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GB1598750A - High-molecular weight amine compositions - Google Patents

High-molecular weight amine compositions Download PDF

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Publication number
GB1598750A
GB1598750A GB23139/78A GB2313978A GB1598750A GB 1598750 A GB1598750 A GB 1598750A GB 23139/78 A GB23139/78 A GB 23139/78A GB 2313978 A GB2313978 A GB 2313978A GB 1598750 A GB1598750 A GB 1598750A
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GB
United Kingdom
Prior art keywords
composition
amine
molecular weight
weight
epoxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB23139/78A
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Hoechst AG
Original Assignee
Hoechst 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 Hoechst AG filed Critical Hoechst AG
Publication of GB1598750A publication Critical patent/GB1598750A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00Compositions of rubber derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules 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
    • C08G59/40Macromolecules 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
    • C08G59/50Amines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/15Heterocyclic compounds having oxygen in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Description

(54) HIGH-MOLECULAR WEIGHT AMINE COMPOSITIONS (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt (Main) 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to high-molecular weight amine compositions and a process for reducing the viscosity of high-molecular weight amines.
It is known that numerous high-molecular weight amines can react with epoxides to give technically interesting products of substantially higher molecular weight. The products obtained, may, for example, be used as binding agents for foundation materials, for cements or gap-filling compositions. In some cases, for example, when amines which are derived from butadiene-acrylonitrile copolymers are used, elastomeric gap-filling compositions. are obtained.
The amines used may be aliphatic, aromatic or heterocyclic. They may be reacted with equivalent amounts of the reaction product of "Bisphenol A" and epichlorohydrin to give high-molecular weight solid products.
The consistency of high-molecular weight amines of this kind depends on the molecular weight and on the number of amino groups, and may vary from viscous to solid. In order to render these amines capable of being mixed with epoxide and fillers, it is necessary to "melt" the amines prior to mixing. Such a step requires a considerable technological expenditure. Accordingly attempts have been made to reduce the viscosity of the amine by dilution with a solvent, for example xylene, furfuryl alcohol or acetone.
Especially when the high-molecular weight amines are used together with fillers, generally silicates, and with epoxides for the preparation of jointless floorings, solvents, for example xylene, must be added as diluent for reasons of better processability. The addition of a solvent furthermore makes it possible to add a greater quantity of filler to the composition. A large portion of the diluent remains in the composition even after hardening. However, the main portion of these retained solvents gradually evaporates, which process may take months or even more than one year. It can easily be understood that the period of volatilization of the solvent from the composition is largely dependent on the vapour pressure of the solvent. It is quite evident that the evaporation of solvents from hardened compositions results in shrinkage, which in the course of time may cause the formation of cracks in the epoxide polyadducts. Further disadvantages of epoxide polyadducts which had to be hardened in the presence of solvents are that they have a lower resistance to chemicals and solvents, an increased thermal expansion, and a reduced heat stability.
The use of solvents in the processing of epoxide compounds involves further serious disadvantages, namely annoyance by the strong odours of the solvents and the toxic properties of those solvents which are volatile.
The present invention provides epoxide-free compositions comprising a high molecular weight amine (as hereinafter defined) and a cyclic acetal of the formula
in which R represents a hydrogen atom or an alkyl group. A composition of the invention has a reduced viscosity compared to the high-molecular weight amine alone.
An alkyl group represented by R preferably contains from 1 to 4 carbon atoms, and is most preferably a methyl group. Using these acetals, the viscosity of the high-molecular weight amine is reduced to an extremely large extent, and the compositions do not give the above-mentioned undesired properties when used for producing epoxide polyadducts.
