1、BRITISH STANDARD BS EN ISO 11401:1998 Plastics Phenolic resins Separation by liquid chromatography The European Standard EN ISO 11401:1998 has the status of a British Standard ICS 83.080.10BSENISO11401:1998 This British Standard, having been prepared under the directionof the Sector Board forMateria
2、ls and Chemicals, waspublished under the authorityof the Standards Boardand comes into effect on 15 October 1998 BSI 05-1999 ISBN 0 580 30270 9 National foreword This British Standard is the English language version of ENISO11401:1998. It is identical with ISO11401:1993. The UK participation in its
3、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 responsible international/European committee any enquiries on the interpretation, or proposals for chan
4、ge, 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 request to its secretary. Cross-references Attention is drawn to the fact that CEN and CENELEC Stand
5、ards normally include an annex which lists normative references to international publications with their corresponding European publications. The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under th
6、e section entitled “International Standards Correspondence Index”, or by using the “Find” facility of the BSI Standards 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 applic
7、ation. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, pages i and ii, theENISOtitle page, page 2, the ISO title page, pageii, pages 1 to 6 and aback cover. This standard has
8、been updated (see copyright date) and may have had amendments incorporated. This will be indicated in the amendment table on the inside front cover. Amendments issued since publication Amd. No. Date CommentsBSENISO11401:1998 BSI 05-1999 i Contents Page National foreword Inside front cover Foreword 2
9、 Foreword ii Text of ISO 11401 1ii blankEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 11401 August 1998 ICS 83.080.10 Descriptors: See ISO document English version Plastics Phenolic resins Separation by liquid chromatography (ISO 11401:1993) Plastiques Rsines phnoliques Sparation par chro
10、matographie en phase liquide (ISO 11401:1993) Kunststoffe Phenolharze Trennung durch Flssigchromatographie (ISO 11401:1993) This European Standard was approved by CEN on 13 June 1998. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving
11、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 to any CEN member. This European Standard exists in three official versions
12、 (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 versions. CEN members are the national standards bodies of Austria, Belgium, Czec
13、hRepublic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. CEN European Committee for Standardization Comit Europen de Normalisation Europisches Komitee fr Normung Central Secretariat: rue d
14、e 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 ISO 11401:1998 EENISO11401:1998 BSI 05-1999 2 Foreword The text of the International Standard from Technical Committee ISO/TC61 “Plastics” of the I
15、nternational Organization for Standardization (ISO) has been taken over as an European Standard by Technical Committee CEN/TC249 “Plastics”, the secretariat of which is held by IBN. This European Standard shall be given the status of a national standard, either by publication of an identical text or
16、 by endorsement, at the latest by February1999, and conflicting national standards shall be withdrawn at the latest by February1999. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austr
17、ia, Belgium, CzechRepublic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and theUnitedKingdom. Endorsement notice The text of the International Standard ISO11401:1993 has been approved by CEN as a European S
18、tandard without any modification. NOTENormative references to International Standards are listed in Annex ZA (normative). Contents Page Foreword 2 1 Scope 1 2 Normative references 1 3 Definitions 1 4 Test methods 1 5 Test report 5 Annex ZA (normative) Normative referencestointernational publications
19、 withtheir relevant European publications 6 Figure 1 Example of a phenol novolakchromatogram 2 Figure 2 Example of a phenol novolak chromatogram produced using a polar column 4 Figure 3 Example of a phenol resol chromatogram produced using a non-polar column 5ENISO11401:1998 ii BSI05-1999 Foreword I
20、SO (the International Organization for Standardization) is 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 c
21、ommittee has been established has the right to be represented 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 electr
22、otechnical standardization. Draft International Standards 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 ISO11401 was prepared by
23、 Technical Committee ISO/TC61, Plastics, Sub-Committee SC12, Thermosetting materials. Later, this International Standard will become part of a general standard concerning liquid chromatography. Descriptors: Plastics, thermosetting resins, phenoplasts, tests, determination of content, separation meth
24、ods, chromatography, high performance liquid chromatography.ENISO11401:1998 BSI 05-1999 1 1 Scope 1.1 This International Standard specifies chromatographic methods for the separation of phenolic resins into their component compounds. Separation takes place according to molecular weight and/or polari
25、ty. There are various liquid chromatographic methods: A: Gel-permeation chromatography B: High-performance liquid chromatography on polar columns C: High-performance liquid chromatography on non-polar columns It is possible to separate a phenolic resin into its components according to molecular size
26、 using method A (gel-permeation chromatography). Whereas free phenol and the sum of the dihydro-xydiphenylmethanes (in novolaks) and various methylolphenols (in resols) are quantitatively separated in this procedure, high-molecular-weight components of the resins are only incompletely separated due
27、to the multitude of isomers. Methods B and C (high-performance liquid chromatography) separate the compounds in the resin according to molecular weight and polarity. Molecular-weight effects predominate on polar stationary phases (method B), and the effect of polarity on non-polar stationary phases
28、(method C). These methods also allow quantitative determination of individual low-molecular-weight resin components. Because of the different resin solubilities, method B is more suitable for novolaks and method C for resols. 1.2 The methods are applicable to phenolic resins that are soluble in the
29、solvents and solvent blends used. 1.3 This test is useful for characterization of products and for research. 2 Normative references The following standards contain provisions which, through reference in this text, constitute provisions of this International Standard. At the time of publication, the
30、editions indicated were valid. All standards are subject to revision, and parties to agreements based on this International Standard are encouraged to investigate the possibility of applying the most recent editions of the standards indicated below. Members of IEC and ISO maintain registers of curre
31、ntly valid International Standards. ISO 472:1988, Plastics Vocabulary. ISO 10082:1991, Plastics Phenolic resins Definitions and test methods. 3 Definitions For the purposes of this International Standard, the following definitions apply. 3.1 phenolic resin generally, a class of resins made by the po
32、lycondensation of phenol, its homologues and/or derivatives, with aldehydes or ketones ISO472 3.2 novolaks non-self-curing, soluble, fusible phenolic resins that remain stable when stored, the phenol nuclei of which are linked primarily by methylene bridges. Novolaks can be made to react further and
33、 crosslink by the addition of hardeners; heating is also usually necessary ISO10082 See also novolak in ISO472 3.3 resols soluble, fusible phenolic resins which, in contrast to novolaks, contain methylol groups and methylene-ether and sometimes also methylene-amine bridges. Resols are self-curing; t
34、hey crosslink into insoluble products when heated and/or mixed with catalysts, without addition of further reaction components. Resols are perishable and can be stored for a limited time only ISO10082 See also resol in ISO472 4 Test methods 4.1 Method A Gel-permeation chromatography NOTE 1The reagen
35、ts, apparatus and test conditions given are examples. Others may be used if similar or better results are obtained. 4.1.1 Principle A test sample of the phenolic resin is dissolved in a suitable solvent and the molecular-weight distribution is determined by separation on columns with polymer gels ha
36、ving different pore diameters. 4.1.2 Reagents 4.1.2.1 Tetrahydrofuran, chromatography grade. 4.1.3 Apparatus 4.1.3.1 Pump, with sample inlet and adjustable, surge-free throughput. 4.1.3.2 UV detector or refractometer 4.1.3.3 Printer/plotter 4.1.3.4 Integrator or computerENISO11401:1998 2 BSI 05-1999
37、 4.1.3.5 Gel-chromatography separation column system, such as 2 100 , 600 mm 7,7mm 2 1 000 , 600 mm 7,7mm 4.1.3.6 Automatic sampler (optional). 4.1.4 Preparation of test sample 4.1.4.1 Since only small quantities of materials are used, it is essential that test samples be representative of the mater
38、ial. 4.1.4.2 For injection, a100mg sample of the material is dissolved in10ml of tetrahydrofuran (4.1.2.1). 4.1.5 Test conditions Temperature: room temperature Carrier: tetrahydrofuran Flow rate: 1 ml/min Injection volume: 20 4l Detector: UV detector at254nm or280nm, or refractometer 4.1.6 Evaluatio
39、n of results Exact calibration for determination of the molecular-weight distribution is difficult since the phenolic hydroxyl groups add to tetrahydrofuran, although this addition is incomplete in long-chain molecules due to steric hindrance. Qualitative evaluation may be carried out by comparison
40、of chromatograms. If a computer with appropriate software is available, chromatograms can be subtracted from one another to emphasize differences in the degree of condensation and the molecular-weight distribution. With good separation, some low-molecular-weight components (phenol, methylolphenols a
41、nd the sum of dihydroxydiphenylmethanes) may also be determined quantitatively (see 4.3.8). 4.1.7 Sample chromatogram of a phenolic novolak See Figure 1. 4.2 Method B High-performance liquid chromatography on polar columns See 4.1, note 1. 4.2.1 Principle A test sample of the phenolic resin is disso
42、lved in a suitable solvent and separated on the polar column. The carrier is a solvent blend run with a concentration gradient. Novolaks and tetrahydrofuran-soluble resols may be analysed. 4.2.2 Reagents 4.2.2.1 Tetrahydrofuran, chromatography grade. 4.2.2.2 Heptane, chromatography grade. Figure 1 E
43、xample of a phenol novolak chromatogramENISO11401:1998 BSI 05-1999 3 4.2.3 Apparatus 4.2.3.1 Pump, with sample inlet and adjustable, surge-free throughput. 4.2.3.2 UV detector 4.2.3.3 Printer/plotter 4.2.3.4 Integrator or computer 4.2.3.5 Column for polar chromatography, such as a12,5mm 4mm column p
44、acked with54m silica gel. 4.2.3.6 Automatic sampler (optional). 4.2.4 Preparation of test sample 4.2.4.1 Since only small quantities of materials are used, it is essential that test samples be representative of the material. 4.2.4.2 For injection, a100mg sample of the material is dissolved in10ml of
45、 tetrahydrofuran(4.2.2.1). 4.2.5 Test conditions Temperature: room temperature Carrier: tetrahydrofuran-heptane Flow rate: 0,5 ml/min Injection volume: 20 4l Detector: UV detector at 254 nm or280nm 4.2.6 Evaluation of results Qualitative evaluation is carried out by comparison of chromatograms. With
46、 good separation, some low-molecular-weight components (phenol, dihydroxydiphenylmethanes and phenolic alcohols) may also be determined quantitatively (see 4.3.8). 4.2.7 Sample chromatogram of a phenolic novolak on a polar column See Figure 2. 4.3 Method C High-performance liquid chromatography on n
47、on-polar (reversed-phase) columns See 4.1, note 1. 4.3.1 Principle A test sample of the phenolic resin is dissolved in a suitable solvent and separated on the non-polar column. The carrier is a solvent blend run with a concentration gradient. 4.3.2 Reagents 4.3.2.1 Water, chromatography grade. 4.3.2
48、.2 Methanol, chromatography grade. 4.3.2.3 Tetrahydrofuran, chromatography grade. 4.3.3 Apparatus 4.3.3.1 Pump, with sample inlet and adjustable, surge-free throughput. 4.3.3.2 UV detector 4.3.3.3 Printer/plotter 4.3.3.4 Integrator or computer 4.3.3.5 Column for non-polar chromatography, such as a12
49、5mm 0,4mm column packed with54m RP18. 4.3.3.6 Automatic sampler (optional). 4.3.4 Preparation of test sample 4.3.4.1 Since only small quantities of materials are used, it is essential that test samples be representative of the material. 4.3.4.2 The following pretreatments may be used with resols; a) alkaline resol samples can be neutralized with formic acid to convert phenates to phenols; b) ammonium hydroxide can be added to resols to destroy the oxymethylene chaining that occurs at each methylol end
