JP2013521257A - Use of linear triethylenetetraamine as a curing agent for epoxy resins - Google Patents

Abstract

  The present invention relates to a tertiary amine derived from the condensation of linear triethylenetetraamine and ethylenediamine and one or more amines selected from the group consisting of methyl substituted compounds derived from linear triethylenetetraamine The present invention relates to an amine composition containing a compound and a method for producing the composition. The invention also relates to the use of linear triethylenetetraamine or the amine composition according to the invention as an amine curing agent. The present invention also relates to an amine curing agent composition containing linear triethylenetetraamine, a curable composition containing linear triethylenetetraamine, and a method for producing the curable composition. Additionally, the present invention relates to a cured epoxy resin containing linear triethylenetetraamine, particularly a reinforced composite, and a method for producing the cured epoxy resin. Furthermore, this invention relates to the reactive polyamide resin obtained from a linear triethylenediamine and a dimer fatty acid. The present invention relates to a tertiary amine derived from the condensation of linear triethylenetetraamine and ethylenediamine and one or more amines selected from the group consisting of methyl substituted compounds derived from linear triethylenetetraamine The present invention relates to an amine composition containing a compound and a method for producing the composition. The invention also relates to the use of linear triethylenetetraamine or the amine composition according to the invention as an amine curing agent. The present invention also relates to an amine curing agent composition containing linear triethylenetetraamine, a curable composition containing linear triethylenetetraamine, and a method for producing the curable composition. Additionally, the present invention relates to a cured epoxy resin containing linear triethylenetetraamine, particularly a reinforced composite, and a method for producing the cured epoxy resin. Furthermore, this invention relates to the reactive polyamide resin obtained from a linear triethylenediamine and a dimer fatty acid.

Description

Detailed Description of the Invention The present invention is selected from the group consisting of linear triethylenetetraamine, and tertiary amines derived from the condensation of ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamine. The present invention relates to an amine composition containing one or more amine compounds and a method for producing the composition.

  The invention also relates to the use of linear triethylenetetraamine or the amine composition according to the invention as an amine curing agent.

  The present invention also relates to an amine curing agent composition containing linear triethylenetetraamine, a curable composition containing linear triethylenetetraamine, and a method for producing the curable composition.

  Additionally, the present invention relates to a cured epoxy resin containing linear triethylenetetraamine, particularly a reinforced composite, and a method for producing the cured epoxy resin.

  Furthermore, this invention relates to the reactive polyamide resin obtained from a linear triethylenediamine and a dimer fatty acid.

  Curable compositions based on amine curing agents and epoxy resins are used on a large scale in the industry to produce cured epoxy resins. Typical applications include flooring, civil engineering, marine and industrial coatings, adhesives, tools, composites, casting, composite layers and encapsulation.

  Epoxy resins are an important class of polymeric materials characterized by the presence of two or more epoxy rings. The epoxy resin is converted to a cured epoxy resin, which is a solid, infusible and insoluble three-dimensional network structure, by a curing agent that can undergo a chemical reaction with the epoxy ring of the epoxy resin.

  In general, amines are used as functional curing agents. These amines can be either primary or secondary amines. Secondary amines can only react with one epoxy group, while primary amine groups can react with two epoxy groups. Usually primary amine groups react much faster than secondary amine groups. A tertiary amine that does not have active hydrogen does not react with the epoxy group at all, but generally acts as a catalyst to promote the epoxy reaction.

  The reactivity of amines also depends on their chemical properties. Aliphatic amines are generally more reactive than cycloaliphatic amines, which are similarly more reactive than aromatic amines. Thus, aliphatic amines are suitable for curing epoxy resins at room temperature, while aromatic amines generally require higher curing temperatures.

Aromatic amines are typically utilized in applications that require high temperature stability because they result in a final material having a high glass transition temperature (T _g ). Aromatic amines also result in materials with good chemical resistance. The light stability of aromatic curing agents, on the other hand, is insufficient for some applications. Many aromatic amines are solid at room temperature and because of their low reactivity, they usually require high temperature curing. Furthermore, the viscosity of the epoxy system is higher than the viscosity of the aliphatic or cycloaliphatic amine. Cycloaliphatic amines can result in a material having a T _g close to the T _g of the aromatic amine.

  A widely used aliphatic amine composition as a curing agent for epoxy resins is commercially available triethylenetetraamine (TETA). "Commercial TETA" is generally produced by the reaction of ethylene dichloride and aqueous ammonia, which produces a higher homologue with the hydrochloride of ethylenediamine. This reaction is usually carried out in the liquid phase without using a catalyst. Treatment with caustic soda liberates free amines. This process yields various derivatives of ethylenediamine (EDA) such as piperazine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine and aminoethylpiperazine, which are separated by distillation. However, although distillation does not yield pure linear TETA, a mixture of linear TETA and cyclic and branched compounds is obtained.

  The composition of “commercially available TETA” is, for example, “Screening Information Data Set of the Organization for Economic Co-Operation and Development (OECD SIDS)” (published by UNEP Publications, July 1998, www.inchem. available under org / documents / sids / sids / 112-24-3.pdf).

の直鎖状ＴＥＴＡの含有率は、６０％〜７０％の間である。 According to the above references, the following formula (I)

The linear TETA content is between 60% and 70%.

The main impurities are:
N, N′-bis (2-aminoethyl) piperazine (DAEPIP): 11-13%;
(Piperazinoethyl) ethylenediamine (PEEDA): 10-13%;
Tris (aminoethyl) amine (TAEA): 4-6%;
Diethylenetriamine (DETA): ≦ 3%; and water: ≦ 0.5%.

  Small amounts of further by-products can also be present, for example aminoethylethanolamine (AEEA), N- (2-aminoethyl) piperazine (AEPIP), hydroxyethylpyrrolidone (HEP) and tetraethylenepentamine (TEPA).

DAEPIP (II), PEEDA (III) and TAEA (IV) are also amine compounds containing tertiary amine groups having the following formula:

  The designation “triethylenetetraamine” or “TETA”, commonly used and known in the epoxy industry, refers to a commercially available mixture without meaning a linear compound of formula I. The use of “triethylenetetraamine” or “TETA” causes some confusion. In general, linear compounds of formula I are not commercially available with a purity higher than 70%. Thus, the notation “TETA” or “triethylenetetraamine” in the literature for epoxy resins generally means a commercially available mixture and not a linear compound of formula I.

  “Pure TETA” or “purified TETA” having a purity of greater than 98% was reported in US-A-2006 / 0041170 and the OECD SIDS mentioned above. US-A-2006 / 0041170 describes the use of substantially pure TETA in pharmaceutical products. However, these publications do not mention the use of “pure” or “purified TETA” in epoxy applications.

  In the context of the present invention, the term “linear TETA” means a compound of formula I. The term “commercially available TETA” means industrial products and commercial products having a content of about 60-70% by weight of the above-mentioned linear TETA. Furthermore, the term “pure TETA” or “purified TETA” refers to a composition comprising linear TETA having a linear TETA content of 98% by weight or more.

  As described above, the use of “commercially available TETA” as a curing agent in an epoxy resin is similarly established for its high availability and is inexpensive. “Commercially available TETA” exhibits good curing properties. These curing properties are due to the presence of a tertiary amine, which acts as a catalyst in the reaction between primary and secondary amines and epoxides. Good curing behavior results in a shorter production cycle as it reduces the time that the molded part is removed. Furthermore, the use of “commercial TETA” results in an epoxy system having low brittleness. The hindrance to using “commercial TETA” is that only a low network density is achieved due to the high content of tertiary amines present above 30% by weight and not participating in the curing reaction. The fact is that an epoxy resin with a low glass temperature typically less than 120 ° C. is obtained. A high glass transition temperature is often desirable to expand the temperature range in which it can be applied to molded parts made of epoxy resin. In the case of “commercially available TETA”, the high glass transition temperature is generally characterized by other properties such as gel time, vulcanization time, cure time or cure time characterized by cure time or cure time or pot life. It cannot be achieved without sacrificing handling properties, or mechanical properties such as brittleness.