The present invention also provides a process for reducing the viscosity of a high-molecular weight amine (as hereinafter defined), which comprises mixing the amine with a cyclic acetal of the above formula. The present invention further provides epoxide resins prepared with the compositions of the invention.
The high-molecular weight amines used in the compositions and process according to the invention are defined as having a molecular weight of from 200 to 10,000, preferably from 1,000 to 5,000, especially from 1,500, to 3,500. Amines which have from 1 to 3, preferably approximately 2, primary amino groups in the molecule on average, and especially those which are derived from copolymers of butadiene and acrylonitrile, are particularly preferred.
High-molecular weight amines which are derived from copolymers consisting of from 10 to 30% by weight of acrylonitrile and from 90 to 70% by weight of butadiene are particularly preferred. These amines may be obtained, for example, by copolymerization of butadiene, acrylonitrile and a small amount of a vinyl compound which contains a reactive halogen atom, according to German Offenlegungsschrift No. 25 57 559, and subsequently reacting the halogen atom with ammonia, or with a low-molecular bivalent amine containing at least one primary amino group, for example ethylene diamine or aminoethylpiperazine.
High-molecular weight amines derived from copolymers of butadiene and acrylonitrile are commercially available under the trade name Hycar ATNB (manufactured by Messrs. B. F. Goodrich Co., Ohio, USA).
It is generally advantageous to mix from 1 to 40, preferably from 5 to 25, parts by weight of the cyclic acetal with 100 parts by weight of the high-molecular weight amine. The most favorable composition may easily be determined by a preliminary test.
The pronounced viscosity reduction achieved by adding a cyclic acetal of the above formula to a high-molecular weight amine is shown in the following Table I: TABLE I: Reduction of the viscosity of a high-molecular weight amine: Composition Viscosity (mPa.s) 100 parts by weight of diamine, molar weight 1600 262000 at 30"C 190 parts by weight of diamine 105 000 at 30"C 10 parts by weight of trioxan 85 parts by weight of diamine 52000 at 30"C 15 parts by weight of trioxan 80 parts by weight of diamine 28000 at 30"C 20 parts by weight of trioxan The diamine used for this test (Hycar ATBN) was derived from a copolymer consisting of 17% by weight of acrylonitrile and 83% by weight of butadiene.
Suitable compounds for hardening the high-molecular weight amines are epoxide compounds commonly used for this purpose, for example the reaction products of epichlorohydrin and 1) 4,4 - dihydroxy - 2,2 - diphenylpropane ("Bisphenol A"), 2) a condensation product of o-cresol and formaldehyde consisting of from 90 to 95 percent of a product which is formed by reaction of 2 mols of o-cresol and 1 mole of formaldehyde 3) phenolic resins, especially novolaks, or 4) aliphatic polyhydroxy compounds.
The compounds which have been obtained by condensation of Bisphenol A with epichlorohydrin or 1,3-dichlorohydrin in the presence of an alkali, and which correspond to the formula
are preferably used.
Liquid bis- or polyepoxides, especially those having a viscosity of from 100 to 15,000 mPa. sec at 250C, react especially easily.
Epoxide resins which have been prepared using compositions according to the invention of amine and cyclic acetal do not become brittle, even after storage for a period of several months at 1100C, in contradistinction to those epoxide resins which have been prepared using amines mixed with solvents. With regard to the usual technological properties, for example the bond strength on solid materials, the products prepared with the compositions of the invention are equal to those prepared with the use of solvents.
Table 2 shows the good mechanical properties of epoxide resins prepared from compositions according to the invention: TABLE 2: 1st mixture 2nd mixture polyamine 85 parts by weight 85 parts by weight trioxymethylene 15 parts by weight 15 parts by weight epoxide resin 20 parts by weight 30 parts by weight processing time about 2 h about 2 h Shore hardness A after 35 50 3 days at 20"C elongation at break 300% 70% ultimate tensile strength 200N/cm2 600 N/cm2 The polyamine employed was the diamine of molar weight 1600 (Table 1). The epoxide resin used was Bisphenol A containing 0.45 mol of epoxide groups per 100 g and having a viscosity of 1 Pa. sec. at 200C.
The degree of reduction of the viscosity according to the process of invention depends to only a small extent on the constitution of the high-molecular weight amines. Table 3 shows the reduction of the viscosity of various amines: TABLE 3: Molar - Viscosity''' Viscosity Amine weight amine mixture aliphatic diamine 242 3800 360 phenoUformaldehyde 302 18200 370 condensate containing amino groups aliphatic polyamide not determined 24000 1500 having terminal amino groups 1) [mPa. sec.] measured at 200C.
2) mixture of 15% by weight of trioxan and 85 ó by weight of amine: [mPa.sl measured to 200 C.

