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Antioxidant capacity, phenol, anthocyanin and ascorbic acid contents in raspberries, blackberries, r

Antioxidant capacity, phenol, anthocyanin and ascorbic acid contents in raspberries, blackberries, r
Antioxidant capacity, phenol, anthocyanin and ascorbic acid contents in raspberries, blackberries, r

Antioxidant capacity,phenol,anthocyanin and ascorbic acid contents

in raspberries,blackberries,red currants,gooseberries and

Cornelian cherries

G.E.Pantelidis,M.Vasilakakis,G.A.Manganaris *,Gr.Diamantidis

Faculty of Agriculture,Aristotle University,54124Thessaloniki,Greece

Received 20November 2005;received in revised form 9April 2006;accepted 8June 2006

Abstract

Raspberry (Rubus idaeus ),blackberry (Rubus fructicosus ),raspberry ·blackberry hybrids,red currant (Ribes sativum ),gooseberry (Ribes glossularia )and Cornelian cherry (Cormus mas )cultivars and native populations of varied pigmentation,originally from the Med-iterranean area of Northern Greece,were assayed for antioxidant activity (determined as ferric reducing antioxidant power (FRAP)and deoxyribose protection),ascorbic acid,phenol,and anthocyanin contents.FRAP values ranged from 41to 149l mol ascorbic acid g à1dry weight and protection of deoxyribose ranged from 16.1%up to 98.9%.Anthocyanin content ranged from 1.3,in yellow-coloured fruit,up to 223mg cyanidin-3-glucoside equivalents 100g à1fresh weight in Cornelian cherry,whereas phenol content ranged from 657up to 2611mg gallic acid equivalents 100g à1dry weight.Ascorbic acid content ranged from 14up to 103mg 100g à1fresh weight.The present study outlines that the native Cornelian cherry population is an extremely rich source of antioxidants,demonstrating its potential use as a food additive.

ó2006Elsevier Ltd.All rights reserved.

Keywords:Berries;Antioxidants;Ascorbic acid;Anthocyanins;Phenols;Small fruit

1.Introduction

Small fruits constitute a good source of natural antiox-idant substances.Extracts of fruits from various black-berry,raspberry and gooseberry cultivars act e?ectively as free radical inhibitors (Heinonen,Meyer,&Frankel,1998;Wang &Lin,2000;Wang &Jiao,2000).In addition,the phenol,anthocyanin and ascorbic acid content of small fruits has been investigated (Kalt,Forney,Martin,&Prior,1999;Wang,Cao,&Prior,1996).Polyphenols comprise a wide variety of compounds,divided into several classes (i.e.,hydroxybenzoic acids,hydroxycinnamic acids,antho-cyanins,proanthocyanindins,?avonols,?avones,?ava-nols,?avanones,iso?avones,stilbenes and lignans),that occur in fruits and vegetables (Manach,Scalbert,Morand,

Remesy,&Jimenez,2004).Particularly,phenols contribute substantially to the antioxidant complement of many small fruit species,having potential health e?ects (Heinonen et al.,1998).

It has been already demonstrated that a wide diversity of phytochemical levels and antioxidant capacities exist within and across genera of small fruit (Moyer,Hummer,Finn,Frei,&Wrolstad,2002).Furthermore,accumulating evi-dence exists,suggesting that genotype may have a profound in?uence on the content of bioactive compounds in berries (Anttonen &Karjalainen,2005).However,to the best of our knowledge few data exist regarding the properties of small fruits originating from the Mediterranean area.In this paper we analysed raspberry,blackberry,raspberry ·blackberry hybrids,red currant,gooseberry and Cornelian cherry cultivars,originating from Greece,for their antioxi-dant capacity,phenol,anthocyanin and ascorbic acid content.

0308-8146/$-see front matter ó2006Elsevier Ltd.All rights reserved.doi:10.1016/j.foodchem.2006.06.021

*

Corresponding author.Tel.:+302310998623;fax:+302310998645.E-mail address:manganar@agro.auth.gr (G.A.Manganaris).

https://www.wendangku.net/doc/a53363637.html,/locate/foodchem

Food Chemistry 102(2007)

777–783

Food Chemistry

2.Materials and methods

2.1.Plant material

Samples of raspberry(Rubus ideaus L.),blackberry (Rubus fructicosus),raspberry·blackberry hybrids,red currant(Ribes sativum)and gooseberry(Ribes grossularia) cultivars were collected from a commercial farm(Thessalo-niki,Northern Greece).Additionally,a native Cornelian cherry population with red colour(Cornus mas cv.Vermio) was collected from mount Vermio(altitude=330m,Veria, Northern Greece).The examined cultivars and their colour are shown in Table1.In raspberry cultivars bearing fruit twice(cvs.Heritage,Autumn Bliss,Fallgold),samples were collected from both periods and examined separately.After harvest,the samples were immediately transferred to the laboratory of Horticulture at the Aristotle University of Thessaloniki and frozen atà20°C,until needed.

2.2.Soluble solids content(SSC)

Samples of the examined cultivars were pooled to obtain a composite sample and analysed for SSC using a digital refractometer(Atago Model PR-1,Tokyo).

2.3.Ascorbic acid content

Ascorbic acid was quanti?ed with the re?ectometer set of Merck Co(Merck RQ?ex)according to their protocol for the juice of red fruit(Ascorbic Acid in Red Coloured Fruit Juices,Merck).Fruit sample(5g)and20ml oxalic acid(1%)were mixed,homogenised for1min,and?ltered. PVPP(polyvinylpolypyrrolidone)(500g)was added to 10ml of the?ltered sample,to remove phenols,and6–7 drops of H2SO4(25%)were added,to reduce the pH to below 1.Results were expressed as mg ascorbic acid (AsA)100gà1fresh weight(fw).

2.4.Anthocyanins

Total anthocyanin content was measured with the pH dif-ferential absorbance method,as described by Cheng and Breen(1991).Brie?y,absorbance of the extract was mea-sured at510and700nm in bu?ers at pH1.0(hydrochloric acid–potassium chloride,0.2M)and 4.5(acetate acid–sodium acetate,1M).Anthocyanin content was calculated using a molar extinction coe?cient of29,600(cyanidin-3-glucoside)and absorbance of A=[(A510àA700)pH1.0à(A510àA700)pH4.5].Results were expressed as mg cyani-din-3-glucoside equivalents100gà1fw.

2.5.Total phenol content

Fruit samples were air-dried at55°C and homogenised. Dry sample(1g)was placed in a test tube with10ml of extraction solution(50%methanol/H2O)according to Vin-son,Su,Zubik,and Bose(2001).The mixture was placed in the dark at4°C for24h.The supernatant was collected and replaced with an equal quantity of extraction solution, then placed in the dark at4°C for a further48h.The two supernatants were mixed and extraction solution was added until a total volume of25ml was obtained.This extract was used for determination of phenol content and FRAP assay.

The amount of total phenolics in extracts was deter-mined according to the Folin–Ciocalteu’s procedure(Sin-gleton&Rossi,1965).Brie?y,0.05ml of diluted extract and0.45ml water were mixed with2.5ml of1:10diluted Folin–Ciocalteu’s phenol reagent,followed by2ml of 7.5%(w/v)sodium carbonate.After5min at50°C,absor-bance was measured at760nm.Phenol content was esti-mated from a standard curve of gallic acid and results expressed as mg gallic acid equivalents(GAE)100gà1dry weight(dw).

