETA and TEPA are in particular 1: 1.5-2.5: 2.5-3.5. Such a ratio of 1 to about 2 to about 3 has proven particularly suitable.
  • the Mannich base so formed is preferably free of unreacted resorcinol, i. that no measurable amounts of resorcinol are present in the Mannich base, and in particular has an amine number of between 800 and 1100 mg / g KOH, in particular in the range between 900 and 1000 mg / g KOH, preferably in the range between 950 and 1000 mg / g KOH , on.
  • the Mannich base can be used as such or in a composition.
  • the Mannich bases are particularly suitable as hardeners for an amine-reactive substance which has at least two amine-reactive functional groups.
  • Suitable amine-reactive functional groups are, in particular, glycidyl ether and / or isocyanate groups.
  • the amine-reactive substance having at least two amine-reactive functional groups is a diglycidyl ether. In particular, it is a diglycidyl ether of bisphenol-A, bisphenol-F or bisphenol-A / F.
  • such a diglycidyl ether is a so-called liquid resin, especially as available on the market under the trade name Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or D.E. R 331 (Dow).
  • the amine-reactive substance having at least two amine-reactive functional groups a Polyisocyanate or a prepolymer having at least two isocyanate groups.
  • HDI 6-hexamethylene diisocyanate
  • TMDI 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • prepolymers having at least two isocyanate groups are, in particular, those prepolymers which are obtainable from at least one of the abovementioned polyisocyanates and at least one polyol.
  • Particularly suitable polyols are polyoxyalkylene polyols or polyester polyols having at least two OH groups, in particular 2 or 3 OH groups.
  • amine-reactive substance which has at least two amine-reactive functional groups
  • novel Mannich base By mixing the amine-reactive substance, which has at least two amine-reactive functional groups, with the novel Mannich base, a reaction of the amine groups of the Mannich bases with the amine-reactive functional groups of the amine-reactive substance occurs and curing takes place.
  • the present invention also includes a two-component composition consisting of a first component K1 and a second component K2.
  • the first component K1 comprises at least one amine-reactive compound having at least two functional groups which can react with amines.
  • the second component K2 comprises at least one Mannich base, as previously described.
  • the compounds which are suitable as amine-reactive compounds which have at least two functional groups which can react with amines have already been described above.
  • the first component K1 advantageously comprises several amine-reactive compounds.
  • the use of a more viscous and a lower viscosity amine-reactive compound is recommended.
  • As the low-viscosity amine-reactive compound special so-called reactive diluents are preferred.
  • the second component K2 may contain, in addition to the Mannich base, further amines.
  • this is an aliphatic or cycloaliphatic amine, preferably isophoronediamine (IPDA).
  • IPDA isophoronediamine
  • the component K2 may contain TETA or TEPA. This additional amine can be added already at the end of Mannich base or only when formulating component K2. Both components K1 and K2 can be added to the
  • Such further ingredients are in particular fillers, plasticizers, solvents, catalysts and / or additives.
  • Particularly suitable fillers are Russian, chalks, in particular coated chalks, sands, silicates, light fillers, such as ceramic or glass spheres, in particular ceramic or glass hollow spheres, pyrogenic silicic acids, fly ash.
  • Particularly preferred solvents are solvents which are not classified as VOC "volatile organic compounds.” Particularly preferred are higher-boiling hydrocarbons.
  • plasticizers are in particular phthalates and adipates, in particular diisodecyl phthalate (DIDP) and dioctyl adipate (DOA).
  • DIDP diisodecyl phthalate
  • DOA dioctyl adipate
  • Such two component compositions can be widely used. Particularly preferred is their use as an adhesive or
  • hardener components can be made available with the novel Mannich bases which are free of phenols but also free of other phenolic compounds, and preferably also free, i. no longer containing measurable amounts of unreacted resorcinol.
  • the adhesive After mixing the components K1 and K2 of the described two-component composition, the adhesive is applied to a substrate surface and joined to another surface of the substrate.
  • the cured composition acts as an adhesive layer capable of transferring forces between the two substrate surfaces of the formed composite.
  • the two-component composition is suitable because of their
  • such a two-component composition especially a two-part epoxy resin composition, ie where component K1 comprises a diglycidyl ether, can be used as an adhesive for the bonding of fiber-reinforced composites.
  • a two-component epoxy resin composition ie where component K1 comprises a diglycidyl ether
  • inventive two-component compositions in particular a two-component epoxy resin composition
  • carbon or glass fibers can be embedded in a two-component composition and can be used in the cured state as a fiber composite, for example in the form of a lamella.
  • fiber fabric or scrim can be applied by means of a two-component composition, in particular by means of a two-component epoxy resin composition, to a building, and together with the building together form a fiber-reinforced composite.
  • the viscosity was measured by means of Rheomat at 2O 0 C cone / plate (40 mm cone, 300 revolutions / sec or 20mm cone, 50 revolutions / s).
  • the residual content of the polyamine was determined by GC / FID (Optima-5MS, 60 mg dissolved in 10 ml ethyl acetate, carrier gas He, external 3 point calibration in the concentration range 2-6 mg / ml) and the residual content of the phenolic compound by HPLC / PDA (Varian , LiChrosphere 100 RP-18, eluent water, acetonitrile, UV 273 nm).
  • the amine number was determined titrimetrically on a Memotritator DL-55 from Mettler, Switzerland.
  • the Mannich bases were used as hardener component K2 for an epoxy resin component K1.
  • the epoxy resin component consisted of either 80% by weight of diglycidyl ether of bisphenol A (Araldite® GY 250, Huntsman) and 20% by weight of hexanediol diglycidyl ether (Araldite® DY-H, Huntsman, Epoxy Number 6.25-6.65) (K1-1) or from 85% by weight of diglycidyl ether of bisphenol-A (Araldite® GY 250, Huntsman) and 15% by weight of trimethylolpropane triglycidyl ether (Araldite® DY-T / CH, Huntsman) (K1-2).
  • the pot life was determined by stirring 100 g of the mixed components at room temperature in a beaker by means of a spatula. The pot life was the time at which the batch gelled.
  • the tensile strength (ZF (1d)) and the elongation at break (BD (ID)) were measured after 1 day of curing at room temperature according to ISO 527 at a measuring speed of 5 mm / min on a Zwick tensile machine.
  • the glass transition temperature was measured as peak maximum by means of DSC (0-25O 0 C 107 min).
  • compositions Z1 and Z2 were aluminum plates as well.
  • Mannich base M1 as hardener component K2 with the A component of Sikadur®-30 (commercially available from Sika GmbH AG), which is based on bisphenol A diglycidyl ether and an epoxy reactive diluent, was prepared as component K1 in a mixing ratio of 1: 10 mixed and glued a concrete slab with a concrete ceiling.
  • the bond had a good adhesion and a good bond strength.

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)
  • Adhesives Or Adhesive Processes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Sealing Material Composition (AREA)

Abstract

La présente invention concerne des bases de Mannich pouvant être produites à partir de résorcine, de formaldéhyde et de triéthylènetétramine et/ou de tétraéthylènepentamine. L'invention concerne en outre un procédé de production de ces bases et leur utilisation comme durcissants pour des composés réagissant avec les amines. Les bases de Mannich sont particulièrement adaptées comme composants de durcissement dans des adhésifs.
EP06754919A 2005-04-29 2006-04-28 Base de mannich a base de resorcine Withdrawn EP1877458A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06754919A EP1877458A1 (fr) 2005-04-29 2006-04-28 Base de mannich a base de resorcine

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP05103574A EP1717253A1 (fr) 2005-04-29 2005-04-29 Base de Mannich à base de résorcinol
PCT/EP2006/061917 WO2006117339A1 (fr) 2005-04-29 2006-04-28 Base de mannich a base de resorcine
EP06754919A EP1877458A1 (fr) 2005-04-29 2006-04-28 Base de mannich a base de resorcine

Publications (1)

Publication Number Publication Date
EP1877458A1 true EP1877458A1 (fr) 2008-01-16

Family

ID=34939608

Family Applications (2)

Application Number Title Priority Date Filing Date
EP05103574A Withdrawn EP1717253A1 (fr) 2005-04-29 2005-04-29 Base de Mannich à base de résorcinol
EP06754919A Withdrawn EP1877458A1 (fr) 2005-04-29 2006-04-28 Base de mannich a base de resorcine

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP05103574A Withdrawn EP1717253A1 (fr) 2005-04-29 2005-04-29 Base de Mannich à base de résorcinol

Country Status (10)

Country Link
US (1) US20090118457A1 (fr)
EP (2) EP1717253A1 (fr)
JP (1) JP2008539207A (fr)
KR (1) KR20080007484A (fr)
CN (1) CN101166772A (fr)
AU (1) AU2006243839A1 (fr)
CA (1) CA2605523A1 (fr)
MX (1) MX2007012959A (fr)
RU (1) RU2007144210A (fr)
WO (1) WO2006117339A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2030965A1 (fr) 2007-08-31 2009-03-04 Sika Technology AG Aldéhyde comprenant des groupes d'hydroxyle
CN101717320B (zh) * 2009-11-26 2014-06-18 安阳师范学院 一种曼尼希碱的制备方法
US9309354B2 (en) * 2011-06-24 2016-04-12 Dow Global Technologies Llc Thermosetting composition and process for preparing fiber-reinforced composites
EP2639252A1 (fr) 2012-03-14 2013-09-18 Sika Technology AG Nouveaux catalyseurs de polymères réactifs pour systèmes de résine époxy 2K
ES2719806T3 (es) 2012-08-16 2019-07-16 Blue Cube Ip Llc Agentes de curado rápido para resinas epoxi
DE102015122435A1 (de) * 2015-12-21 2017-06-22 Endress + Hauser Flowtec Ag Feldgerät der Automatisierungstechnik und Verfahren zu dessen Herstellung
WO2019221796A2 (fr) * 2018-02-16 2019-11-21 Massachusetts Institute Of Technology Nanofibres de carbone microporeuses
CN108864966A (zh) * 2018-06-21 2018-11-23 四川中建华兴科技有限公司 一种新型加固型碳布胶及其制备工艺
JP2021004270A (ja) * 2019-06-25 2021-01-14 住友ベークライト株式会社 フェノール樹脂
CN111675990B (zh) * 2020-06-23 2022-04-19 山东北方现代化学工业有限公司 一种聚醚胺预固化环氧快速固化胶粘剂及其制备方法

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Also Published As

Publication number Publication date
US20090118457A1 (en) 2009-05-07
RU2007144210A (ru) 2009-06-10
MX2007012959A (es) 2007-12-13
JP2008539207A (ja) 2008-11-13
CN101166772A (zh) 2008-04-23
CA2605523A1 (fr) 2006-11-09
KR20080007484A (ko) 2008-01-21
AU2006243839A1 (en) 2006-11-09
WO2006117339A1 (fr) 2006-11-09
EP1717253A1 (fr) 2006-11-02

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