Claims (19)

WHAT WE CLAIM IS:
1. An epoxide-free composition comprising a high-molecular weight amine (as hereinbefore defined) and a cyclic acetal of the formula
in which each R, which may be the same or different represents a hydrogen atom or an alkyl group.
2. A composition as claimed in claim 1, wherein an alkyl group represented by R has from 1 to 4 carbon atoms.
3. A composition as claimed in claim 2, wherein an alkyl group represented by R is a methyl group.
4. A composition as claimed in any one of claims I to 3, wherein each R is the same.
5. A composition as claimed in any one of claims 1 to 4, wherein the amine has a molecular weight of from 1000 to 5000.
6. A composition as claimed in claim 5, wherein the molecular weight of the amine is from 1500 to 3500.
7. A composition as claimed in any one of claims 1 to 6, wherein the amine contains from 1 to 3 primary amino groups in the molecule on average.
8. A composition as claimed in claim 7, wherein the amine contains approximately 2 primary amino groups in the molecule on average.
9. A composition as claimed in any one of claims 1 to 8, wherein the amine is derived from a copolymer of butadiene and acrylonitrile.
10. A composition as claimed in claim 9, wherein the amine is derived from a copolymer comprising from 10 to 30% by weight of structural units derived from acrylonitrile and from 90 to 70% by weight of structural units derived from butadiene.
11. A composition as claimed in any one of claims 1 to 10 wherein the weight ratio of cyclic acetal to -high-molecular weight amine is from 1:100 to 40:100.
12. A composition as claimed in claim 11, wherein the weight ratio of cyclic acetal to high-molecular weight amine is from 5:100 to 25:100.
13. A composition as claimed in claim 1 and described herein.
14. A process for reducing the viscosity of a high-molecular weight amine (as hereinbefore defined), which comprises mixing the amine with a cyclic acetal of the formula
in which each R, which may be the same or different, represents a hydrogen atom or an alkyl group.
15. A process as claimed in claim 14, wherein a composition as claimed in any one of claims 2 to 13 is prepared.
16. A process for preparing an epoxide resin which comprises reacting an epoxide compound with a composition as claimed in any one of claims 1 to 13.
17. A process as claimed in claim 16, wherein the epoxide compound is a condensation product of 4,4- dihydroxy- 2,2- diphenylpropane with epichlorohydrin or 1,3-dichlorohydrin.
18. A process as claimed in claim 18, substantially as described herein.
19. An epoxide resin prepared by a process as claimed in any one of claims 16 to 18.
GB23139/78A 1977-05-27 1978-05-26 High-molecular weight amine compositions Expired GB1598750A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2724063A DE2724063C2 (en) 1977-05-27 1977-05-27 Diluent for high molecular weight amines

Publications (1)

Publication Number Publication Date
GB1598750A true GB1598750A (en) 1981-09-23

Family

ID=6010081

Family Applications (1)

Application Number Title Priority Date Filing Date
GB23139/78A Expired GB1598750A (en) 1977-05-27 1978-05-26 High-molecular weight amine compositions

Country Status (10)

Country Link
BE (1) BE867589A (en)
BR (1) BR7803354A (en)
CA (1) CA1097665A (en)
DE (1) DE2724063C2 (en)
FR (1) FR2392066A1 (en)
GB (1) GB1598750A (en)
IT (1) IT1096234B (en)
LU (1) LU79708A1 (en)
NL (1) NL7805777A (en)
SE (1) SE7806089L (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1034855B (en) * 1956-09-05 1958-07-24 Gen Aniline & Film Corp Process for the multi-stage curing of epoxy resins by m-phenylenediamine
US3026285A (en) * 1959-09-18 1962-03-20 Frank N Hirosawa Curing agent comprising the reaction product of an aliphatic polyamine and an aldehyde, and epoxy resin cured therewith
DE1110407B (en) * 1959-10-23 1961-07-06 Hoechst Ag Process for curing epoxy resins
BE606055A (en) * 1960-07-14
CH487835A (en) * 1967-06-22 1970-03-31 Ciba Geigy Process for the preparation of new adducts from polyepoxides and cycloaliphatic diprimary diamines

Also Published As

Publication number Publication date
DE2724063A1 (en) 1978-12-07
BR7803354A (en) 1979-01-02
SE7806089L (en) 1978-11-28
IT1096234B (en) 1985-08-26
FR2392066B1 (en) 1982-12-03
CA1097665A (en) 1981-03-17
IT7823808A0 (en) 1978-05-25
BE867589A (en) 1978-11-29
NL7805777A (en) 1978-11-29
DE2724063C2 (en) 1986-10-30
FR2392066A1 (en) 1978-12-22
LU79708A1 (en) 1979-02-02

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Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee