1、BRITISH STANDARD BSENISO 9702:1999 Incorporating Amendment No. 1 to BSISO9702:1996 (renumbers the BS as BS EN ISO9702:1999) Plastics Amine epoxide hardeners Determination of primary, secondary and tertiary amine group nitrogen content The European Standard EN ISO9702:1998 has the status of a British
2、 Standard ICS 83.040.30BSENISO9702:1999 This British Standard, having been prepared under the direction of the Sector Board for Materials and Chemicals, was published under the authority of the Standards Board and comes into effect on 15April1997 BSI 05-1999 ISBN 0 580 27213 3 National foreword This
3、 British Standard is the English language version of ENISO9702:1998. The UK participation in its preparation was entrusted to Technical Committee PRI/42, Fibre reinforced thermosetting plastics and prepregs, which has the responsibility to: aid enquirers to understand the text; present to the respon
4、sible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. A list of organizations represented on this committee can be obtained on req
5、uest. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Find” facility of the BSI Standards
6、 Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages T
7、his document comprises a front cover, an inside front cover, pages i and ii, theEN ISO title page, page 2, the ISO title page, page ii, pages 1 to 6 and a back cover. This standard has been updated (see copyright date) and may have had amendments incorporated. This will be indicated in the amendment
8、 table on the inside front cover. Amendments issued since publication Amd. No. Date Comments 10346 April 1999 Implementation of the European StandardBSENISO9702:1999 BSI 05-1999 i Contents Page National foreword Inside front cover Foreword 2 Text of ISO 9702 1ii blankEUROPEAN STANDARD NORME EUROPENN
9、E EUROPISCHE NORM EN ISO 9702 August 1998 ICS 83.080.10 Descriptors: See ISO document English version Plastics Amine epoxide hardeners Determination of primary, secondary and tertiary amine group nitrogen content (ISO 9702:1996) Plastiques Durcisseurs pour rsines poxy Dtermination de la teneur en az
10、ote des groupes amine primaire, secondaire, tertiaire (ISO 9702:1996) Kunstoffe Aminische Epoxidhrter Bestimmung von primren, sekundren und tertiren Amingruppen als Stickstoffgehalt (ISO 9702:1996) This European Standard was approved by CEN on 12 June 1998. CEN members are bound to comply with the C
11、EN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the Central Secretariat or t
12、o any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official version
13、s. CEN members are the national standards bodies of Austria, Belgium, CzechRepublic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and UnitedKingdom. CEN European Committee for Standardization Comit Europen d
14、e Normalisation Europisches Komitee fr Normung Central Secretariat: rue de Stassart 36, B-1050 Brussels 1998 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO9702:1998EENISO9702:1998 BSI 05-1999 2 Foreword The text of the Interna
15、tional Standard from Technical Committee ISO/TC61, Plastics, of the International Organization for Standardization (ISO) has been taken over as a European Standard by Technical Committee CEN/TC249, Plastics, the Secretariat of which is held byIBN. This European Standard shall be given the status of
16、a national standard, either by publication of an identical text or by endorsement, at the latest by February1999, and conflicting national standards shall be withdrawn at the latest by February1999. According to CEN/CENELEC Internal Regulations, the following countries are bound to implement this Eu
17、ropean Standard: Austria, Belgium, CzechRepublic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the UnitedKingdom. Endorsement notice The text of the International Standard ISO9702:1996 has been appoved b
18、y CEN as a European Standard without any modification. Contents Page Foreword 2 1 Scope 1 2 Principle 1 3 Reagents 2 4 Apparatus 3 5 Procedure 3 6 Expression of results 4 7 Precision 6 8 Test report 6BSENISO9702:1999 ii BSI 05-1999 Foreword ISO (the International Organization for Standardization) is
19、 a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represen
20、ted on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. Draft International Standards
21、adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least75% of the member bodies casting a vote. International Standard ISO9702 was prepared by Technical Committee ISO/TC61, Plastics, Subcommittee SC12,
22、 Thermosetting materials. Descriptors: Plastics, epoxy resins, resin hardeners, amines, chemical analysis, determination of content, nitrogen, potentiometric methods.BSENISO9702:1999 BSI 05-1999 1 1 Scope This International Standard specifies a method for the determination of the primary, secondary
23、and tertiary amine group nitrogen content of aliphatic or aromatic amine hardeners for epoxy resins. 2 Principle 2.1 Aliphatic amines 2.1.1 Determination of total amine group nitrogen content (X T ) The total alkalinity is determined by potentiometric titration against hydrobromic or perchloric acid
24、 in glacial acetic acid, as described by the following reactions: RNH 2+ H +F RNH 3 + (RR9NH + H +F (RR9) NH 2 + (RRR )N+H + F (RRR )NH + The results are expressed as percentage nitrogen. NOTE 1Perchloric acid is not suitable for use with amine hardeners such as N-aminoethylpiperazine. 2.1.2 Determi
25、nation of tertiary amine group nitrogen content (X 3 ) The primary and secondary amine groups are converted into amide groups with acetic anhydride, as described by the following reactions: The tertiary amine group alkalinity is determined by potentiometric titration against hydrobromic or perchlori
26、c acid in glacial acetic acid/acetic anhydride, as described by the following reaction: (RR9R0)NH+H + F (RR9R0)NH + The results are expressed as percentage nitrogen. 2.1.3 Determination of primary amine group nitrogen content (X L1 ) The primary amine groups are reacted with a measured excess of2,4-
27、pentanedione (acetylacetone) in N,N-di-methylformamide to form imines, as described by the following reaction: The excess acetylacetone is determined by potentiometric titration against potassium hydroxide (the reaction products of acetylacetone and primary amine groups are neutral under these condi
28、tions). The results are expressed as percentage nitrogen. 2.1.4 Determination of secondary amine group nitrogen content (X L2 ) The secondary amine group nitrogen content is determined by calculating the difference between the total amine group nitrogen content and the sum of the primary and tertiar
29、y amine group nitrogen contents. 2.2 Aromatic amines 2.2.1 Determination of total amine group nitrogen content (X T ) The total alkalinity is determined by potentiometric titration against hydrobromic or perchloric acid in glacial acetic acid, as described by the following reactions: ArNH 2 +H + F A
30、rNH 3 + (ArAr9)NH+H + F (ArAr9)NH 2 + (ArAr9Ar0)N+H + F (ArAr9Ar0)NH + The results are expressed as percentage nitrogen. 2.2.2 Determination of tertiary amine group nitrogen content (X 3 ) The primary and secondary amine groups are converted into amide groups with acetic anhydride as described by th
31、e following reactions: The tertiary amine group alkalinity is determined by potentiometric titration against hydrobromic or perchloric acid in glacial acetic acid/acetic anhydride, as described by the following reaction. (ArAr9Ar0)N+H + F (ArAr9Ar0)NH + The results are expressed as percentage nitrog
32、en. 2.2.3 Determination of the sum of the secondaryand tertiary amine group nitrogencontents(X R2+3 ) The primary amine groups are converted into Schiff bases by salicylaldehyde in glacial acetic acid, as described by the following reaction: RNH 2 +(CH 3 CO) 2 O F RNHCOCH 3 +CH 3 COOH (RR)NH+(CH 3 C
33、O) 2 O F (RR9)NCOCH 3 +CH 3 COOH RNH 2 +CH 3 COCH 2 COCH 3 F CH 3 CNRCH 2 COCH 3 +H 2 O ArNH 2 +(CH 3 CO) 2 O F ArNHCOCH 3 +CH 3 COOH (ArAr9)NH+(CH 3 CO) 2 O F (ArAr9)NCOCH 3 +CH 3 COOH ArNH 2 +C 6 H 4 (OH)CHOF ArN=CHC 6 H 4 (OH)+H 2 OBSENISO9702:1999 2 BSI 05-1999 With strongly basic amines, the se
34、condary and tertiary amine group alkalinity is determined by potentiometric titration against hydrochloric acid in glacial acetic acid, as described by the following reactions: (ArAr)NH+H + F (ArAr)NH 2 + (ArArAr )N+H + F (ArArAr )NH + The results are expressed as percentage nitrogen. NOTE 2Weakly b
35、asic amines, such as4,4-diamino-diphenylsulfone, are titrated with hydrobromic or perchloric acid in glacial acetic acid. 2.2.4 Determination of primary amine group nitrogen content (X R1 ) The primary amine group nitrogen content is determined by calculating the difference between the total amine g
36、roup nitrogen content and the sum of the secondary and tertiary amine group nitrogen contents. 2.2.5 Determination of secondary amine group nitrogen content (X R2 ) The secondary amine group nitrogen content is determined by calculating the difference between the sum of the secondary and tertiary am
37、ine group nitrogen contents and the tertiary amine group nitrogen content. 3 Reagents During the analysis, use only reagents of recognized analytical grade and only distilled water or water of equivalent purity. 3.1 Acetic acid, glacial. 3.2 Acetic anhydride. 3.3 2,4-Pentanedione (acetylacetone). 3.
38、4 N,N-diamethylformamide. 3.5 Acetylacetone, 1,5mol/l solution in N,N-dimethylformamide. Dissolve15ml of acetylacetone (3.3) in90ml of N,N-dimethylformamide (3.4). 3.6 Salicylaldehyde. 3.7 Ethan-1,2-diol (ethylene glycol). 3.8 Propan-2-ol. 3.9 Ethylene glycol/propan-2-ol mixed solvent Mix500ml of et
39、hylene glycol (3.7) and500ml of propan-2-ol (3.8). 3.10 Potassium hydrogen phthalate. 3.11 Hydrobromic acid, 250g/l solution in acetic acid. 3.12 Perchloric acid, 70% or 60% solution in water. 3.13 Potassium hydroxide. 3.14 Hydrochloric acid, concentrated. 3.15 Sodium carbonate. 3.16 Hydrobromic aci
40、d, 0,1mol/l standard volumetric solution in glacial acetic acid. 3.16.1 Preparation Add25ml of hydrobromic acid (3.11) slowly to100ml of glacial acetic acid (3.1) in a1000ml brown-glass volumetric flask (4.9) and stir carefully. Dilute to the mark with glacial acetic acid. 3.16.2 Standardization Wei
41、gh out, to the nearest 0,1mg, 0,1g to 0,2g of potassium hydrogen phthalate (3.10) and dissolve in50ml of glacial acetic acid (3.1). Titrate this solution potentiometrically against the solution of hydrobromic acid prepared in 3.16.1 (V 1 ). Perform a blank test by titrating50ml of glacial acetic aci
42、d against the solution of hydrobromic acid prepared in3.16.1 (V 2 ). Calculate the concentration c 1of the hydrobromic acid solution, expressed in moles of HBr per litre to the nearest0,001mol HBr/l, using the equation where 3.17 Perchloric acid, 0,1 mol/l standard volumetric solution in glacial ace
43、tic acid. 3.17.1 Preparation Mix 8,5ml of70% perchloric acid (or9,9ml of60% perchloric acid)(3.12) with500ml of glacial acetic acid (3.1) in a1000ml brown-glass volumetric flask(4.9). Add30ml (or35ml if60% perchloric acid was used) of acetic anhydride (3.2) and mix well. Dilute to the mark with glac
44、ial acetic acid. 3.17.2 Standardization Use the same procedure as that in3.16.2, calculating the concentration using the same equation. In this case, c 1is the concentration of the perchloric acid solution prepared in3.17.1. m 0 is the mass, in grams, of potassium hydrogen phthalate used; V 1 is the
45、 volume, in millilitres, of the solution of hydrobromic acid prepared in3.16.1 required to reach the end point in the titration; V 2 is the volume, in millilitres of the above solution (3.16.1) required in the blank test. c 1 1 000 m 0 204,23 V 1 V 2 () - =BSENISO9702:1999 BSI 05-1999 3 3.18 Potassi
46、um hydroxide, 0,5 mol/l standard volumetric solution in propan-2-ol. 3.18.1 Preparation Take1000ml of propan-2-ol (3.8) in a round-bottomed flask and add30g of potassium hydroxide (3.13). Reflux for several hours to dissolve completely. Leave the solution in a carbon-dioxide-free atmosphere for a fe
47、w days, then transfer the clear upper solution to a polyethylene bottle and keep it in the bottle equipped with a guard tube filled with soda lime. Take care that the solution does not touch a cork or rubber stopper or stopper grease, which may be saponified. 3.18.2 Standardization Weigh, to the nea
48、rest0,1mg,0,5g to1,0g of potassium hydrogen phthalate (3.10) and dissolve in100ml of water. Titrate this solution potentiometrically against thepotassium hydroxide solution prepared in3.18.1 (V 3 ). Perform a blank test separately (V 4 ). Calculate the concentration c 2of the potassium hydroxide sol
49、ution, expressed in moles of KOH per litre to the nearest 0,001mol KOH/l, using the equation where 3.19 Hydrochloric acid, 0,1mol/l standard volumetric solution in mixed solvent. 3.19.1 Preparation Add1000ml of the ethylene glycol/propan-2-ol mixed solvent (3.9) to9ml of concentrated hydrochloric acid (3.14). 3.19.2 Standardization Weigh out, to the nearest0,1mg,0,13g to0,16g of sodium carbonate (3.15) and dissolve in 100ml of water. Titrate this solution potentiometrically against th