  Curing time, gel time, vulcanization time or curing time all usually mean the time required to efficiently solidify the resin at the molding temperature. In the context of the present invention, the term curing time is used to mean this property. Shortening of the curing time allows for shorter removal times of the molded parts or allows for faster release of the molded parts from their molds, thereby allowing for a shorter production cycle.

  Both waiting time or pot life usually means the length of time that the resin system retains a sufficiently low viscosity to be used in processing. In the context of the present invention, the term pot life is used to mean this property. The long pot life allows the filling of complex molded parts to produce complex molded parts and ensures a high level of processing stability.

  For example, the addition of additional linear amines, such as ethylenediamine (EDA), results in an increase in glass transition temperature, which also leads to increased cure time due to dilution of the tertiary amine component. Furthermore, the characteristic mechanical properties of “commercially available TETA” are adversely affected by substitution with other linear amines. Furthermore, lower amines, such as EDA, have a low boiling point and thus contribute to an increase in undesirable volatile organic compounds (VOC).

  Addition of alicyclic or aromatic amines also increases the glass transition temperature. However, alicyclic amines and aromatic amines are generally less available and significantly more expensive than aliphatic amines. Thus, the use of alicyclic amines and aromatic amines significantly reduces the economic viability of epoxy systems and is unattractive for large scale applications. Aromatic amines and cycloaliphatic amines generally have a high viscosity, which affects the flowability and processing of the epoxy mixture. Aromatic amines and alicyclic amines also result in increased cure times due to their reduced reactivity. In addition, the use of aromatic amines reduces light stability and causes resin discoloration.

  The object of the present invention is to have a high glass transition temperature without increasing the curing time and reducing the pot life in order to achieve the excellent mechanical properties of the resulting cured epoxy resin and the excellent processing properties of the curable composition. It is to provide an aliphatic amine curing agent that results in a cured epoxy resin.

のＴＥＴＡの質量とエチレンジアミンの縮合から誘導された第３級アミン及び直鎖状トリエチレンテトラアミンから誘導されたメチル置換化合物からなる群から選択されるアミン化合物の質量との合計を基準にして、８５〜９８質量％の式Ｉのトリエチレンテトラアミン並びに１５質量％以下の、エチレンジアミンの縮合から誘導された第３級アミン及び直鎖状トリエチレンテトラアミンから誘導されたメチル置換化合物からなる群から選択される１種以上のアミン化合物を含むアミン組成物によって解決される。 The subject of the present invention is the following formula I

Based on the sum of the mass of the TETA of the amine and the mass of the amine compound selected from the group consisting of a tertiary amine derived from the condensation of ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine, From the group consisting of 85 to 98% by weight of triethylenetetraamine of the formula I and up to 15% by weight of tertiary amines derived from the condensation of ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamines. Solved by an amine composition comprising one or more selected amine compounds.

  The composition of the present invention comprises linear TETA of formula I, which means “linear TETA” as defined above.

  The composition of the present invention also includes one or more amine compounds selected from the group consisting of tertiary amines derived from condensation of ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamine.

  In a preferred embodiment of the invention, the amine compound selected from the group consisting of tertiary amines derived from the condensation of ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamine is derived from the condensation of ethylenediamine. Tertiary amine.

  Within the framework of the present invention, “tertiary amines derived from the condensation of ethylenediamine” are called “TADE”. The term “TADE” refers to cyclic and branched derivatives of ethylenediamine (EDA), which are believed to be made by the condensation of two or more EDA molecules and contain at least one tertiary amine group per molecule. Have. The tertiary amine derived from the condensation of ethylenediamine usually has a degree of condensation of 2 or more, preferably 2 to 10, more preferably 2 to 6, especially 2 to 4. Within the context of the present invention, the degree of condensation means the number of EDA molecules that condense to obtain the respective TADE.

  TADE can be subdivided into cyclic tertiary amines (“cyclic TADE”), which are derivatives of EDA, and branched tertiary amines (“branched TADE”), which are derivatives of EDA.

（式中、Ｒ^１はＨであり且つＲ^２はＣＨ_２ＣＨ_２Ｘであるか又は
Ｒ^１及びＲ^２は両方ともＣＨ_２ＣＨ_２Ｘであり；
Ｘ＝ＮＲ^３ _２であり；且つ
Ｒ^３は両方とも又は個々にＨ又はＣＨ_２ＣＨ_２Ｘであり；且つ
縮合度は好ましくは２〜１０、更に好ましくは２〜６、更に好ましくは２〜４である）
を特徴とし得る。 The cyclic TADE has the general formula (V)

Wherein R ¹ is H and R ² is CH ₂ CH ₂ X or R ¹ and R ² are both CH ₂ CH ₂ X;
X = NR ³ ₂ ; and R ³ are both or individually H or CH ₂ CH ₂ X; and the degree of condensation is preferably 2-10, more preferably 2-6, more preferably 2-4. Is)
Can be characterized.

  Cyclic TADE includes, but is not limited to, bis (aminoethyl) piperazine (DAEPIP) (condensation degree = 4) of formula II and (piperazinoethyl) ethylenediamine (PEEDA) (condensation degree = 4) of formula III.

Branched TADE is represented by the general formula (VI)
N (CH ₂ CH ₂ X) ₃ (VI)
(Wherein X may be both or individually NR ³ ₂ ; and R ³ may be both or individually H or CH ₂ CH ₂ X; and the degree of condensation is preferably 2-10, More preferably 2-6, most preferably 2-4)
Can be characterized.

  Branched TADE includes, but is not limited to, tris (aminoethyl) amine (TAEA) of formula IV (degree of condensation = 3).

  In another preferred embodiment of the invention, the amine compound selected from the group consisting of a tertiary amine derived from the condensation of ethylenediamine and a methyl substituted compound derived from linear triethylenetetraamine is a linear compound. A methyl-substituted compound derived from triethylenetetraamine.

In the context of the present invention, a methyl-substituted compound derived from linear triethylenetetraamine is one, two or more hydrogen bonded to the four amino functional groups of unsubstituted linear TETA. It is understood to mean a derivative of linear triethylenetetraamine (linear TETA) in which the atoms are substituted by the corresponding number of methyl groups (CH ₃ —). In the following, these compounds belong to the term “Me-TETA”.

（式中、ＲはＨ又はＣＨ_３のいずれかであるが、但し、少なくとも１つの置換基ＲはＣＨ_３であることを条件とする）
を特徴とし得る。 Me-TETA has the formula (VII)

(Wherein R is either H or CH ₃ provided that at least one substituent R is CH ₃ )
Can be characterized.

Me-TETA according to the present invention is shown by the examples of Scheme 1 below as compounds (2)-(13).

  Methyl-substituted compounds derived from linear triethylenetetraamine have one methyl substituent (mono-Me-TETA; compounds 2 and 3), two methyl substituents (bis-Me-TETA; compounds 4-8 ) And three methyl substituents (Tris-Me-TETA; compounds 9-13). Furthermore, the term Me-TETA also includes Me-TETA, in which all 4, 5 or 6 hydrogen atoms of unsubstituted TETA are replaced by methyl groups (not shown in Scheme 1).

  The methyl-substituted compound derived from linear triethylenetetraamine is preferably mono-Me-TETA. More particularly, methyl-substituted TETA compounds include N-2-aminoethyl-N ′-(2-N ″ -methylaminoethyl) -1,2-ethanediamine (sec-Me-TETA) and N-2. -Selected from aminoethyl-N-methyl-N'-2-aminoethyl-1,2-ethanediamine (tert-Me-TETA). sec-Me-TETA and tert-Me-TETA are described in Scheme 1 as compounds 2 and 3, respectively.

  The amine composition of the present invention is an amine selected from the group consisting of a mass of TETA of Formula I and a methyl-substituted compound derived from a tertiary amine derived from the condensation of ethylenediamine and a linear triethylenetetraamine. 85 to 98% by weight, preferably 90 to 98% by weight, more preferably 92 to 98% by weight, in particular 93 to 98% by weight of linear TETA of the formula I, based on the total weight of the compound.

  The composition of the present invention also comprises an amine compound selected from the group consisting of a tertiary amine derived from the condensation of TETA of formula I and ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. 90 to 97% by weight, more preferably 92 to 96% by weight of linear TETA of the formula I, based on the total weight, may be included.

  The composition of the present invention comprises an amine compound selected from the group consisting of a tertiary amine derived from the condensation of a TETA mass of formula I and ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. 15% by weight or less, preferably 10% by weight or less, more preferably 8% by weight or less, especially 7% by weight or less of tertiary amines and linear chains derived from the condensation of ethylenediamine, based on the total weight And an amine compound selected from the group consisting of methyl-substituted compounds derived from gaseous triethylenetetraamine. The composition of the present invention also comprises an amine compound selected from the group consisting of a tertiary amine derived from the condensation of TETA of formula I and ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. 0.01 to 10%, 0.1 to 8% or 1 to 5% by weight of tertiary amine and linear triethylene derived from the condensation of ethylenediamine, based on the total weight of An amine compound selected from the group consisting of methyl-substituted compounds derived from tetraamines may be included.

  Preferably, the amine composition is an amine compound selected from the group consisting of a tertiary amine derived from the condensation of TETA of formula I and ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. Less than 5% by weight of bis (aminoethyl) -piperazine (DAEPIP).

  More preferably, the amine composition is an amine selected from the group consisting of a tertiary amine derived from the condensation of TETA of formula I and ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. Contains less than 2% by weight of DAEPIP, particularly preferably less than 1% by weight of DAEPIP, based on the total with the weight of the compound.

  Preferably, the amine curing agent composition contains less than 5% by weight (piperazinoethyl) ethylenediamine (PEEDA), based on the total mass of the amine curing agent composition. More preferably, the amine curing agent composition contains less than 2% by weight of PEEDA, particularly preferably less than 1% by weight of PEEDA. Preferably, the amine curing agent composition is selected from the group consisting of a tertiary amine derived from the condensation of a TETA mass of Formula I and ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. Contains less than 3% by weight of tris (aminoethyl) amine (TAEA) based on the total weight of the amine compound.

  Particularly preferably, the amine curing agent composition contains less than 2% by weight of piperazine derivatives such as DAEPIP and PEEDA. In particular, the total content of piperazine derivatives is less than 1% by weight.

  The amount of water and other organic by-products is selected from the group consisting of tertiary amines derived from the condensation of TETA of Formula I and ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamine. Preferably, it is less than 5% by mass, more preferably less than 2% by mass, and most preferably less than 1% by mass, based on the total amount of the amine compound.

  The content of linear TETA of Formula I and the content of a second amine component selected from the group consisting of tertiary amines that are derivatives of ethylenediamine (TADE) and methyl-substituted TETA compounds (Me-TETA) are: It can be measured using gas chromatography.

  The amine composition according to the invention can be obtained by distillation of the reaction effluent obtained from the reaction of ethylene oxide and ammonia or by distillation of the reaction effluent obtained from the catalytic hydrogenation of ethylenediaminediacetonitrile (EDDN).

  The amine composition of the present invention can advantageously be obtained as either a top stream or a side stream in the distillation of the reaction effluent.

  In a preferred embodiment, the amine composition according to the invention can be obtained by distillation of the reaction effluent obtained from the reaction of ethylene oxide and ammonia.

  The outline of the reaction between ethylene oxide and ammonia is described in SRI-Report "CEH Product Review Ethylenamines"; SRI International, 2003, pp. 7-8 and PERP Report No. 138, "Alkyl-Amines", SRI International 03/1981, Pages 81-99 and 117 are shown.

  The reaction effluent of the reaction between ethylene oxide and ammonia is typically ammonia, water, EDA, DETA, TETA and higher boiling amines (eg, diethanolamine (DEOA), tetraethylenepentamine (TEPA), N- [ 1- (2-piperazin-1-yl-ethyl)]-ethane-1,2-diamine (C8-PIP)), piperazine and piperazine derivatives, in particular AEPIP, and aminoethylethanolamine (AEEA). The reaction effluent is usually liberated from low-boiling components such as ammonia and water, for example, by the method described in the above PERP Report.

  The remaining product is usually introduced into a separate distillation column where a low boiling mixture of EDA and piperazine is taken overhead. This tower is usually operated at 1 bar.

  The high boiling fraction is fed to a distillation column, which can usually operate at 400 mbar, with unreacted monoethanolamine (MEOA) being removed at the top of the column.

  The bottom product, which contains DETA, TETA, AEPIP and AEEA and high boiling compounds, is then fed to another column, which can usually be operated at 100 to 150 mbar, with DETA at the top of the column. Take out at. The bottom product contains TETA, AEPIP and AEEA and other high boiling amines.

  This mixture is generally fed to another distillation column, where AEPIP is removed at the top of the distillation column, usually operated at a pressure of 1 to 50 mbar. High boiling amines such as AEEA and TETA are removed at the bottom.

  In a subsequent step, the bottom product comprising AEEA, TETA and high boiling amine is fed to another distillation column which can be operated at a pressure of 1-50 mbar. AEEA is removed at the top of the column where TETA and high boiling amine are obtained as bottom product.

  In the last distillation step, the TETA composition according to the invention is separated from the high-boiling amine, usually at a pressure of 1 to 50 mbar. The TETA composition according to the invention may be removed at the top of the column or as a side stream. If a small amount of AEEA continues to be present, it is advantageous to remove the TETA composition as a side stream.

  The detailed operating conditions of each distillation column can be routinely calculated and arranged by those skilled in the art taking into account the separation efficiency of each distillation column using known vapor pressure and vapor pressure equilibrium.

  The TETA composition according to the present invention may be obtained by distillation of a commercially available diethylenetriamine residue, which contains AEEA, TETA and a high boiling amine and is obtained by reaction of ethylene oxide with ammonia and subsequent distillation. Such diethylenetriamine residue is commercially available, for example, as AMIX1000 (BASF SE). The amine composition according to the invention is obtained by feeding commercially available diethylenetriamine residue to a distillation column which can be operated at a pressure of 1 to 50 mbar. AEEA is removed at the top of the column where TETA and high boiling amine are obtained as bottom product. In the second distillation step, the TETA composition according to the invention is separated from the high-boiling amine, usually at a pressure of 1 to 50 mbar. The TETA composition according to the invention may be removed at the top of the column or as a side stream. If a small amount of AEEA continues to be present, it is advantageous to remove the TETA composition as a side stream. The detailed operating conditions of each distillation column will vary slightly depending on the exact composition of the diethylenetriamine residue and take into account the separation efficiency of each distillation column using known vapor pressure and vapor pressure equilibrium, It can be routinely calculated and arranged by those skilled in the art.

  The amine composition obtained as a side stream is usually selected from the group consisting of tertiary amines derived from the condensation of the mass of TETA of formula I and ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamine. Based on the total amount of the amine compound to be produced, it has a linear TETA content of 85 to 98% by mass, preferably 90 to 98% by mass, and more preferably 93 to 98% by mass.

  The amine composition obtained as a side stream is also selected from the group consisting of tertiary amines derived from the condensation of the mass of TETA of formula I and ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamine 90 to 97% by weight, more preferably 92 to 96% by weight of linear TETA of the formula I, based on the total weight of the amine compound to be produced. Further, the amine composition comprises an amine compound selected from the group consisting of a tertiary amine derived from the condensation of a TETA mass of Formula I and ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. 15% by mass or less, more preferably 10% by mass or less, and more preferably 8% by mass or less of tertiary amine derived from condensation of ethylenediamine (TADE), based on the total mass.

  The amine composition is also preferably selected from the group consisting of a mass of TETA of formula I and a methyl-substituted compound derived from a tertiary amine derived from the condensation of ethylenediamine and a linear triethylenetetraamine. 0.01 to 10% by weight, 0.1 to 8% by weight or 1 to 5% by weight of tertiary amine derived from the condensation of ethylenediamine, based on the total with the weight of the amine compound. .

  In another preferred embodiment, the amine composition according to the invention may be obtained by rectification or distillation of the reaction effluent obtained from the catalytic hydrogenation of ethylenediaminediacetonitrile (EDDN).