2.6.Antioxidant activity

The FRAP assay was developed to measure the ferric reducing ability of plasma at low pH(Benzie&Strain, 1996).A sample containing3ml of freshly prepared FRAP solution(0.3M acetate bu?er(pH3.6)containing10mM 2,4,6-tripyridyl-s-triazine(TPTZ)and40mM FeCl3?6H2O)and100l l of extract(prepared as for phenol deter-mination)was incubated at37°C for4min and the absor-bance was measured at593nm.An intense blue colour is formed when the ferric-tripyridyltriazine(Fe3+-TPTZ)

Table1

The examined raspberry,blackberry,raspberry·blackberry hybrids,red

currant,gooseberry and cornelian cherry cultivars and their colour

Cultivars Colour

Rubus ideaus(raspberries)

Heritage(Fallbearing)Red

Autumn Bliss(Fallbearing)Red

Fallgold(Fallbearing)Yellow

Meeker(Junebearing)Red

Rubus fructicosus(blackberries)

Choctaw Red-black

Thornless Evergreen Red-black

Chester Thornless Red-black

Hull Thornless Red-black

Rubus ideaus·Rubus fructicosus

Tayberry Red

Sunberry Red

Silvan Black

Ribes sativum(red currants)

London Market Red

Rovada Red

White Versailles Yellow

Ribes grossularia(goosberries)

Whinham’s Industry Red

White Smith Yellow

Cornus mas(Cornelian cherry)

Vermio Red

778G.E.Pantelidis et al./Food Chemistry102(2007)777–783

complex is reduced to the ferrous(Fe2+)form at593nm.A standard solution of1mM L-ascorbic acid in distilled water was prepared.The absorbance change was converted into a FRAP value,by relating the change of absorbance at 593nm of the test sample to that of the standard solution of L-ascorbic acid(AsA)and results were expressed as l mol AsA gà1dw.

In addition,non-site speci?c?OH radical scavenging activity was determined according to the deoxyribose method in the presence of100l M EDTA(Halliwell,Gut-teridge,&Aruoma,1987).FeCl3?6H2O and ascorbic acid solutions were prepared in degassed water prior to use.The reaction tube contained 1.5mM deoxyribose, 1.5mM H2O2,450l M L-ascorbic acid,50l M FeCl3?6H2O in 10mM phosphate bu?er(pH7.4),1.0ml total volume. Following incubation at38°C for30min,100l l100mM EDTA,1.0ml1.0%thiobarbituric acid+0.02%butylated hydroxyanisole in0.05M NaOH and1.0ml2.8%trichlo-roacetic acid were added to the reaction mixture,which was then heated in a boiling water bath for15min.Once samples were cooled,the absorbances were measured at 532nm.The percent inhibition of hydroxyl radical was cal-culated as follows:

%Inhibition?eA ControlàA SampleT

?100=A ControleAbs:532nm ControlT: Prooxidant activity was determined,using a modi?ca-tion of the deoxyribose assay(Moran,Klucas,Grayer, Abian,&Becana,1997).

2.7.Statistical analysis

At least three analyses were run for each cultivar for SSC,ascorbic acid,anthocyanin,phenol,total antioxidant and pro oxidant activity.Each analysis consisted of tripli-cate measurements of each sample and data were averaged over the three measurements.Data were treated for multi-ple comparisons by analysis of variance(ANOVA),fol-lowed by the Duncan’s Multiple Range test with signi?cance level P<0.05.Data in percentages were sub-jected to arcsine transformation prior to statistical analysis. ANOVA was performed using the statistical software SPSS (SPSS Inc.,Chicago,USA).Correlation coe?cients(r) were also calculated.

3.Results and discussion

3.1.Soluble solids content

Great variability existed among the examined berry fruits,regarding their content in SSC.The highest SSC was in the Cornelian cherry cultivar(14.4%),followed by the blackberry(9.8–11.5%)and raspberry cultivars(7.1–10.8%).The lowest content of soluble solids was recorded in the tayberry hybrid(6.1%)(Table2).3.2.Ascorbic acid

Signi?cant di?erences in ascorbic acid content among the di?erent species were recorded(Table3).Cornelian cherry had the highest content of ascorbic acid(103mg 100gà1fw)which was up to7.2-fold higher than the black-berry and blackberry·raspberry cultivars.The red currant cultivars and the autumn raspberry cultivars‘Heritage’and ‘Autumn Bliss’had the next highest in ascorbic acid con-tent(31.0–40.0mg100gà1fw),whereas June bearing rasp-berry and blackberry cultivars contained16.8–37.7and 14.3–17.5mg100gà1fw,respectively.These data are in agreement with those reported for other raspberry(21.2–31.1mg100gà1fw)(de Ancos,Gonzalez,&Cano,2000) and blackberry cultivars(12.3–16.4mg100gà1fw)(Deigh-ton,Brennan,Finn,&Davies,2000).

The native Cornelian cherry population of the present study showed higher ascorbic acid content compared to other cornelian cherry cultivars(48.4–73.1mg100gà1fw) (Demir&Kalyoncu,2003).In addition,its content was sig-ni?cantly higher than other fruits well known for their high ascorbic acid content,such as strawberries(46mg 100gà1fw)(Roberts&Gordon,2003),oranges(31mg 100gà1fw)(Roberts&Gordon,2003)and kiwi fruits (29–80mg100gà1fw)(Nishiyama et al.,2004).

3.3.Anthocyanins

Signi?cant di?erences in anthocyanin content were recorded,since these pigments are responsible for the red and blue colour.The Cornelian cherry cultivar contained Table2

Soluble solids content(%)of the examined cultivars after harvest Cultivar SSC(%) Heritage a,*10.0±0.1def Heritage b8.0±0.5abc Autumn Bliss a9.0±1.2bcde Autumn Bliss b7.1±1.5ab Fallgold a8.6±2.0bcd Fallgold b10.8±2.6ef Meeker7.3±0.1ab Tayberry 6.1±0.8a Sunberry7.6±0.9ab Silvan11.3±1.9f Choctaw11.5±1.5f Thornless Evergreen11.5±1.6f Chester Thornless10.6±1.6ef Hull Thornless9.8±2.2cdef London Market7.4±1.2ab Rovada10.7±0.8ef White Versailles8.4±1.1bcd Whinham’s Industry8.5±1.4bcd White Smith8.5±2.1bcd Vermio14.4±2.1g

a June harvest.

b Autumn harvest.

*Data are the means of three replications±standard error.Values within column followed by the same letter are not signi?cantly di?erent at P=0.05(Duncan’s Multiple Range test).

G.E.Pantelidis et al./Food Chemistry102(2007)777–783779

the highest anthocyanin content expressed as cyanidin-3-glucoside(223mg100gà1fw),followed by the blackberry and raspberry·blackberry cultivars(104–198mg 100gà1fw),whereas raspberry and red gooseberry culti-vars contained lower amounts of anthocyanins(35–49mg 100gà1fw)(Table3).The yellow raspberry(cv.Fallgold) and gooseberry(cv.White Smith)cultivars,as well as the red currant cultivars,were characterised by the lowest anthocyanin content(1.3–7.8mg100gà1fw).

Similar results for anthocyanin content have been reported by others researchers,both in raspberry(de Ancos et al.,2000)and blackberry(Wang&Lin,2000)cultivars, and therefore anthocyanins are regarded as important anti-oxidants in berry fruits(Mullen et al.,2002).However,in humans the bioavailability of dietary anthocyanins is low(-Mazza,Kay,Cottrell,&Holub,2002;Wu,Cao,&Prior, 2002).

3.4.Phenol content

Red currant cultivars contained small quantities of phe-nols expressed as gallic acid equivalents(GAE)(657–1193mg100gà1dw),followed by the gooseberry cultivars (1257–1321mg100gà1dw)(Table3).Signi?cantly higher phenol content was recorded in the second harvest of the autumn bearing red raspberries,whereas no di?erences between the harvest period were detected in the yellow raspberry cultivar bearing fruit twice.Our data indicated, besides the fact that raspberry genotype in?uence of total phenol content(Anttonen&Karjalainen,2005),that late harvest in particular cultivars signi?cantly increased their phenol content.Blackberry and the raspberry·blackberry cultivars were characterised by the highest phenol,content compared to other species,with values up to2611mg 100gà1dw.Similar results have been reported by other researchers in blackberries(1786–2310mg100gà1dw) and raspberries(1137–2112mg100gà1dw),whereas lower contents in other red currant cultivars have been observed (290–450mg100gà1dw)(de Ancos et al.,2000;Deighton et al.,2000;Prior et al.,1998;Wang&Lin,2000).

