1、BRITISH STANDARD Plastics - Phenolic resins - Separation by liquid chromatography * * rn The European Standard EN IS0 11401:1998 has the status of a British Standard ICs 83.080.10 BS EN IS0 11401:1998 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW u STD-BSI BS EN IS0 LL40L-EN
2、GL 1778 m Lb24bb9 0731q5 4L m Amd. No. BS EN IS0 11401:1998 Date Text affected This British Standard, having been prepared under the direction of the Sector Board for Materiais and Chemicals, was published under the authority of the Standards Board and comes into effect on 15 October 1998 O BSI 1998
3、 ISBN O 580 30270 9 National foreword This British Standard is the English language version of EN IS0 11401:1998. It is identical with IS0 11401: 1993. The UK participation in its preparation was entrusted to Technical Committee PW42, Fibre reinforced thermosetting plastics and prepregs, which has t
4、he responsibility to: - aid enquirers to understand the text; - present to the responsible internationaVEuropean committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; - monitor related international and European developments and promulgae them in
5、 the UK A list of organizations represented on this commitee can be obtained on request to its secretary. Cross-references Attention is drawn to the fact that CEN and CENELEC Standards normally include an annex which lists normative references to international publications with their correspondmg Eu
6、ropean publications. The British Standards which implement international or European publications referred to in this document may be found in the BSI Standarcls Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Fnd” facility of the BSI Standards E
7、lectronic 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 Thi
8、s document comprises a front cover, an inside front cover, the EN IS0 title page, the EN IS0 foreword page, the IS0 title page, page ii, pages 1 to 6, the annex ZA page and a back cover. I I EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN IS0 11401 August 1998 ICs 83.080.1 O Descriptors: see IS
9、0 document English version Plastics - Phenolic resins - Separation by liquid chromatography (IS0 1 1 401 : 1 993) Plastiques - Rsines phnoliques - Sparation par chromatographie en phase liquide (IS0 11401 :1993) Kunststoffe - Phenolharze - Trennung durch Flssigchromatographie (ISO 11401:1993) This E
10、uropean Standard was approved by CEN on 13 June 1998. CEN members are bound to comply with the CEWCENELEC 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 blbliographical references co
11、ncerning 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 (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its o
12、wn 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, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, S
13、weden, Switzerland and United Kingdom. EUROPEAN COMMiTEE FOR STANDARDIZATION COMITE EUROPEEN DE NORMALISATION EUROPAISCHES KOMITEE FUR NORMUNG Central Secretariak rue de strimart, 36 8-1050 Brussels 0 1998 CEN All rights of exploition in any form and by any means reserved worldwide for CEN national
14、Members. Ref. No. EN IS0 11401:1998 E STD-BSI BS EN IS0 LLiIOL-ENGL 1998 D Lb2LibbS 073LiI7 254 D EN IS0 11401:1998 Foreword The text of the International Standard from Technical Committee ISOTTC 61 “Plastics“ of the International Organization for Standardization (ISO) has been taken over as an Euro
15、pean Standard by Technical Committee CENTTC 249 “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 by endorsement, at the latest by February 1999, and conflicting national standar
16、ds shall be withdrawn at the latest by February 1999. According to the CENKENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland,
17、 Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of the International Standard IS0 11401:1993 has been approved by CEN as a European Standard without any modification. NOTE: Normative references to Internationa
18、l Standards are listed in annex ZA (normative). STD.8SI BS EN IS0 LlqDL-ENGL 1998 ICI Lb24bb 1173LB48 190 EN IS0 11401:1998 1 NTERNATIONAL S TA N DA R D IS0 11401 First edition 1993-1 2-01 Plastics - Phenolic resins - Separation by liquid chromatography Plastiques - Rsines phnoliques - Sparation par
19、 chromatographie en phase liquide Reference number IS0 11401:1993E) Foreword IS0 (the International Organization for Standardization) is a worldwide federation of national standards bodies (IS0 member bodies). The work of preparing International Standards is normally carried out through IS0 technica
20、l committees. Each member body interested in a subject for which a technical committee 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. IS0 collaborates closely wit
21、h the International Electrotechnical Commission (IEC) on all matters of electrotechnical 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 least 75 YO of
22、the member bodies casting a vote. International Standard IS0 1 1401 was prepared by Technical Committee ISOTTC 61, Plastics, SubCommittee SC 12, Thermosetting materials. Later, this International Standard will become part of a general standard concerning liquid chromatography. Doscriptor8: plastics,
23、 thermosetting resins, Phenoplasts, tests, determination of content, separation methods, chromatography, high performance liquid chromatography. i STD-BSI BS EN IS0 21401-ENGL 1778 Lb24bb7 0733850 847 D EN IS0 11401:1998 Plastics - Phenolic resins - Separation by liquid chromatography 1 Scope 2 Norm
24、ative references The following standards contain provisions which, 1.1 This international Standard Specifies chromato- through reference in this text, provisions graphic methods for the separation of phenolic resins of this International Standard, At the time of pub!- into their component compounds.