  EDDN is then obtained by reaction of EDA with formaldehyde and hydrogen cyanide (HCN). The reaction of EDA with formaldehyde and hydrogen cyanide can be performed in various variations, for example, by first reacting formaldehyde with hydrogen cyanide in the absence of EDA to form formaldehyde cyanohydrin (FACH) intermediate. The reaction mixture resulting from the hydrogenation of EDDN is disclosed in the examples of WO-A-20008104553. These reaction mixtures generally contain linear TETA, aminoethylpiperazine (AEPIP) and C4 components such as diethylenetriamine (DETA) and piperazine (PIP) and a solvent such as THF. The content of TETA in the hydrogenation effluent according to the examples of WO-A-20008104553 is generally between 30% and 85% by weight.

  In a preferred embodiment, the amine composition according to the invention is obtained by releasing the reaction effluent obtained from the solvent according to the examples of WO-A-20008104553. Solvents, particularly THF, can generally be removed by expanding the effluent to normal pressure and then feeding the effluent to a distillation column operating at normal pressure. THF is generally removed at the top of the column. If an additional solvent is used, an additional distillation step may be required.

  The amine fraction obtained as a bottom product and substantially free of solvent is generally fed to a separate distillation step.

  This distillation step is preferably operated at 100 to 500 mbar, and low-boiling byproducts and low-boiling components such as DETA are removed at the top of the column.

  The mixture containing AEPIP and TETA and other high boiling amines are usually fed to another distillation column, preferably operated at 1-50 mbar, where AEPIP is usually removed at the top of the column, but TETA And high boiling amines are removed at the bottom.

  The bottom product from the previous distillation stage is usually further distilled in a subsequent distillation column, which is also operated in the range of 1-50 mbar. The TETA composition according to the invention is usually removed at the top of the column or as a side stream. High boiling amines are generally removed at the bottom of the column.

  The detailed operating conditions of each distillation column can be routinely calculated and arranged by those skilled in the art, taking into account the separation efficiency of each distillation column using known vapor pressure and vapor pressure equilibrium.

  The amine composition obtained as a side stream is generally selected from the group consisting of tertiary amines derived from the condensation of the mass of TETA of formula I and ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamine. Based on the total amount of the amine compound to be produced, it has a linear TETA content of 85 to 98% by mass, preferably 90 to 98% by mass, and more preferably 93 to 98% by mass.

  The amine composition obtained as a side stream is also selected from the group consisting of tertiary amines derived from the condensation of the mass of TETA of formula I and ethylenediamine and methyl-substituted compounds derived from linear triethylenetetraamine 90 to 97% by weight, more preferably 92 to 96% by weight of linear TETA of the formula I, based on the total weight of the amine compound to be produced.

  Furthermore, the amine composition is generally 15% by weight or less of methyl-substituted TETA compound (Me-TETA), more preferably 10% by weight or less of methyl-substituted TETA compound (Me-TETA), most preferably 8% by weight or less of methyl-substituted TETA compound. Contains a TETA compound (Me-TETA).

  The amine composition also has a mass of amine compound selected from the group consisting of a tertiary amine derived from the condensation of TETA of formula I and a condensation of ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. 0.01 to 10% by weight derived from linear triethylenetetraamine, 0.01 to 10% by weight, 0.1 to 8% by weight or 1 to 5% by weight, based on the total .1-8 mass% or 1-5 mass% of methyl-substituted compounds may be included.

  Unexpectedly, the cured epoxy resin in which the amine composition of the present invention is used as an amine curing agent has been found to have a significantly higher glass transition temperature compared to an epoxy resin obtained from “commercially available TETA”. did. Furthermore, at the same time as the curing time is shortened, the pot life of the curable composition containing the amine composition according to the present invention is prolonged. Moreover, the characteristic mechanical properties resulting from “commercially available TETA” are maintained.

  However, the improvement in properties in the epoxy system is not limited to the use of the amine composition of the present invention as an amine curing agent, but by formula I above 98% by weight as an amine curing agent for epoxy applications. It has also been discovered that it may be extended to the use of “pure” or “purified TETA” with a linear TETA content. Such “pure” or “purified TETA” may be obtained according to the method described in US-A-2006 / 0041170. “Pure” or “purified TETA” may also be used for the amine composition according to the present invention, either by further purification of the amine composition according to the present invention, or in the same manner as described for the preparation of the amine composition of the present invention. It may be obtained by adapting the distillation conditions and sequence described above for production, for example by increasing the number of theoretical plates in the final distillation stage.

  The invention therefore also relates to the use of triethylenetetraamines of the formula I having a purity of 98% by weight or more and / or amine compositions according to the invention as amine curing agents.

  In principle, the amine composition according to the present invention may be used as a single amine curing agent or optionally mixed with other amine curing agents, for example as follows to form an amine curing agent composition. Good.

  Similarly, “pure” or “purified TETA” having a linear TETA content of greater than 98% by weight may be used as the sole amine curing agent or optionally: Such amine curing agents may be mixed to form an amine curing agent composition.

  An advantageous effect is to use an amine composition according to the invention having a TETA according to formula I (“pure” or “purified TETA”) of greater than 98% by weight or a high content of linear TETA of formula I The advantageous effect achieved by the method becomes less pronounced when diluted with other curing agents compared to the prior art “commercially available TETA”, but continues to exist.

  Accordingly, the present invention provides an amine curing agent selected from the group consisting of the amine composition of claim 1 and a triethylenetetraamine of formula I having a purity of 98% by weight or more, and one or more other amines It also relates to an amine curing agent composition comprising a curing agent.

  The other amine curing agent is an amine compound having at least one, preferably two or more reactive amine hydrogen atoms in the molecule capable of reacting with the epoxy functional group.

Preferably, other amine curing agents that can be used in combination with an amine curing agent selected from the group consisting of triethylenetetraamine of formula I having a purity of 98% by weight or more and an amine composition according to the present invention are: Is:
Heterocyclic amines such as piperazine, N-aminoethylpiperazine; cycloaliphatic amines such as isophoronediamine, 1,2- (1,3; 1,4) -diaminocyclohexane, cyclohexylaminopropylamine (CHAPA), tri Cyclododecanediamine (TCD);
Aromatic amines such as isomeric phenylene diamines such as o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, isomer tolylene diamines such as 2,4-diaminotoluene and / or 2,6 diaminotoluene, Isomeraminonaphthalene, such as 1,5-diaminonaphthalene, bis (4-aminophenyl) methane (MDA), isomer xylenediamine, such as meta-xylenediamine (MXDA), bis (4-amino-3-methyl-phenyl) ) Methane and bis (4-amino-3,5-dimethylphenyl) -methane;
Substituted aliphatic amines such as ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4 (2,4,4) -trimethylhexamethylenediamine, 2-methylpenta-methylenediamine;
Ether amines such as 1,7-diamino-4-oxaheptane, 1,10-diamino-4,7-dioxydecane, 1,14-diamino-4,7,10-trioxatetradecane, 1,20-diamino- 4,17-dioxyeicosane, especially 1,12-diamino-4,9-dioxadodecane;
Ether diamines based on propoxylated diols, triols and polyols;
Polyalkylene polyamines such as dipropylene triamine, tripropylene tetraamine;
As well as high molecular weight amines containing free amine hydrogen or addition or condensation products, especially Mannich bases.

  Most preferably, the other amine curing agent is isophorone diamine, 1,2- (1,3; 1,4) -diaminocyclohexane, cyclohexylaminopropylamine (CHAPA), tricyclododecanediamine (TCD), xylylenediamine , Ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4 (2,4,4) -trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1,7-diamino-4-oxaheptane, 1,10- Diamino-4,7-dioxydecane, 1,14-diamino-4,7,10-trioxatetradecane, 1,20-diamino-4,17-dioxyeicosane and 1,12-diamino-4,9-di Oxadodecane.

  In a preferred embodiment, an amine curing agent selected from the group consisting of an amine composition according to the invention and a triethylenetetraamine of formula I having a purity of 98% by weight or more (present in an amine curing agent composition according to the invention). ) Content is 25% by mass or more, preferably 50% by mass or more, more preferably 75% by mass or more, and particularly 90% by mass or more, based on the mass of the amine curing agent composition.