However,even when good experimental evidence exists, results need to be interpreted with caution in relation to human health bene?ts,as polyphenols may have limited bio-availability and may also be extensively metabolised(Dut-hie,Gardner,&Kyle,2003).Bioavailability di?ers greatly between the various polyphenols,and the most abundant polyphenols are not necessarily those that have the best bio-availability pro?le,either because they have a lower intrinsic activity or because they are poorly absorbed from the intes-tine,highly metabolised,or rapidly eliminated.

3.5.FRAP values

Red currant and gooseberry cultivars had the lowest FRAP values(40.7–65.1l mol AsA gà1dw)(Table4). The highest antioxidant activity was recorded in blackberry and in raspberry·blackberry cultivars(113.6–169.0l mol AsA gà1dw).The raspberry cultivars had FRAP values in the range77.7–145.4l mol AsA gà1dw.However,the autumn bearing red raspberry cultivars‘Autumn bliss’and‘Heritage’recorded higher FRAP values in fruits of the second harvest,the same as for phenol content(Table 3),whereas no di?erences between the two harvest periods of the yellow-coloured cultivar‘Fallgold’were observed.

Table3

Ascorbic acid,anthocyanin and phenol contents of the examined cultivars

Cultivar Ascorbic acid(mg100gà1fw)Anthocyanin(mg cyanidin-3-glucoside equivalents100gà1fw)Phenol(mg GAE100gà1dw) Heritage a,*32.4±2.1def49.1±7.8c1280±39de

Heritage b31.0±1.0cde48.2±6.4c1905±58i

Autumn Bliss a37.7±0.7fg35.1±2.6b1052±75b

Autumn Bliss b31.0±0.8cde39.1±6.8bc2494±77m

Fallgold a18.5±2.0a 1.3±0.4a1489±33f

Fallgold b16.8±0.2a 3.4±0.3a1459±66f

Meeker20.1±1.1ab42.6±5.3bc2116±44k

Tayberry19.7±1.6ab103.5±7.8d1891±76i

Sunberry28.0±2.3cd175.8±11.3g2611±69n

Silvan18.4±2.9a197.8±18.3h2016±89j

Choctaw14.6±1.2a125.6±1.6e1703±71h

Thornless Evergreen17.5±2.7a146.8±10.0f2061±148jk

Chester Thornless14.3±0.9a134.6±16.3e2008±99j

Hull Thornless14.5±1.3a152.2±8.4f2349±153l

London Market35.6±2.2efg7.8±0.8a1115±42bc

Rovada40.0±2.3g7.5±1.6a1193±64cd

White Versailles38.1±5.2fg 1.4±0.3a657±34a

Whinham’s Industry25.4±2.6bc43.3±2.5bc1257±65de

White Smith20.3±1.5ab 2.4±0.3a1321±69e

Vermio103.3±12.6h223.0±4.2i1592±132g

a June harvest.

b Autumn harvest.

*Data are the means of three replications±standard error.Values within column followed by the same letter are not signi?cantly di?erent at P=0.05 (Duncan’s Multiple Range test).

780G.E.Pantelidis et al./Food Chemistry102(2007)777–783

FRAP values were highly correlated with phenol con-tent(r=0.947),whereas a less linear correlation between total antioxidant capacity and anthocyanin content was recorded(r=0.635)(Table5).Inversely,ascorbic acid con-tent was negatively correlated with FRAP values (r=à0.363).

Similar results have been reported by other researchers (Wang&Lin,2000),who found a linear correlation between total antioxidant capacity and phenol content both in blackberries(r=0.961)and raspberries (r=0.911).In addition,Deighton et al.(2000)reported that there were apparent linear relationships between anti-oxidant capacity(assessed FRAP)and total phenols (r=0.965),whereas anthocyanin content had a minor in?uence on antioxidant capacity(r=0.588)and ascorbic acid contributed only minimally to the antioxidant poten-tial of Rubus juices.

Cornelian cherry,which was characterised by the high-est ascorbic acid and anthocyanin content and one of the highest phenol contents,possessed a relatively low FRAP value(83.9l mol AsA gà1dw),which may be due to the fact that during the air-drying of the sample at55°C for the FRAP assay,a signi?cant part of the ascorbic acid and anthocyanin content was destroyed.Piga,del Caro, and Corda(2003)found losses in ascorbic acid of55% and in anthocyanins of90%in plum fruits after drying at 60°C.

The assessment of antioxidant activity can be done by using di?erent in vitro methods.The FRAP assay is one of the most rapid tests and very useful for routine analysis, since a lot of samples can be analysed within a short time, although it has the limitation that it is conducted at non-physiological pH values.FRAP assay works employing metals ions for oxidation,measuring the formed ferrous ions by increased absorbance,instead of the use of organic radical producers(Schlesier,Harwat,Bohm,&Bitsch, 2002).The same authors strongly suggested the application of at least two methods for determination of antioxidant activity,due to di?erences between the test systems.

3.6.Deoxyribose protection

Red currants(16.1–27.0%)and gooseberry(34.1–35.3%) cultivars showed the lowest deoxyribose protection com-pared to other species(Table4).Among red currant culti-vars,the red-coloured had a higher percentage of deoxyribose protection,compared to the yellow-coloured, whereas non signi?cant di?erences were detected among gooseberry cultivars.The deoxyribose protection among raspberry cultivars was in the range65.2–92.2%,with the June bearing cultivar‘Meeker’possessing the highest per-centage.The raspberry·blackberry and the blackberry cultivars showed higher deoxyribose protection compared

Table4

Antioxidant capacity of the examined cultivars expressed as FRAP values(l mol gà1dw)and%deoxyribose protection

Cultivar l mol Ascorbic acid gà1dw%Deoxyribose protection Heritage a,*86.5±5.8c65.2±2.0g

Heritage b118.2±4.8d66.4±1.0g

Autumn Bliss a77.7±6.7c53.0±1.5e

Autumn Bliss b145.4±10.9ef70.5±1.4h

Fallgold a87.2±4.0c57.1±1.0f

Fallgold b88.8±7.7c65.8±1.5g

Meeker133.3±4.6e92.2±0.5jk

Tayberry149.3±11.2f93.7±0.4k

Sunberry169.7±18.2g86.7±0.5i

Silvan135.6±12.4ef91.1±0.6j

Choctaw113.6±7.2d96.4±0.2l

Thornless Evergreen146.6±17.1ef95.9±0.5l

Chester Thornless147.7±18.4f95.9±0.3l

Hull Thornless169.0±22.4g98.9±0.1m

London Market60.2±2.9b18.4±2.7b

Rovada63.3±2.2b27.0±2.3c

White Versailles40.7±1.4a16.1±4.2a

Whinham’s Industry62.8±2.6b34.1±3.4d

White Smith65.1±3.1b35.3±2.7d

Vermio83.9±5.4c98.6±0.3m

a June harvest.

b Autumn harvest.

*Data are the means of three replications±standard error.Values within column followed by the same letter are not signi?cantly di?erent at P=0.05 (Duncan’s Multiple Range test).

Table5

Correlation coe?cients(r)of antioxidant capacity with ascorbic acid,

anthocyanin and phenol contents

Correlation coe?cient(r)

FRAP Deoxyribose assay

Ascorbic acidà0.363à0.082

Anthocyanins0.6350.789

Phenols0.9470.773

FRAP–0.838

Deoxyribose protection0.838–

G.E.Pantelidis et al./Food Chemistry102(2007)777–783781

to raspberry,gooseberry and red currant cultivars,whereas the Cornelian cherry cultivar showed the highest deoxyri-bose protection(98.6%),along with the blackberry cultivar ‘Hull Thornless’(98.9%).It has been reported that black-berries had the highest antioxidant capacity for the inhibi-tion of free radicals(Wang&Jiao,2000),and our?ndings agree with these data.