25、 SeParation takes cation, the editions indicated were valid. All standards place according to molecular weight and/or polarity. are subject to revision, and parties to agreements based on this International Standard are encouraged to investigate the possibility of applying the most re- cent editions
26、 of the standards indicated below. Members of IEC and IS0 maintain registers of cur- rently valid International Standards. IS0 472:1988, Plastics - Vocabulary. There are various liquid chromatographic methods: - A: Gel-permeation chromatography - = 6: High-performance liquid chromatography on I = -
27、polar columns - E C: High-performance liquid chromatography on It is possible to separate a phenolic resin into its components according to molecular size using method A (gel-permeation chromatography). Whereas free phenol and the sum of the dihydro- xydiphenylmethanes (in novolaks and various methy
28、lolphenols (in resols) are quantitatively separ- ated in this procedure, high-molecular-weight compo- nents of the resins are only incompletely separated due to the multitude of isomers. Methods B and C (high-performance liquid chroma- tography) separate the compounds in the resin ac- cording to mol
29、ecular weight and polarity. Molecular-weight effects predominate on polar sta- tionary phases (method BI, and the effect of polarity on non-polar stationary phases (method Cl. These methods also allow quantitative determination of in- dividual low-molecular-weight resin components. Be- cause of the
30、different resin solubilities, method B is more suitable for novolaks and method C for resols. * * IB non-polar columns IS0 10082:1991, Plasrics - Phenolic resins - Defi- nitions and rest methods. 3 Definitions For the purposes of this International Standard, the following definitions apply. 3.1 phen
31、olic resin: Generally, a class of resins made by the polycondensation of phenol, its homologues and/or derivatives, with aldehydes or ke- tones. IS0 4721 3.2 novolaks: Non-selfturing, soluble, fusible phenolic resins that remain stable when stored, the phenol nuclei of which are linked primarily by
32、methylene bridges. Novolaks can be made to react further and crosslink by the addition of hardeners; heating is also usually necessary. IS0 100823 See also novolak in IS0 472. 3.3 resols: Soluble, fusible phenolic resins which, in 1.2 The methods are applicable to phenolic resins contrast to novolak
33、Sl contain methyl01 groups and that are soluble in the solvents and solvent blends methylene-ether and sometimes also methylene- used. amine bridges. Resols are selfturing; they crosslink into insoluble products when heated and/or mixed with catalysts, without addition of further reaction 1.3 This t
34、est is useful for characterization of pro- components. Resols are perishable and can be stored ducts and for research. for a limited time only. IS0 100821 1 EN IS0 11401:1998 See also resol in IS0 472. 4 Test methods 4.1 Method A - Gel-permeation chromatography NOTE 1 The reagents, apparatus and tes
35、t 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 having different pore d
36、iameters. 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 Prnter/plotter 4.1.3.4 Integrator or computer. 4.1.3.5 Gel-chromatography separation column sys
37、tem, such as 2 x 100 A, 600 mm x 0 7,7mm 2 x 1 O00 A, 600 mm x 0 7,7 mm 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 represen- tative of the material. 4.1.4.2 For injection, a 10
38、0 mg sample of the ma- terial is dissolved in 10 ml of tetrahydrofuran (4.1.2.1). 4.1.5 Test conditions Temperature: room temperature Carrier: tetrahydrofuran Flow rate: 1 ml/min Injection volume: 20 pI Detector: UV detector at refractometer 4.1.6 Evaluation of results 254 nm or 280 nm, or Exact cal
39、ibration 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 compari- son of chromatograms. I
40、f a computer with appropriate software is available, chromatograms can be sub- tracted from one another to emphasize differences in the degree of condensation and the molecular-weight distri bution. With good separation, some low-molecular-weight components (phenol, methylolphenols and the sum of di
41、hydroxydiphenylmethanes) may also be deter- mined 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 dissolved in a su
42、itable 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. 2 STD.BS1 BS EN IS0 lL
43、40L-ENGL 1778 Lb24bb 0731852 bll = EN IS0 11401:1998 f ln VI VI =. m p. rn *. v) O E f E % d h c c P O h 8 oz c 01 c I Time - Figure 1 - Example of a phenol novolak chromatogram 4.2.3 Apparatus 4.2.3.1 Pump, with sample inlet and adjustable, surge-free throughput. * * LC 4.2.3.2 UV detector. 4.2.3.3
44、 Printer/plotter. 4.2.3.4 Integrator or computer. 4.2.3.5 Column for polar chromatography, such as a 125 mm x 0 4 mm column packed with 5 krn 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
45、that test samples be represen- tative of the material. 4.2.4.2 For injection, a 100 mg sample of the ma- terial is dissolved in 10 ml of tetrahydrofuran (4.2.2.11. 4.2.5 Test conditions Temperature: room temperature Carrier: tetrahydrofuran-heptane Time (min) O 10 40 44 47 55 THF (% 1 25 50 I O0 1 O
46、0 25 25 Flow rate: 0,5 ml/min Injection volume: 20 FI Heptane (%I 75 50 O O 75 75 Detector: UV detector at 254 nm or 280 nm 4.2.6 Evaluation of results Qualitative evaluation is carried out by comparison of chromatograms. With good separation, some low-molecular-weight components (phenol, dihydroxyd
47、iphenylmethanes and 3 STD-BSI BS EN IS0 LL40L-ENGL 1798 Lb24bb7 0731853 558 EN IS0 11401:1998 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
48、 non-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 col- N umn. The carrier is a solvent blend run with a con- centration gradient. 4.3.2 Reagents 4.3.2.1 Water, chromatography grad
49、e. 4.3.2.2 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 Printerlplotter. 5 10 15 20 25 30 35 60 Time - Figure 2 - Example of a phenol novolak chromatogram produced using a polar column 4 STD-BSI BS EN IS0 LLLiU1-ENGL 1978 lb24bb7 073L85Li 49Li EN IS0 11401:1998 between individual peaks are too small. It may be done with external standards (see 4.3.8). 4.3.3.4 Integrator or computer. 4.