  Within the context of the present invention, the mass of the amine curing agent composition is the group consisting of the amine composition according to the present invention and the triethylene-tetraamine of formula I having a purity of 98% by weight or more, used in the production of epoxy resins. Is the sum of the masses of the amine curing agent selected from as well as the other amine curing agents defined above.

  In another preferred embodiment, an amine curing agent selected from the group consisting of an amine composition according to the invention and a triethylenetetraamine of the formula I having a purity of 98% by weight or more (in the amine curing agent composition according to the invention). Is present) is 25 to 99% by mass, preferably 50 to 95% by mass, and more preferably 75 to 90% by mass, based on the mass of the amine curing agent composition.

  Mixing an amine composition according to the present invention or an amine composition with a triethylenetetraamine of formula I having a purity of 98% by weight or more, or an amine curing agent composition according to the present invention and an epoxy resin, yields a curable composition. It is done.

  Accordingly, the present invention also provides one or more epoxy resins and the amine curing agent composition according to any one of claims 4 to 6 or the amine composition according to claim 1 and a purity of 98% by mass or more. A curable composition comprising at least one amine curing agent selected from the group consisting of triethylenetetraamine of formula I having a third derived from the condensation of triethylenetetraamine of formula I to ethylenediamine It also relates to a curable composition wherein the mass ratio of the amine compound selected from the group consisting of a methyl-substituted compound derived from a primary amine and a linear triethylenetetraamine is 85:15 or greater.

  In a preferred embodiment, the curable composition according to the invention comprises the amine curing agent composition according to the invention as a triethylenetetraamine of formula I having a purity of 98% by weight or more or as the sole amine curing agent.

  In a further preferred embodiment, the curable composition according to the invention comprises an amine curing agent composition according to the invention.

  In addition to the amine curing agent and the amine curing agent composition according to the present invention, the curable composition also includes one or more epoxy resins.

  Epoxy resins are an important class of polymeric materials characterized by the presence of two or more epoxy rings.

  Epoxy resins suitable for a considerable number of curable compositions are described in the handbook "Epoxidverbindungen und Epoxidharze" by AM Paquin, Springer Verlag Berlin, 1958, Chapter IV; "Handbook of Epoxy Resins" by Lee & Neville, 1967. Chapter 2; Ullmann Industrial Chemistry Encyclopedia, Wiley VCH Verlag GmbH, Electronic Edition 2005, Chapter "Epoxy Resins" and CA May's "Epoxy Resins, Chemistry and Technology", Marcel Dekker Inc, New York, 1988, Chapter 2 It was found.

  Commercially important epoxy resins are produced in particular by dehydrohalogenation after a coupling reaction between a compound containing at least two active hydrogen atoms and epichlorohydrin. Compounds containing at least two active hydrogen atoms include polyphenol compounds, monoamines and diamines, aminophenols, heterocyclic imides and amides, aliphatic diols and polyols, and dimer fatty acids.

  Epoxy resins derived from epichlorohydrin are called glycidyl-based resins. Alternatively, epoxy resins based on epoxidized aliphatic or alicyclic dienes are produced by direct epoxidation of olefins with peracids.

  The epoxy resin also includes a reaction product of epichlorohydrin and bisphenol A. These products are commonly referred to as DGEBA (diglycidyl ether of bisphenol A).

When the degree of polymerization, n is very low (n≈0.2), DGEBA is usually called a liquid epoxy resin (LER), but the degree of polymerization, i.e., the n value ranges from 2 to about 35. High molecular weight (Mw) epoxy resins based on DGEBA, characterized by repeating units containing secondary hydroxyl groups, generally mean solid epoxy resins (SER).

  Epoxy resins also include so-called epoxy novolac resins. The polyfunctionality of these resins provides a high crosslink density, which provides improved heat and chemical resistance to bisphenol A epoxide. Epoxy novolac is a polyfunctional epoxide based on phenol formaldehyde novolac. Both epoxy phenol novolac resin (EPN) and epoxy cresol novolac resin (ECN) have achieved commercial importance. The former is made by epoxidation of a phenol-formaldehyde condensate (novolak) obtained from acid-catalyzed condensation of phenol and formaldehyde.

  Epoxy compounds that can be used for the curable compositions and the cured epoxy resins derived therefrom are those resins mentioned above or described in the literature, especially those having an average of two or more epoxy groups per molecule. Which are derived from monovalent and / or polyvalent and / or polynuclear phenols, in particular bisphenols and novolacs such as bisphenol A and bisphenol-F-diglycidyl ether.

  The epoxy resin is preferably bisphenol A bisglycidyl ether (DGEBA), bisphenol F bisglycidyl ether, bisphenol S bisglycidyl ether (DGEBS), tetraglycidylmethylenedianiline (TGMDA), epoxy novolac (epichlorohydrin and phenol resin ( Reaction product with novolak), and alicyclic epoxy resins, for example, epoxy resins selected from the group of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and diglycidyl hexahydrophthalate.

  Two or more epoxy resin compositions may be used as well.

  The curable composition may contain further additives such as those commonly found in epoxy resin technology. It should be noted that, for example, gravel, sand, silicate, graphite, silica, talc, mica, etc. are often used in the particle size distribution of this area. Suitable additives include, for example, antioxidants, UV absorbers / light stabilizers, metal deactivators, antistatic agents, reinforcing materials, fillers, biocides, lubricants, emulsifiers, colorants, pigments, flow Contains additives, mold release agents, catalysts or accelerators, flow control agents, fluorescent whitening agents, flame retardants, anti-dripping agents and swelling agents.

  An overview of additives, adjuvants and curing agents that can be used in the curable composition is given in Ullmann Industrial Chemistry Encyclopedia, Wiley VCH Verlag GmbH, Electronic Edition 2005. Chapter "Epoxy Resins", CA May by "Epoxy Resins, Chemistry and Technology ", Marcel Dekker Inc, New York, 1988, Chapter 3, and" Epoxy Resins, Curing Agents, Compounds and Modifiers "by EW Flick, Noyes Publications, Park Ridge, 1987.

  The weight ratio of the epoxy resin and amine curing agent composition and additives and adjuvants may be varied to achieve and purify the final cured epoxy resin of the desired applicability and is routinely by those skilled in the art. For example, the amine curing agent has a molar ratio of epoxy groups of the epoxy resin to active hydrogen atoms of the amine curing agent in the range of 0.7 to 1.1, preferably 0.8 to 1.0. May be included in the composition.

  A curable composition according to the invention is an amine hardener composition according to any one of claims 4 to 6 or an amine composition according to claim 1 and a formula I tri having a purity of 98% by weight or more. Regardless of whether it contains at least one amine curing agent selected from the group consisting of ethylenetetraamine, the curable composition according to the present invention is derived from the condensation of linear triethylenetetraamine of formula I to ethylenediamine. The mass ratio of the amine compound selected from the group consisting of a tertiary amine and a methyl-substituted compound derived from a linear triethylenetetraamine is 85:15 or more, preferably 92: 8 or more, more preferably 93 : 7 or more. A mass ratio of an amine compound selected from the group consisting of a tertiary amine derived from the condensation of linear triethylenetetraamine of formula I with ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine is also included. , Preferably 85:15 to 99: 1, more preferably 90:10 to 98: 2, especially 92: 8 to 97: 3.

  In a preferred embodiment, an amine selected from the group consisting of a tertiary amine derived from the condensation of linear triethylenetetraamine of formula I with ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. The mass ratio of the compound is 98: 2 or more. Such curable compositions are obtained by using “purified TETA” as the sole amine curing agent or by mixing “purified TETA” with other amine curing agents.

  The invention also provides an amine curing agent composition according to any one of claims 4 to 6 or an amine composition according to claim 1 and a triethylenetetraamine of the formula I having a purity of 98% by weight or more. The method for producing a curable composition according to claim 7, wherein at least one amine curing agent selected from the group consisting of and at least one epoxy resin is mixed.

  Mixing processes of amine curing agents and one or more epoxy resins are well known to those skilled in the art. In general, mixing is performed by a mixing device. The mixing device may be of any type capable of producing a highly homogeneous mixture of epoxy resin and amine curing agent composition (and any components that are also mixed at this time). Various types of mechanical mixers and stirrers may be used. Two preferred types of mixers are static mixers and collision mixers. Mixing can be performed batchwise, semi-continuously or continuously.

  Since the epoxy resin and the amine curing agent are generally heated separately above room temperature before mixing them together, the curable composition is formed just prior to mixing them. The epoxy resin and amine curing agent may each be heated to a temperature of up to 25 ° C., preferably up to 50 ° C., more preferably up to 80 ° C. or higher before mixing.

  Other additives, such as those described above, may be mixed with the amine curing agent or epoxy resin prior to mixing the amine curing agent with the epoxy resin. It is also possible to mix the amine curing agent and the epoxy resin simultaneously with or after mixing the other additive and the curable composition.

  After mixing, the curable composition thus obtained is typically applied to the surface by transferring it to a suitable mold (structural use) or by spraying the curable composition onto the surface, for example. (Coating use) A cured epoxy resin is obtained.

  Therefore, the present invention further relates to a method for producing a cured epoxy resin by transferring the curable composition according to the present invention to a mold or applying the curable composition to a surface.

  Suitable process techniques are known to those skilled in the art and can be found, for example, in B. Ellis, “Chemistry and Technology of Epoxy Resins”, Kluwer Academic Publishers (Februar 1993).

  Generally, the cured epoxy resin is obtained by curing the curable composition after mixing and transferring it to a mold, or after application to the surface. During curing, the amine curing agent reacts with the epoxy resin present in the curable composition.

  In a preferred embodiment of the invention, the mixing and transfer of the curable composition is performed in one stage, for example by reaction injection molding. The epoxy resin and amine curing agent composition (and any other ingredients that are mixed at the same time) are pumped under pressure to a mixing head where they are rapidly mixed together. The operation pressure in the high-pressure machine is typically in the range of 7 to 14 MPa, although operation at a low pressure is possible. The resulting curable composition then provides further additional mixing, preferably through a static mixing device, which is then transferred to the mold cavity.

  In another embodiment, the curable composition is preferably prepared by mixing as described above and then applying to the surface, in particular by spraying the curable composition into a mold.

  Typically, the mold is a metal mold, but may be a ceramic or polymer composite provided that the mold can withstand the pressure and temperature conditions of the molding process. Typically, the mold includes one or more inlets into which the reaction mixture is introduced. The mold may include a vent that allows gas to escape so that the reaction mixture is injected. Typically, the mold is held in a press or other device, which can open and close the mold, and apply pressure to the mold to keep the mold closed during the filling and curing operations. Can be maintained. The mold or press is equipped with a means by which heat can be applied.

  In a preferred embodiment of the invention, the curable composition is applied to a reinforcement and cured in the presence of the reinforcement to form a reinforced composite.

  The reinforcement may be blended with an epoxy resin or an amine curing agent (or both), for example, to obtain a curable composition prior to mixing. Alternatively, the reinforcement is added to the curable composition at the same time as the epoxy resin and amine curing agent are mixed, or after mixing but before introducing the curable composition into the mold or The curable composition may be added prior to application to the surface by spraying the curable composition onto a mold.

  Suitable reinforcements are fiber materials or non-fiber materials. Examples of the fiber material include glass fiber, quartz fiber, polyamide resin fiber, boron fiber, carbon fiber, and gel spun polyethylene fiber.

  Non-fiber reinforcements include glass flakes, aramid particles, carbon black, carbon nanotubes, various clays such as montmorillonite, and other mineral fillers such as wollastonite, talc, mica, titanium dioxide, barium sulfate, Examples include calcium carbonate, calcium silicate, flint powder, carborundum, molybdenum silicate, and sand.

  Examples of the non-fiber reinforcing material include conductive materials such as aluminum and copper, carbon black, carbon nanotube, carbon fiber, and graphite.

  The reinforcement may be in a plurality of forms, for example, fiber preforms, continuous fiber rovings, cut fibers or chopped fibers.

  Preferably, the reinforcement is in the form of a fiber preform, i.e. in the form of a fiber web or mat. The fiber preform may be made of a continuous filament mat, where the continuous filaments are woven together, intertwined or intimately bonded, and the size and shape of the finished composite article (or part thereof requiring reinforcement). A preform close to is formed. Alternatively, short fibers may be formed in the preform through entanglement or adhesive methods. Continuous or short fiber mats may be stacked and pressed together to form various thickness preforms, if desired. The fiber preform is typically placed in a mold prior to introducing the curable composition. The curable composition may be introduced into a closed mold containing the preform by injecting the curable composition into a mold, wherein the curable composition is interposed between the fibers in the preform. And then cured to form a cured epoxy resin. A reaction injection molding and / or resin transfer molding apparatus is suitable for such a case. Alternatively, the preform may be deposited in an open mold and the curable composition may be sprayed over and into the preform. After the mold is filled in this manner, the mold is closed and the curable composition is cured. In either approach, the mold and preform are preferably heated prior to contacting them with the curable composition.

  Short fibers can be used instead of or in addition to fiber preforms. Short fibers (up to about 20 cm long, preferably up to 5 cm long, more preferably up to about 2 cm long) are blended with the curable composition and injected into the mold together with the curable composition. It's okay. Such short fibers may be blended with, for example, an epoxy resin or an amine curing agent (or both) prior to mixing to obtain a curable composition. Alternatively, short fibers may be added to the curable composition at the same time as the epoxy resin and amine curing agent are mixed, or after introducing the curable composition into the mold. Short fibers may be sprayed into the mold. In such cases, the curable composition may also be sprayed into the mold at the same time or after the short fibers are sprayed into the mold. When the fiber and curable composition are sprayed simultaneously, they may be mixed together before spraying. Alternatively, the fiber and curable composition may be sprayed into the mold separately but simultaneously.

  Various manufacturing processes for reinforced composites known to those skilled in the art may be used, for example, RTM, VARTM, RFI, and SCRIMP. In these processes, the reinforcement is inserted into the mold cavity in the form of a woven or matt fiber preform. The mold is closed and the resin is injected into the mold. The resin is cured in the mold to form a composite and then removed from the mold.

  Reinforced composites may also be produced by a pultrusion process.

  The pultrusion process uses continuous fibers oriented parallel to each other in the direction of extrusion. The pultrusion process is performed in the same way as the mold process, the main difference being that the high temperature reaction mixture is delivered into the resin bath rather than into the mold. The resin bath is a reservoir filled with a curable resin through which continuous resin is drawn. As soon as the fibers are wetted with the high temperature reaction mixture, they are pulled through one or more dies, where the fibers are consolidated and formed into the desired cross-sectional shape.

The amine curing agent composition of the present invention comprising a high content of linear TETA has a higher glass transition temperature compared to commercially available prior art TETA mixtures containing linear TETA, DAEPIP, PEEDA and TAEA. it has been found that results in a cured epoxy resin having a T _g. A high Tg _{broadens the} temperature range in which the cured epoxy resin can be applied. Mechanical properties of the epoxy resin is immediately drastically decreases when more than T _g.

  Furthermore, the curable composition according to the invention may be cured at high temperatures, in particular according to the method according to US-A-2008 / 0197526, which makes it possible to manufacture reinforced composites, in particular for parts in the automotive and aerospace field. to enable.

To the content of catalytically active tertiary amine is reduced as compared with "commercial TETA", increase a T _g does not involve an increase in the curing time of the curable composition as predicted. It has been found that the amine curing agent composition according to the present invention significantly shortens the curing time compared to the prior art “commercial TETA”. Reduced cure times result in shorter cycle times, which is generally advantageous for the production of formed parts such as carbon fiber reinforced composites (CFK) in parts of the automotive industry where high throughput is desirable.

Increase T _g of even without deterioration of pot life, therefore, the use of amine curing agent composition for use in the curable compositions according to the invention provides excellent processability and high processing stability. Increase T _g of do not adversely affect the mechanical properties characterized by "commercial TETA" of the prior art.

  Amine curing agents and cured resins used in the process of the present invention for the production of curable compositions are automotive parts and parts, wind turbines, filament wound pipes, printed circuits, aircraft / aerospace industry, weapons, sports / Particularly suitable for applications in the fields of recreation, fiber composites, construction and adhesives.

  Cured epoxy resins based on curable compositions based on epoxy resins made from curable compositions containing LER (liquid epoxy resins) usually have excellent electrical properties, chemical resistance, heat resistance and adhesion Have sex. Cured LER generally provides good strength and hardness.

  Cured epoxy resins based on curable compositions containing DGEBA-based LER are widely used in the paint industry. Longer backbones generally provide additional spacing between crosslinks when cross-linked through terminal epoxy groups, resulting in improved flexibility and toughness. In addition, the resin can be cured through multiple hydroxyl groups along the backbone with a cross-linking agent such as phenol formaldehyde resole or isocyanate to create different networks and performance.

  Curable epoxy resins based on curable compositions containing novolak resins usually have a high crosslink density, which provides improved heat and chemical resistance to bisphenol A epoxide. Therefore, these resins are often used for high temperature applications such as aerospace composites. Filament wound pipes and storage tanks, pump liners and other chemical process equipment, corrosion resistant coatings are other typical applications that utilize high chemical resistance.

  The amine composition of the invention and / or “pure” or “purified” TETA may also be advantageously used for the production of reactive polyamide resins.

  Accordingly, the present invention also provides a reactive polyamide resin obtained from the reaction of the amine composition according to claim 1 and / or a triethylenetetraamine of formula I having a purity of 98% by weight or more and a dimer fatty acid. It mentions.

  Reactive polyamides are low molecular weight (1,000-2,000 g / mol) products obtained from the condensation of dimer fatty acids with one of higher ethyleneamines (diethylenetriamine, triethylenetetraamine, etc.). Reactive polyamides are used almost exclusively as curing agents in two-component epoxy systems, thermosetting adhesive systems, electronic component sealing and floor grout and trowel coating for industrial and marine repair coatings. These amine groups provide reactive sites for cross-linking interactions with epoxy resin molecules.

  Reactive polyamides are usually produced by a batch condensation process. The reactants (dimeric fatty acids and amine compositions according to the invention and / or “pure” or “purified” TETA) are generally heated to 150-250 ° C. By-product water is usually removed by vacuum distillation. The resulting polyamide is then removed and converted to a form suitable for shipping.

  Dimer fatty acids are most often obtained by polymerization of monocarboxylic acids containing ethylenic unsaturates. Monocarboxylic unsaturated acids generally contain about 16 to 26 carbon atoms and include, for example, oleic acid, linoleic acid, eleostearic acid and similar single or double unsaturated acids. In order to obtain the preferred dimer acid, 2 moles of unsaturated monocarboxylic acid react, i.e. dimerize. Oleic acid, linoleic acid and linolenic acid are generally used as unsaturated fatty acids. The dimer acid obtained in this way can then be hydrogenated.

  Reactive polyamide resins obtained from the reaction of dimer fatty acids with amine compositions according to the invention and / or “pure” or “purified” TETA are compared to reactive polyamide resins obtained from conventional TETA. And high functionality. High functionality improves the mechanical properties of the resulting system. Surprisingly, the reactive polyamide resin obtained from the reaction of the dimer fatty acid with the amine composition according to the invention and / or “pure” or “purified” TETA is a carboxylic acid group of the dimer fatty acid. It was found to have a high content of imidazoline ring formed as a by-product in the reaction with TETA of formula I. It is conceivable that imidazoline ring formation occurs simultaneously with improved adhesion between films.

  The invention is illustrated by the following examples.

Examples Gas chromatography (column: Rtx-5 amine, 30 m, 0.32 mm, 1.50 μm; gas chromatography: HP5890 equipped with autosampler; injection temperature: 250 ° C .; detection temperature : 300 ° C; temperature program: 60 ° C-5 minutes constant temperature-15 ° C / min-280 ° C; internal standard: diethylene glycol dimethyl ether (DEGDME)).

Example 1:
A reaction eluate composed of the following composition was obtained by reaction of monoethanolamine (MEOA) with ammonia followed by distillation:
Low boiling point amine: 4% by mass (for example, AEPIP, DETA, EDA, methyl-EDA, piperazine)
AEEA: 23% by mass
TETA of formula I: 24% by weight
High boiling point amine: 49% by mass (for example, diethanolamine (DEOA), tetraethylenepentamine (TEPA), N- [1- (2-piperazin-1-yl-ethyl)]-ethane-1,2-diamine (C8 -PIP)).

  This eluate was fed to the middle part of the distillation column operated at 50 mbar and 154 ° C. head temperature. The fraction of AEEA and low boiling amine was removed at the top of the column and a mixture of high boiling amine and TETA was removed at the bottom of the column. The bottom product of the first reaction column was fed to the middle of a second distillation column operated at 30 mbar and a top temperature of 164 ° C. The amine composition was withdrawn as a top stream.

The composition of the amine composition was as follows:
Linear TETA of formula I: 95.8% by weight
AEEA: 1.7% by mass
Tertiary amine derived from EDA (TADE): 3.3% by weight

Example 2:
100 g of Epilox® A18-00 epoxy resin (Epilox® A18-00 is a low viscosity and solventless bisphenol A epoxy resin from LEUNA-Harze GmbH) obtained in Example 1. 14 g of an amine curing agent composition comprising the amine composition was mixed.

The following tests were performed with the resin mixture.
a) Measurement of initiation temperature of crosslinking reaction by DSC (differential scanning calorimetry) The initiation temperature of crosslinking reaction was 62 ° C.

b) Measurement of pot life 100 g of the resin mixture was placed in a cardboard beaker at room temperature. Measure the temperature of the sample as a function of time using a data logger.

  The latency of the resin mixture with pure linear TETA as curing agent was longer at the start than that of the comparative example (see below), but then the mixture was cured very quickly .

c) Measurement of gel point by rheological test The activity of the resin system was determined by monitoring the progress of the reaction using a rheometer. This involves plotting a variable known as storage modulus against a variable known as loss modulus. The point where the two curves intersect means the gel point. The corresponding reaction time is known as the gel time and is a measure of the reactivity of the epoxy resin system.

  A gel time of 8.3 minutes was found.

  d) Measure the glass transition temperature of the cured epoxy resin using DSC. The cured epoxy resin has good mechanical properties when the use temperature is lower than the glass transition temperature. Above the glass transition temperature, the mechanical properties of the epoxy resin deteriorate dramatically.

  The glass transition temperature was found to be 136 ° C.

Example 3 (comparative example)
Epilox® A18-00 epoxy resin 100 g and Akzo “commercially available TETA” 14 g were mixed, which was about 69% by weight linear triethylenetetraamine, about 6% by weight TAEA, Contains about 15% by weight DAEPIP and about 10% by weight PEEDA.

The above test was performed with a resin mixture.
a) The starting temperature of the crosslinking reaction was 58 ° C.
b) The waiting time of the comparative resin mixture was shorter than the waiting time of the resin mixture of the examples of the present invention.
c) The gel time was found to be 9.3 minutes.
d) Glass transition temperature The _{T g} was found to be 115 ° C..

  The glass transition temperature of the epoxy resin cured with the amine curing agent composition comprising the amine composition according to the present invention was about 21 ° C., which was higher than the glass transition temperature of the comparative resin. Thus, the resins of the examples of the present invention can be used at significantly higher temperatures. The higher initiation temperature of the crosslinking reaction and the longer waiting time of the cured epoxy resin of the present invention is technically advantageous from a processing point of view and provides additional safety, as the autocatalytic curing reaction does not begin until late To do.

  The cure time (gel time) of the epoxy resin is reduced by about 15% compared to the comparative example by the use of pure linear TETA. This is achieved by shortening the cycle time and has a beneficial effect on the investment costs, for example in the production of large moldings such as small carbon fiber reinforced plastic (CRP) parts in the automotive sector.

Example 4:
Raney cobalt (4.7 g) and tetrahydrofuran (THF) (40 g) were charged into a 300 ml autoclave. The autoclave was heated to 120 ° C. and a hydrogen pressure of 100 bar was applied. During 120 minutes, 16 g of ethylenediaminediacetonitrile (EDDN), 0.5 g of ethylenediaminomonoacetonitrile (EDMN), 1.3 g of biscyanomethylimidazolidine (BCMI) and 100 g of THF were fed to the autoclave. The reaction mixture was stirred for a further 60 minutes at 120 ° C. and 100 bar hydrogen pressure.

  The reaction mixture was narrowed under water jet vacuum and the remaining residue was rectified at 20 mbar. The fraction withdrawn at the top temperature of 150 ° C. had the following composition: 96.5% by weight linear TETA, 3.1% by weight Me-TETA and 0.4% by weight etc. The organic component of.

Example 5:
100 grams of Epilox® A18-00 epoxy resin (Epilox® A18-00 is a low viscosity and solventless bisphenol A epoxy resin from LEUNA-Harze GmbH) a) in Example 1 The resulting amine composition, b) the amine composition obtained in Example 4, or c) about 69% by weight linear triethylenetetraamine, about 6% by weight TAEA, about 15% by weight DAEPIP, and 14 g of an amine hardener composition consisting of a commercial TETA mixture obtained from Huntsman, containing about 10% by weight of PEEDA was mixed.

a) Initial viscosity:
A mixture of Epilox and TETA composition was heated to 23 ° C. and poured into a cardboard beaker, and the initial viscosity of the mixture was measured. The following values were measured:

a) In the case of the TETA composition according to Example 1, 2625 mPas;
b) In the case of the TETA composition according to Example 3, 2485 mPas;
c) 2903 mPas for the commercially available TETA composition.

b) The viscosity increases at 23 ° C .:
The viscosity progression of the initial mixture obtained according to Example 5a) continued. The time at which the maximum viscosity was obtained was as follows:

a) 61 minutes for the TETA composition according to Example 1;
b) 63 minutes for the TETA composition according to Example 3;
c) 57 minutes for commercially available TETA compositions.

  The linear TETA composition according to the present invention (a) and (b) has a lower initial viscosity than the commercially available TETA composition. This is advantageous for filling large assemblies or construction parts or for assembly. The time until maximum viscosity is achieved is proportional to the latency of the system. Longer waiting times are technically advantageous from a processing point of view and provide additional safety, since the autocatalytic curing reaction does not begin until late.

c) Measurement of the start time of the crosslinking reaction by DSC (differential scanning calorimetry) The starting temperature of the crosslinking reaction was as follows:

a) 63 ° C. for the TETA composition according to Example 1;
b) in the case of the TETA composition according to Example 3, 64 ° C .;
c) 61 ° C. for commercially available TETA compositions.

  As mentioned above, a higher start time of the crosslinking reaction is technically advantageous from a processing point of view and provides additional safety.

d) Measurement of gel point by rheological test The activity of the resin system was determined by monitoring the progress of the reaction using a rheometer. This involves plotting a variable known as storage modulus against a variable known as loss modulus. The point where the two curves intersect means the gel point. The corresponding reaction time is known as the gel time and is a measure of the reactivity of the epoxy resin system.

The following gel times were measured:
a) 8.6 minutes for the TETA composition according to Example 1;
b) 8.3 minutes for the TETA composition according to Example 3;
c) 9.3 minutes for commercially available TETA compositions.

  The curing time (gel time) of the epoxy resin using the linear TETA composition according to the present invention is reduced by about 8-10% over the comparative example by the use of pure linear TETA. This is achieved by shortening the cycle time and has a beneficial effect on the investment costs, for example in the production of large moldings such as small carbon fiber reinforced plastic (CRP) parts in the automotive sector.

  e) Measure the glass transition temperature of the cured epoxy resin using DSC. The cured epoxy resin has good mechanical properties when the use temperature is lower than the glass transition temperature. Above the glass transition temperature, the mechanical properties of the epoxy resin deteriorate dramatically.

The glass transition temperature was found to be as follows:
a) In the case of the TETA composition according to Example 1, 149 ° C .;
b) for the TETA composition according to Example 3, 147 ° C .;
c) 124 ° C. for commercially available TETA compositions.

  The glass transition temperature of the epoxy resin cured with the amine curing agent composition containing the amine composition according to the present invention was (a) and (b) which was about 20 ° C. higher than the temperature of the resin of the comparative example.

  Thus, the resins of the examples of the present invention can be used at significantly higher temperatures.

Claims (15)

An amine composition having the formula I

And based on the sum of the mass of the TETA and the mass of the amine compound selected from the group consisting of a tertiary amine derived from the condensation of ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine. From 85% to 98% by weight of a triethylenetetraamine of the formula I and up to 15% by weight of a tertiary amine derived from the condensation of ethylenediamine and a methyl-substituted compound derived from linear triethylenetetraamine An amine composition comprising one or more amine compounds selected from the group consisting of:   The process for producing an amine composition according to claim 1, wherein the reaction effluent obtained from the reaction between ethylene oxide and ammonia is distilled or the reaction effluent obtained from catalytic hydrogenation of ethylenediaminediacetonitrile is distilled.   Use of a triethylenetetraamine of the formula I having a purity of 98% by weight or more and / or the amine composition according to claim 1 as an amine curing agent.   An amine curing agent comprising an amine curing agent selected from the group consisting of the amine composition of claim 1 and a triethylenetetraamine of formula I having a purity of 98% by weight or more, and one or more other amine curing agents. Agent composition.   The amine curing agent content selected from the group consisting of the amine composition of claim 1 and a triethylenetetraamine of formula I having a purity of 98% by weight or more based on the weight of the amine curing agent composition. The amine curing agent composition according to claim 4, which is 25% by mass or more.   The amine curing agent content selected from the group consisting of the amine composition of claim 1 and a triethylenetetraamine of formula I having a purity of 98% by weight or more based on the weight of the amine curing agent composition. The amine hardening | curing agent composition of Claim 5 which is the range of 25 mass%-99 mass% or more.   7. One or more epoxy resins and the amine curing agent composition according to any one of claims 4 to 6 or the amine composition according to claim 1 and a triethylene of formula I having a purity of 98% by weight or more. A curable composition comprising at least one amine curing agent selected from the group consisting of tetraamines, wherein the tertiary amines derived from the condensation of triethylenetetraamine of formula I with ethylenediamine and linear triamines. The curable composition whose mass ratio of the amine compound selected from the group which consists of a methyl substituted compound induced | guided | derived from ethylene tetraamine is 85:15 or more.   A selected from the group consisting of the amine curing agent composition according to any one of claims 4 to 6 or the amine composition according to claim 1 and a triethylenetetraamine of the formula I having a purity of 98% by weight or more. The manufacturing method of the curable composition of Claim 7 by mixing the at least 1 sort (s) of amine hardening | curing agent and at least 1 sort (s) of epoxy resin.   The manufacturing method of the cured epoxy resin by transferring the curable composition of Claim 7 to a type | mold, or apply | coating the said curable composition to the surface.   The method for producing a cured epoxy resin according to claim 9, wherein the curable composition is applied to a reinforcing material and cured in the presence of the reinforcing material to form a reinforced composite material.   A cured epoxy resin obtained by the method according to claim 9.   Use of an amine composition comprising more than 85% by weight of a triethylenetetraamine of formula I or an amine curing agent composition according to any one of claims 4 to 6 for the production of epoxy resins.   A reactive polyamide resin obtained from the reaction of an amine composition according to claim 1 and / or a triethylenetetraamine of formula I having a purity of 98% by weight or more and a dimer fatty acid.   Reactivity by heating the amine composition according to claim 1 and / or triethylenetetraamine of formula I having a purity of 98% by weight or more together with a dimer fatty acid and removing the water of the condensation product by distillation. A method for producing a polyamide resin.   Use of the amine composition according to claim 1 and / or the triethylenetetraamine of the formula I having a purity of 98% by weight or more for the production of reactive polyamide resins.