Deoxyribose protection had a relatively high correlation with FRAP values(r=0.838),anthocyanin(r=0.789)and phenol content(r=0.773).Considerable data suggest that higher contents of total phenolics,?avonoids,and anthocy-anins in red raspberry fruits contribute to their higher anti-oxidant activity(Wang&Lin,2000).Our data are in agreement with those reported by other researchers(Kalt et al.,1999)who postulated that antioxidant capacity was strongly correlated with the total phenol(r=0.830)and anthocyanin(r=0.900)content in other small fruits. Inversely,ascorbic acid made only a small contribution (0.4–9.4%)to the total antioxidant capacity of the fruit (Kalt et al.,1999).In addition,when Kalt et al.(1999) made a comparative study,examining the antioxidant properties of small fruits,they divided them into two dis-tinct groups:(a)those with high phenolics,anthocyanins, and antioxidant capacity(measured as oxygen radical absorbing capacity)and low ascorbate;and(b)those with low phenolics,anthocyanins,and antioxidant capacity and high ascorbate.These data strengthen the hypothesis that no direct correlation between ascorbic acid content and total antioxidant capacity can be established.A strong cor-

relation(r=0.930–0.960)between total phenolics and anti-oxidant activity has been also reported in stone fruits(Gil, Toma¨s-Barbera¨n,Hess-Pierce,&Kader,2002).

In most samples,a close correlation of antioxidant capacity,as measured by the two methods,was recorded, except for the Cornelian cherry fruit.This might be attrib-uted to di?erent phenol compositions among di?erent spe-cies.It is well documented that deoxyribose protection varies among di?erent phenolic substances(Moran et al., 1997).Therefore,deoxyribose protection is highly depen-dent,not just on total phenol content,but on phenol type, and antioxidant capacity.A multitude of phenolic com-pounds have been detected in berries,including?avanols (kaempferol,quercetin,myricetin)and phenolic acids(ella-gic,gallic,p-hydroxybenzoic,ferulic,ca?eic,p-coumaric acid),and great di?erences among berry species exist,with regard to their phenolic pro?les(Hakkinen et al.,1999).

3.7.Prooxidant activity

Prooxidant activity was monitored in gallic acid(50l M) and ascorbic acid(50l M)solutions,for comparative stud-ies.Results indicated that their absorbance were132%and 228%,respectively,compared to the control(100%).Pro-oxidant activity was recorded solely in the second harvest of the raspberry cultivar‘Autumn bliss’(103%),in the red currant cultivars‘London Market’(102%)and ‘Rovada’(106%),and in the two gooseberry cultivars (101%).No prooxidant activity was observed in any of the other cultivars.These results indicate that the extracts of almost all the examined cultivars possessed antioxidant capacity greater than their ability to degrade deoxyribose. Furthermore,the Cornelian cherry samples showed the lowest prooxidant activity.R?dtjer,Skibsted,and Ander-sen(2006)monitored the antioxidant and prooxidant activ-ities of pure phenolic compounds and illustrated the very di?erent properties that these compounds can have in oxi-dation reactions.Therefore,prooxidant activity cannot be correlated with antioxidant capacity and especially with ascorbic acid and anthocyanin content(see Table6).

4.Conclusions

Small fruits are a signi?cant source of phenolic com-pounds and ascorbic acid.Antioxidant activity varied greatly among the berry cultivars used in this study and was highly correlated with their contents of phenolic com-pounds.The present study indicates that the Cornelian cherry is an extremely rich source of ascorbic acid,antho-cyanin,phenols and antioxidants,demonstrating its poten-tial use as a food additive.

Cornelian cherry is found at relative high altitude,only in the Mediterranean area and to the best of our knowl-edge,few data exist regarding their quality attributes (Demir&Kalyoncu,2003).Since commercial Cornelian cherry cultivars do not exist,further studies should be con-Table6

Prooxidant activity expressed as%absorbance compared with control (not containing sample)

Cultivar%Absorbance Heritage a84.7±1.0ef Heritage b92.3±2.1gh Autumn Bliss a80.1±2.5bc Autumn Bliss b103.1±1.4l Fallgold a95.3±1.6ij Fallgold b94.2±2.0hi Meeker97.0±2.2j Tayberry79.8±1.5bc Sunberry90.8±0.7g Silvan74.6±1.6a Choctaw79.4±5.5b Thornless Evergreen86.0±3.3f Chester Thornless81.8±0.5cd Hull Thornless82.5±1.5de London Market101.8±1.7kl Rovada106.0±1.4m White Versailles93.8±0.3hi Whinham’s Industry100.8±0.1kl White Smith100.9±0.9kl Vermio76.3±0.6a Control*100.0±0.0k Gallic acid,50l M131.5±2.1n Ascorbic acid,50l M227.6±0.4o

a June harvest.

b Autumn harvest.

*Data are the means of three replications±standard error.Values within column followed by the same letter are not signi?cantly di?erent at P=0.05(Duncan’s Multiple Range test).

782G.E.Pantelidis et al./Food Chemistry102(2007)777–783

ducted among native populations,in order to determine those high in antioxidant properties,which could be used as breeding material.

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G.E.Pantelidis et al./Food Chemistry102(2007)777–783783

聚氨酯新材料项目职业病危害检测评价分析

聚氨酯新材料项目职业病危害检测评价分析 根据5中华人民共和国职业病防治法6和5建设项目职业病危害评价规范6等法律法规、卫生标准要求, 我们对某聚氨酯( PU )新材料工程项目职业病危害控制效果进行评价。现将评价结果报告如下。 1 评价内容、方法 1. 1 评价内容1 分析评价该项目生产或操作过程中产生的有毒有害物质、生产性噪声等职业病危害因素的种类、分布、浓度或强度及其对工人健康的影响。o 分析评价职业病防护措施实施情况, 包括总平面布置、生产工艺及设备布局、车间建筑设计卫生要求、卫生工程防护设施的控制效果、应急救援措施、个人防护设施, 辅助卫生用室设置、职业卫生管理措施等。 1. 2 评价方法按5建设项目职业病危害评价规范6 [ 1] 要求,用检查表和定量分级法评价该扩建项目中职业病危害因素对健康的影响、职业病防护措施实施情况[2] 。 1. 2. 1 职业卫生检测方法按5全国疾病预防控制机构工作规范6 [ 3] ( 2001年版)选择采样点。粉尘浓度检测用称重法( DS-21B 粉尘采样器), 噪声强度检测用直读方法( AWA6218B 噪声统计分析仪), TDI和二氯甲烷的检测用色谱分析法; CO2 用直读式仪器法。 1. 3 控制效果评价主要依据1 5中华人民共和国职业病防治法6 ( 2002- 05- 01); o 5建设项目职业病危害评价规范6 [ 1] ;. 5工业企业设计卫生标准6 [4] GBZ 1- 2002; . 5工作场所有害因素职业接触限值6 [ 5] GBZ 2- 2002; . 委托方提供的有关技术文件和资料。 2 结果分析 2. 1 项目工程分析及主要职业病危害因素 2. 1. 1 项目工程分析该新建项目主要产品为聚氨酯软泡塑料,生产工艺流程如下: 将原料罐的物料聚醚( PPG)、甲苯-2, 4二异氰酸酯(TDI)、三乙烯二胺、硅油、辛酸亚锡、水、色料、填料、阻燃剂、抗氧化剂、CO2 按一定量的配比经计量泵送入混合头。通过自控仪表装置将混合头的物料送入发泡头, 发泡头的压力为2. 5MPa, 通过发泡段输送带经走纸装置、红外线加热装置和真空抽气装置, 成形后由输送带送入切割输送带, 得成品, 发泡温度控制在20~ 24 c,再将成品经平切机分别切出所需成品。 2. 1. 2 主要职业病危害因素根据现场职业卫生调查, 该新建工程项目主要职业病危害因素有粉尘、TDI、二氯甲烷、CO2 及噪声等等。 2. 2 现场检测结果分析 2. 2. 1 作业场所粉尘对生产车间颜料粉碎机、混配槽等作业岗位粉尘浓度进行检测, 并按5生产性粉尘作业危害程度分级6 [ 6] ( GB 5817- 86)对粉尘危害程度进行分级, 结果见表1。

石墨电极的原料及制造工艺

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石墨电极在黄磷冶炼中的应用 近年来我国的黄磷企业迅速扩增,其产品不仅遍及全国各地,而且已形成了大量出口的趋势。黄磷冶炼行业的崛起,为炭素厂家又增加了一大市场。仅我国西南地区年产黄磷制品就近百万吨,年耗石墨电极约3万t。因此,石墨电极如何适用于电炉冶炼黄磷的技术课题,已经提到电极生产厂家的面前。人造石墨电极具有良好的导电、导热、耐高温氧化、耐腐蚀性能,是黄磷冶炼炉理想的导电电极。石墨电极的生产工艺过程,一般是将石油焦、沥青焦等炭质原料经煅烧后,再加粘结剂沥青进行混捏、凉料后经挤压成型而形成生制品,生制品再经过1 300 ℃焙烧后成为半成品,半成品再经过2 300 ℃石墨化、机械加工而得到石墨电极成品。目前,炭素企业生产的石墨电极,其部分规格的理化指标列于表1。表1 石墨电极的主要理化指标 规格/mm 品种电阻率/μΩ.m 体积密度/kg/cm3 抗折强度/MPa 弹性模量/GPa 热膨胀系数/×10-6/℃灰分/% 本体接头本体接头本体接头本体接头本体接头 600 UHP 6.5 4.5 1.66 1.75 10.0 18.0 14.0 22.0 1.40 1.20 0.5 500 HP 7.0 6.5 1.60 1.70 9.8 14.0 12.0 14.0 2.20 2.40 0.3 500UHP NP 9.0 8.5 1.52 1.68 6.4 12.7 9.3 13.7 2.90 3.20 0.5 1 黄磷冶炼与石墨电极的消耗 工业上依黄磷冶炼中的热源不同,黄磷冶炼方法可分为电炉法和高炉法。目前我国的黄磷冶炼工业主要以电炉法为主,这种冶炼方法实收率高,产品纯度高。电炉法生产是将磷矿石、硅石和焦炭的混合料加入电炉内,由通过炉盖的石墨电极(作为导电极)将电能转变成热能,从而把混合料加热至熔融状态,使元素磷升华后再将含磷气体进行冷凝、分离和精制而得到元素磷。黄磷冶炼的工艺过程如图1。

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二、适用范围 本文针对不同方法学的第三类体外诊断试剂技术要求附录中的主要材料、生产工艺及半成品检定等内容进行规范,明确附录内容编写要求,适用于第三类体外诊断试剂注册、延续注册及注册变更申请。 三、基本要求 (一)主要材料 1.通用要求。 主要原材料来源一般有两种途径,生产企业自行制备或外购于其他供货商。申请人在编写产品技术要求附录时,针对不同来源的原材料须明确的内容也不相同,具体要求如下。 (1)企业外购原材料:生产企业应明确供货商名称,供货商应相对固定,不得随意更换。生产企业还应确定主要原材料的质量控制标准,下面对几种常见的原材料进行描述。 a、抗原:应明确抗原名称、生物学来源、供货商名称等信息,应对抗原技术指标的要求进行详述。 b、抗体:应描述抗体名称、克隆号、生物学来源,供货商名称及刺激免疫原等信息,应对抗体技术指标的要求进行详述。 c、引物、探针:应明确所有引物、探针的供货商、核酸序列及主要技术指标要求。 (2)企业自制原材料:生产企业应明确原材料的制备原理,摘要性描述制备过程,确定主要原材料的质量控制标准。 a、抗原:如为天然抗原,例如病原体检测试剂所用抗原应明确

新型聚氨酯固化剂的研究与发展

新型聚氨酯固化剂的研究与发展 张修景(菏泽学院化学与化工系,山东菏泽274015) 摘要:阐述了颜色低于铁钴比色计1号,游离TDI含量小于0.5%,贮存稳定性达2年以上的新型聚氨酯固化剂的生产工艺;确定了含羟基丙烯酸树脂与该固化剂的质量比为:m(含羟基丙烯酸树脂)∶m(新型聚氨酯固化剂)=10∶4~6;分析了碱性物质是导致聚氨酯固化剂成胶的原因;提出了保证聚氨酯固化剂低色值、低游离TDI含量和高贮存稳定性的方法。 关键词:新型聚氨酯固化剂;色值;游离TDI含量;稳定性 0.引言 国内科研单位及相关企业、院校对于聚氨酯固化剂的研究做了大量工作,朱吕民[1]介绍了色泽为8号(铁钴比色计)TDI加成物的制法;彭红为,等[2-3]报道的产品的游离TDI含量高达3.0%~5.0%,配制的涂料在施工过程中对人体伤害很大,环境污染严重,不仅远远高出世界卫生组织游离TDI含量≤0.5%的要求,而且很难达到我国《室内装饰装修材料溶剂型木器涂料中有害物质限量》GB18581—2001强制标准中≤0.7%的规定。国外通常采用薄膜蒸发法,如Bayer公司采用该技术产品的游离TDI含量<0.5%。国内相关研究[4-10]对于降低游离TDI做了大量积极工作,并提出了在聚氨酯生产中推行清洁生产的建议和措施,但实现工业化生产的报道很少。赵文斌,等[10]的产品通过热重分析(TG)显示,改性TDI三聚体的热稳定性有一定下降。为此,本文研究了颜色低于铁钴比色计1号,游离TDI<0.5%,贮存稳定性达2年以上的TDI-TMP加成物,找到了该固化剂与含羟基丙烯酸树脂的最佳配比,可赋于漆膜多种优良的性能。 1.实验部分 1.1原料 甲苯二异氰酸酯(TDI):80/20,国产;三羟甲基丙烷(TMP):美国产;乙酸丁酯:工业一级品,无水;二月桂酸二丁基锡、缩二脲:工业一级品;磷酸(85%)、三正丁基膦、对硝基苯甲酰氯:分析纯;氮气(99199%)。 1.2反应原理 TDI-TMP加成物主要是指3分子的甲苯二异氰酸酯(TDI)与1分子的三羟甲基丙烷(TMP)的加成物,反应如式1。 1.3方法 新型聚氨酯固化剂的中试配方见表1。

石墨电极

石墨电极 石墨电极(graphite electrode) 以石油焦、沥青焦为颗粒料,煤沥青为黏结剂,经过}昆捏、成型、焙烧、石墨化和机械加工而制成的一种耐高温的石墨质导电材料。石墨电极是电炉炼钢的重要高温导电材料,通过石墨电极向电炉输入电能,利用电极端部和炉料之间引发电弧产生的高温为热源,使炉料熔化进行炼钢,其他一些电冶炼或电解设备也常使用石墨电极为导电材料。2000年全世界消耗石墨电极100万t左右,中国2000年消耗石墨电极25万t左右。利用石墨电极优良的物理化学性能,在其他工业部门中也有广泛的用途,以生产石墨电极为主要品种的炭素制品工业已经成为当代原材料工业的重要组成部门。 简史早在1810年汉佛莱?戴维(Humphry Davy)利用木炭制成通电后能产生电弧的炭质电极,开辟了使用炭素材料作为高温导电电极的广阔前景,1846年斯泰特(Stair)和爱德华(Edwards)用焦炭粉及蔗糖混合后加压成型,并在高温下焙烧从而制造出另一种炭质电极,再将这种炭质电极浸在浓糖水中以提高其体积密度,他们获得了生产这种电极的专利权。1877年美国克利夫兰(Cleveland)的勃洛希(C.F.Brush)和劳伦斯(https://www.wendangku.net/doc/a53363637.html,wrence)采用煅烧过的石油焦研制低灰分的炭质电极获得成功。1899年普利查德(O.G.Pritchard)首先报道了用锡兰天然石墨为原料制造天然石墨电极的方法。1896年卡斯特纳(H.Y.Gastner)获得了使用电力将炭质电极直接通电加热到高温,而生产出比天然石墨电极使用性能更好的人造石墨电极的专利权。1897年美国金刚砂公司(Carborundum Co.)的艾奇逊(E.G.Acheson)在生产金刚砂的电阻炉中制造了第一批以石油焦为原料的人造石墨电极,产品规格为22mm×32m mX380mm,这种人造石墨电极当时用于电化学工业生产烧碱,在此基础上设计的“艾奇逊”石墨化炉将由石油焦生产的炭质电极及少量电阻料(冶

石墨电极的生产工艺流程和质量指标的及消耗原理知识讲解

石墨电极的生产工艺流程和质量指标的及 消耗原理

目录 一、石墨电极的原料及制造工艺 二、石墨电极的质量指标 三、电炉炼钢简介及石墨电极的消耗机理 石墨电极的原料及制造工艺 ●石墨电极是采用石油焦、针状焦为骨料,煤沥青为粘结剂,经过混 捏、成型、焙烧、浸渍、石墨化、机械加工等一系列工艺过程生产出来的一种耐高温石墨质导电材料。石墨电极是电炉炼钢的重要高温导电材料,通过石墨电极向电炉输入电能,利用电极端部和炉料之间引发电弧产生的高温作为热源,使炉料熔化进行炼钢。其他一些冶炼黄磷、工业硅、磨料等材料的矿热炉也用石墨电极作为导电材料。利用石墨电极优良而特殊的物理化学性能,在其他工业部门也有广泛的用途。生产石墨电极的原料有石油焦、针状焦和煤沥青 ●石油焦是石油渣油、石油沥青经焦化后得到的可燃固体产物。色黑 多孔,主要元素为碳,灰分含量很低,一般在0.5%以下。石油焦属于 易石墨化炭一类,石油焦在化工、冶金等行业中有广泛的用途,是生产人造石墨制品及电解铝用炭素制品的主要原料。 ●石油焦按热处理温度区分可分为生焦和煅烧焦两种,前者由延迟 焦化所得的石油焦,含有大量的挥发分,机械强度低,煅烧焦是生焦经煅烧而得。中国多数炼油厂只生产生焦,煅烧作业多在炭素厂内进行。 ●石油焦按硫分的高低区分,可分为高硫焦(含硫1.5%以上)、中 硫焦(含硫0.5%-1.5%)、和低硫焦(含硫0.5%以下)三种,石墨电极及其它人造石墨制品生产一般使用低硫焦生产。 ●针状焦是外观具有明显纤维状纹理、热膨胀系数特别低和很容易石 墨化的一种优质焦炭,焦块破裂时能按纹理分裂成细长条状颗粒(长宽比一般在1.75以上),在偏光显微镜下可观察到各向异性的纤维状结 构,因而称之为针状焦。 ●针状焦物理机械性质的各向异性十分明显, 平行于颗粒长轴方向具 有良好的导电导热性能,热膨胀系数较低,在挤压成型时,大部分颗粒的长轴按挤出方向排列。因此,针状焦是制造高功率或超高功率石墨电极的关键原料,制成的石墨电极电阻率较低,热膨胀系数小,抗热震性能好。 ●针状焦分为以石油渣油为原料生产的油系针状焦和以精制煤沥青 原料生产的煤系针状焦。 ●煤沥青是煤焦油深加工的主要产品之一。为多种碳氢化合物的混合 物,常温下为黑色高粘度半固体或固体,无固定的熔点,受热后软化,继而熔化,密度为1.25-1.35g/cm3。按其软化点高低分为低温、中温和高温沥青三种。中温沥青产率为煤焦油的54-56%。煤沥青的组成极为复杂,与煤焦油的性质及杂原子的含量有关,又受炼焦工艺制度和煤焦油加工条件的影响。表征煤沥青特性的指标很多,如沥青软化点、甲苯不溶物(TI)、喹啉不溶物(QI)、结焦值和煤沥青流变性等。

腰果酚应用研究进展..

12应用化学(职教本科1班彭思20120651 腰果酚应用研究进展 摘要:本文从官能团改性方面,综述了近几年国内外腰果酚衍生物的化学合成及在材料与精细化学品中的潜在应用,其中包括腰果酚酚羟基、腰果酚苯环及腰果酚侧链的改性。 关键词:腰果酚;腰果壳油;衍生物;应用;进展 前言:随着全球化石资源日趋减少,可再生资源的开发利用越来越引起人们的重视[1]。腰果壳液(CNSL)是腰果加工中的一种副产品,其含量约占腰果的25%-30%,世界年产量约50万吨,是一种价廉丰富的可再生资源[2-3]。CNSL 的最主要成分是腰果酚(cardanol)(1),含量可达90%。从结构来看,腰果酚属于苯酚的衍生物,在苯酚的间位被15个碳的直链(含0-3个碳碳双键)所取代(图1)(如无特殊说明,本文其它图中的R基团都代表腰果酚的侧链)。腰果酚可改性合成很多衍生物,包括功能小分子与聚合物,它们在涂料、摩擦材料、抗氧化剂、杀虫杀菌剂等方面都极具应用价值[4]。本文主要从腰果酚所含的三种官能团出发,总结通过酚羟基、苯环、不饱和侧链上的反应来制备各种有价值的腰果酚衍生物。 1利用腰果酚的羟基制备腰果酚衍生物 1.1腰果酚的酯类衍生物 腰果酚分子中含有活泼的酚羟基,可通过酯化、醚化反应制备相应的衍生物。例如张中云等[5]在-15℃左右使腰果酚与ClCN反应,生成腰果酚氰酸酯(2),2再与双酚A型氰酸酯(NCO-BPA-OCN)反应,制得了新型热固性树脂(图2)。由于树脂中引进了腰果酚所含的15个碳的柔性链,有效地提高了氰酸酯树脂的柔韧性,同时提高了其介电性能和耐吸水性能。

林金火课题组[6]用马来酸酐和腰果酚反应得到马来酸腰果酚单酯,然后与乙二醇进一步发生酯化反应 (图3),最后将酯化产物进行缩甲醛化反应,合成了同时具有软段结构(顺丁烯二酸乙二醇酯结构单元)和硬段结构(酚醛结构单元)的多羟基腰果酚醛树脂,该树脂具有优良的涂膜性能;所得的多羟基腰果酚醛树脂 也可与聚氨酯预聚体组成性能优良的双组分聚氨酯漆,可改善普通腰果漆的柔韧性和附着力。 为了制备新型抗氧化剂,Lomonaco等[7]用腰果酚和强心酚(cardol,腰果壳油的另一种成分)与二乙氧基硫代磷酰氯反应,制备了相应的硫代磷酸酯化合物(3)和(4)(图4)。将所制硫代磷酸酯在聚甲基丙烯酸甲酯中掺入1%的量,结果聚合物的热稳定性提高了很多。特别是化合物4中既含有硫代磷酸酯结构,又含有酚羟基结构,同时具有一类和二类抗氧化剂的功能,因此对材料的热稳定性提高最明显。

聚氨酯

聚氨酯基本理论知识 一. 聚氨酯(polyurethane)大分子主链上含有许多氨基甲酸酯基: 它由二(或多)异氰酸酯、二(或多)元醇与二(或多)元胺通过逐步聚合反应生成,除了氨基甲酸酯基(简称为氨酯基)外,大分子链上还往往含有 醚基 、酯基、脲基、 酰胺基 等基团,因此大分子间很容易生成氢键。 二.聚氨酯主要原料 N H C O O O C O O NH O NH NH O

1、异氰酸酯及其结构特征 一、结构特点 在分子结构中含有异氰酸酯基团(-N=C=O)的化合物,均称为异氰酸酯(isocyanate),其结构通式如下:R-(NCO)n式中R为烷基、芳基、脂环基等;n=1、2、3….整数。在聚氨酯材料合成中,主要使用n≥2的异氰酸酯化合物。 二、异氰酸酯的分类 (1)异氰酸酯基团数量 1.异氰酸酯 异氰酸酯(Isocyanate)是一大类含有异氰酸基(—N=C=O)的 有机化合物。异氰酸酯基由于其累积双键和碳原子两边的电负性很 大的氮氧原子作用,使之具有很高的反应活性,能与绝大多数含活 泼氢的物质发生反应。常用的异氰酸酯主要有芳香族类和脂肪类两种。⑴芳香族类的主要有:TDI(2, 4—甲苯二异氰酸酯或2, 6—甲 苯二异氰酸酯)、MDI(二苯基甲烷- 4, 4’二异氰酸酯)、NDI (1, 5—萘二异氰酸酯)、PAPI(多亚甲基多苯基多异氰酸酯)等;芳 香族多异氰酸酯合成的聚氨酯树脂户外耐候性差,易黄变和粉化, 属于“黄变性多异氰酸酯”,但价格低,来源方便,在我国应用广泛,如TDI常用于室内涂层用树脂;聚氨酯树脂中90%以上属于芳香族

多异氰酸酯。与芳基相连的异氰酸酯基对水和羟基的活性比脂肪基异氰酸酯基团更活泼。基于TDI 的聚氨酯由于高的苯环密度,其力学性能也较脂肪族多异氰酸酯的聚氨酯更为优异。以下是一些常用的产品。 (1)甲苯二异氰酸酯(tolulene diisocyanate ,TDI ) 甲苯二异氰酸酯是最早开发、应用最广、产量最大的二异氰酸酯单体;根据其两个异氰酸酯(—NCO )基团在苯环上的位置不同,可分为2,4-甲苯二异氰酸酯(2,4-TDI,简称2,4-体)和2,6-甲苯二异氰酸酯(2,6-TDI ,2,6-体)。 室温下,甲苯二异氰酸酯为无色或微黄色透明液体,具有强烈的刺激性气味。市场上有3种规格的甲苯二异氰酸酯出售,T-65为2,4-TDI 、2,6-TDI 两种异构体质量比为65%/35%的混合体;T-80为2,4-TDI 、2,6-TDI 两种异构体质量比为80%/20%的混合体,其产量最高、用量最大,性价比高,涂料工业常用该牌号产品;T-100为2,4-TDI 含量大于95%的产品,2,6-TDI 含量甚微,其价格较贵。2,4-TDI 其结构存在不对称性,由于-CH3的空间位阻效应,4位上的-NCO 的活性比2位上的-NCO 的活性大,50℃反应时相差约8倍,随着温度的提高,活性越来越靠近,到100 ℃时,二者即具有相同的活性。因此,设计聚合反应时,可以利用这一特点合成出结构规整的聚合物。TDI 的弱点是蒸汽压大,易挥发,毒性大,通常将其转变成齐聚物(oligomer )后使用;而且由其合成的聚氨酯制品存在比较严重的黄变性。黄变性的原因在于芳香族聚氨酯的光化学反应,生成芳胺,进而转化成了醌式或偶氮结构的生色团。2,4-TDI 凝固点6-20度,TDI 的含量越高凝固点。 NCO CH 3NC O O CH 3 OCN 2,6-TDI 2,4-TDI

碳素材料简介

碳素材料简介 炭和石墨材料是以碳元素为主的非金属固体材料,其中炭材料基本上由非石墨质碳组成的材料,而石墨材料则是基本上由石墨质碳组成的材料。为了简便起见,有时也把炭和石墨材料统称为炭素材料(或碳材料)。 主要分类: 碳素散热片是以不干胶的形色直接将碳素散热片贴在芯片表面,碳素散热片因其柔软可与所贴附对象十分紧密的粘合,另外因其高热传导性(树脂的5-15倍)、横向的高热传导性(铜的两倍),与传统使用中的导热硅胶、硅胶片、金属片等比较,高碳素散热片能将热量均匀扩散更大幅度的散热。 高热传导平面用散热片: 利用其平面的高热传导性(铜的两倍),可将热迅速传递到金属壳以及散热型材上,降低发热点的温度,从而达到更好的散热效果。 炭素制品按产品用途可分为石墨电极类、炭块类、石墨阳极类、炭电极类、糊类、电炭类、炭素纤维类、特种石墨类、石墨热交换器类等。石墨电极类根据允许使用电流密度大小,可分为普通功率石墨电极、高功率电极、超高功率电极。炭块按用途可分为高炉炭块、铝用炭块、电炉块等。炭素制品按加工深度高低可分为炭制品、石墨制品、炭纤维和石墨纤维等。炭素制品按原

料和生产工艺不同,可分为石墨制品、炭制品、炭素纤维、特种石墨制品等。炭素制品按其所含灰分大小,又可分为多灰制品和少灰制品(含灰分低于l%)。 我国炭素制品的国家技术标准和部颁技术标准是按产品不同的用途和不同的生产工艺过程进行分类的。这种分类方法,基本上反映了产品的不同用途和不同生产过程,也便于进行核算,因此其计算方法也采用这种分类标准。下面介绍炭素制品的分类及说明。 主要制品 碳素行业的上游企业主要有:1、无烟煤的煅烧企业;2、煤焦油加工生产企业;3、石油焦生产及煅烧企业。炭和石墨制品: (一)石墨电极类 主要以石油焦、针状焦为原料,煤沥青作结合剂,经煅烧、配料、混捏、压型、焙烧、石墨化、机加工而制成,是在电弧炉中以电弧形式释放电能对炉料进行加热熔化的导体,根据其质量指标高低,可分为普通功率、高功率和超高功率。石墨电极包括:(1)普通功率石墨电极。允许使用电流密度低于17A/厘米2的石墨电极,主要用于炼钢、炼硅、炼黄磷等的普通功率电炉。 (2)抗氧化涂层石墨电极。表面涂覆一层抗氧化保护层的石墨电极,形成既能导电又耐高温氧化的保护层,降低炼钢时的电极消耗。

(整理)体外诊断试剂分析性能评估系列指导原则.

附件: 《体外诊断试剂分析性能评估系列指导原则(征求意见稿)》

目录 1.体外诊断试剂分析性能评估指导原则――编制说明 2.体外诊断试剂分析性能评估指导原则——检测限 3.体外诊断试剂分析性能评估指导原则——线性范围 4.体外诊断试剂分析性能评估指导原则——可报告范围 5.体外诊断试剂分析性能评估指导原则——准确度(回收实验) 6.体外诊断试剂分析性能评估指导原则——准确度(方法学比对) 7.体外诊断试剂分析性能评估指导原则——精密度 8.体外诊断试剂分析性能评估指导原则——干扰实验 9.体外诊断试剂分析性能评估指导原则——稳定性 10.体外诊断试剂分析性能评估指导原则——参考值(参考区

间) 附件1: 体外诊断试剂分析性能评估指导原则 编制说明 《体外诊断试剂注册管理办法(试行)》颁布后,体外诊断试剂产品的注册过程中要求提供申报产品的分析性能评估资料,产品性能评估是产品研发、制定产品标准等过程的重要技术支持研究过程,并可能对产品的质量造成一定的影响。 目前国际上对体外诊断试剂的性能评估通常是以美国临床实验室标准化组织(Clinical and Laboratory Standards Institude以下称为CLSI)的相关标准为依据,也是美国FDA 推荐采用的评价标准,但我国还没有相关的标准及指导原则的要求。 为进一步明确体外诊断试剂分析性能评估的技术要求,

我中心组织有关专家起草产品分析性能评估指导原则,以明确体外诊断试剂产品性能评估的技术要求。体外诊断试剂产品性能评估包括检测限、线性范围、可报告范围、准确度(回收实验)、准确度(方法学比较)、精密度、干扰实验、稳定性、参考区间共九个项目。起草的主要依据CLSI发布的以下标准: 1. C28-A2: How to define and determine reference intervals in the clinical laboratory; Approved Guideline-Second Edition. 2. EP5-A: Evaluation of precision performance of clinical chemistry devices; Approved Guideline. 3. EP6-A: Evaluation of the linearity of quantitative measurement procedures; A Statistical Approach; Approved Guideline. 4. EP7-A: Interference testing in clinical chemistry; Approved Guideline. 5. EP9-A2: Method comparison and bias estimation using patient samples; Approved Guideline-Second Edition. 每项性能的主要研究方法均采用以上标准和国内实际采用的评价方法相结合的方法。 我中心对于专家起草的指导原则的初稿进行了适当的文字调整,之后将分析性能评估指导原则发给十位相关专业的专家征求意见。意见返回后我们对专家的回复意见进行了

石墨电极编程作业

目的: 为了完善公司的编程管理制度,电脑文档管理,编程方法,加工参数,程序单制做,各种类型的工件的刀路编写能有固定.统一的制度及方法。以达到公司各类型产品制做周期准时,确保生产编排运作正常,产品质量稳定,赢得客户信任。和提高编程技术人员编程技能之目的。 目录: 1.电脑管理制度。 2.图档管理及NC程序管理规范。 3.程序单编写归定。 4.一般类型电极编程技巧及实例。 5.超行程电极的编程方法。 6.喇叭网孔电极编程方法。 7.EROWA制具使用方法。 8.长条(小电极用)夹具组使用方法。 电脑管理制度 1.1 每台电脑责任人必须管理好所用电脑及其各组件之保护及保养,

以确保无遗失,无损坏,能够长期正常运作。 1.2 电脑外表面必须每天清理.主机箱每周清理一次。 1.3 电脑不得私自更改.添加及删除用户名和密码。 1.4 未经主管批准.不得安装工作必须使用的软件之外的任何电脑程序及软件.如:游戏.音乐.非本公司常用编程软件等。 1.5不得私自拷贝.删除公司电脑内的任何资料。 1.6电脑如有硬件方面故障要及时填写“电脑维修申请单”交由电脑 部处理。 图档管理及NC程序管理规范 电极编程技巧及实例 特别说明:骨位电极侧面光刀一般选用平底刀或平底R角刀,其加工步距一定要跟据骨位斜度设定加工下切步距.我公司归定为:从0到0.5度每刀下切0.22MM, 从0.5到1度每刀下切0.2MM, 从1到2度每刀下切0.17MM, 从2到5度每刀下切0.12---0.15MM,如斜度大于5度可跟据电极型壮选合理的刀具及步距(一般用球头刀)。 扫顶程序:(目的:铲掉高度方向多余材料)每个电极必须要有扫顶程序,编程用“偏置粗加工策略”分2层加工,每层下2MM,高度方

聚氨酯用新型抗氧化剂

聚氨酯用新型抗氧化剂 氨纶(聚氨酯弹性纤维)具有高断裂伸长(400%以上) 、低模量和高弹性回复率,目前已是一种广泛应用于各类纺织品、服装面料的功能性化纤,可以说在高端服装面料上“无氨不成布”。自1959年美国杜邦工业化生产以来,迄今全球已有60万吨产能,其中,中国占60%以上。目前,氨纶生产工艺最主要的是干法纺丝,少部分是熔融纺丝。干法纺丝的生产方法是将MDI 和PTMEG 预聚,再以二元胺扩链,最后封端,以上化学反应都是在DMAC 溶剂中进行的,反应完的氨纶原液经由高温纺丝甬道抽丝,去除并回收溶剂,而纺出的氨纶单丝则经过加捻,上油,熟化后成为氨纶产品。氨纶丝的耐热、耐UV 都不是很好,所以需要在生产中额外添加耐老化助剂(一般在聚合结束后添加),以达到用户的要求。因干法工艺的加工温度较高,要求添加剂具有很好的耐高温挥发,耐溶剂抽提的性能。 常用的氨纶耐老化助剂有: 紫外线吸收剂:通常使用苯并三唑类紫外线吸收剂234 化学名称:2-(2’-羟基-3’,5’-二[1,1-二甲基苯基]) –苯并三唑 化学结构式: 抗氧化剂:通常使用受阻酚类抗氧剂245,1790或GA-80 抗氧剂245: 化学名称:双[β(3-叔丁基-5-甲基-4-羟基苯基)丙酸]三甘醇酯 化学结构式: O O O O O O O H OH 抗氧剂1790: 化学名称:1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮 化学结构式: 抗氧剂GA-80: N N N O H N N N O O O OH O H OH

化学名称:3,9-双[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基] -2,4,8,10-四氧杂螺[5.5]十一烷 化学结构式: 耐NOx 助剂:通常使用脲肼类添加剂CHN-150 化学名称:双(N,N-二甲基肼碳酰-4-氨基苯基)甲烷 化学结构式: N H N H O N H N N H N O 台湾双键化工是世界排名前列的耐老化添加剂生产商,目前,紫外线吸收剂234生产量亚洲最大,脲肼类添加剂生产量全球最大,同时也一直致力于开发特种新型的氨纶抗氧剂。 其实,近十多年来,氨纶用抗氧剂并没有改进和突破,基本上维持着美系(英威达)工艺主要使用1790,韩系(晓星)工艺和国内东洋纺工艺主要使用245,日清纺工艺使用GA-80的格局,究其原因还是国内的氨纶厂对于聚合工艺与耐候性能之间的关系了解不够,工艺和设备技术供应商相关技术开发开放程度不高以及添加剂供应商的新品研发能力不够有关。其实,近十年来,在聚氨酯领域的耐老化添加剂市场格局有了显著的改观,大量新型、高效的耐老化助剂推出已使得聚氨酯制品的耐老化、黄变的性能发生了很大改善。双键化工见证和领导了聚氨酯耐黄变市场的发展,在最容易黄变的聚氨酯海绵的耐候应用方面可以说无出其右,还是氨纶用紫外线吸收剂的最大供应商。对于氨纶抗氧剂的开发,双键化工也一直努力进取,近期推出了新型抗氧剂Chinox 30N 。 因专利审核的原因,双键化工还未公布Chinox 30N 的化学结构,但据介绍这是一种多官能基,大分子量的受阻酚抗氧剂,具有很好的耐热挥发性和耐迁移析出的效果,同时拥有很高的耐热氧化功效。添加了Chinox 30N 的氨纶丝或TPU 具有很好的耐热氧化性能和很好的耐室内氧化变色的特性。在氨纶生产中,抗氧剂的添加量通常需要至少0.5-1%以上,而使用Chinox 30N 基本在0.5%即可达到很好的耐热氧化和室内耐黄变的效果。 以和氨纶结构最接近的聚醚型TPU 作为参照物,抗氧剂Chinox 30N 比245具有更优的 测试方法 实验数据 废气烟熏 50℃×16小时 烘箱老化 70℃×168小时 室内放置 1周 室内放置 3周 黄色指数 △YI 30N 2.18 2.98 1.46 1.64 245 4.67 3.79 2.49 5.29 色差指数 △E 30N 2.87 3.05 2.12 2.26 245 3.44 3.45 2.42 3.30 实物照片:室内放置3周后TPU 试片的颜色变化:

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