2882 B:!" 2018#8$(B)%32&%8' 犃狏狉犪犿犻 S c & ( ()* & ( (+ )*,-.& $ N'?! 7#,$?, %,4 & ("Q M M, ) 5 ) > Y > O! R ) c /,( " ) > Q, a) F W (PQ <> )

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1 2882 犃狏狉犪犿犻 S c & ( ()* & ( (+ )*,-.& $ N'?! 7#,$?, %,4 & ("Q M M, ) 5 ) > '@c/ Y > O! R ) c /,( " ) > Q, a) F W (PQ <> )5 9 ) N Avrami ( M O )( ( )* ( +)* (PBS b PDGS), )c/ \]Y R!,Avra mi J- )c/,pdgs)l- ) E ) F N,GS ) F PDGS N!",PDGS).O (!") F PBS b PDGS )c/ \]! 01> R // Q Q 6S Q W6S P M Avrami T :TQ323.4;O :A 犇犗犐 : /j.issn X 犖狅狀犻狊狅狋犺犲狉犿犪犾犆狉狔狊狋犪犾犻狕犪狋犻狅狀犓犻狀犲狋犻犮狊狅犳犅犻狅犱犲犵狉犪犱犪犫犾犲犘狅犾狔 ( 犫狌狋狔犾犲狀犲狊狌犮犮犻狀犪狋犲 ) 犫犘狅犾狔 ( 犱犻犲狋犺狔犾犲狀犲犵犾狔犮狅犾狊狌犮犮犻狀犪狋犲 ) 犕狌犾狋犻犫犾狅犮犽犆狅狆狅犾狔犿犲狉狊犫狔狋犺犲犃狏狉犪犿犻犪狀犱狋犺犲犕狅狊犕犲狋犺狅犱狊犈狓犮犾狌狊犻狏犲犾狔 LIShaolong,XU Yi,CHEN Nongtian,YANG Wenfeng (AviationEngineeringInstitute,CivilAviationFlightUniversityofChina,Guanghan618307) 犃犫狊狋狉犪犮狋 Thepolymerprocessingisusualyoperatedundernonisothermalconditions,thestudyonnonisothermalcrystaliza tionbehaviorsofpolymershaveveryimportantlypracticalmeaningforchoosingsuitableprocessingmethod,equipment,temperature andtimetopreparepolymermaterialswithexcelentcomprehensiveordesiredproperties.weinvestigatedtheisothermalcrystaliza tionkineticsofbiodegradablepoly(butylenesuccinate) b poly(diethyleneglycolsuccinate)multiblockcopolymersbytheavramiand themo smethod.theresultsshowedthatavramiandthemo smethodscanbeusedtodescribethenonisothermalcrystalization behaviorsofthefoursamples.thecrystalizationmechanismalmostkeptunchangedwhilethecrystalizationratedecreasedwithan increaseofpdgscontent.theresultsalsodemonstratedthatthedecreaseofcrystalizationrateswasatributedtothediluteefectof PDGSwithanincreaseofPDGScontentinPBS b PDGScopolyesters.ThestudyonthenonisothermalcrystalizationkineticsofPBS b PDGSprovidetheorybasisfortheactualprocessingmolding. 犓犲狔狑狅狉犱狊 poly(butylenesuccinate) b poly(diethyleneglycolsuccinate),nonisothermalcrystalizationkinetics,avrami equation,mo smethod 0 9: Q Q 6S (PBS)U P &,B $114 (# 5 (LDPE) U),EW 9! 5$-32 ( a5 (PE) Q (PP) ), $1.25g/cm 3 (#24 5 6S(PET) U),E a PE PP, F? # PE PP U, #L 6 &,L + Z,XY,T 6 %&"L,T$L, & 0 VH B 3 W XN [1 2] PBSK9 <101,T-30~ 100,6 ayn 9 N ]F%&, & %&F? N R [ %% [3 4] V,T9:Z " Z,I#2 PBS [[9V PBS6FT 4 Z\ ] Z "],L,AQ Q 6^6 MW" 7, "! 7, & c, + Ac,PBSR M F? B [5 6],`a S (PHA) U (PLA) 6 S/7, b,pbs`a' * STZ ) " :P 8, PBS N., ]L, b# 2 PBS [2,7 8] `a. # PBS, b 2 PBS # [ :!L(U ); ( ) '(Q ); ( ) *(BJ ) + :4,1988',, 7, 89,- E mail:zlishaolong@163.com

2 N Avrami \]/7# /!( ( )* ( +)*, )c/ 2883 U< H Q [9 11] 9M# E -.,T ) "!6! E 7 6DP 3 F? PBS# [12 13] ), I*# % & B _., a, a7 [14 15] H ' 0 PBS # `a #' *,B G PBS, b R, [16] $]2 PBS,` Q (SA)# W 6 (DEG) Q W6S (HO PDGS OH)H, HO PDGS OH PBS' ", Q Q 6S Q W 6 S (PBS b PDGS) #,? P] HO PDGS OH O 2 P $-. [17] P #T Y (), O,U F 7 8 7, a J P %&T B W V H 3 7 ) ", T 0 ] P, b2%& P M P,6 F $ J + P FB_0 T P,# P, P ) Ma %&7 ),2 L 3 P 8 7, (DSC)2 HO PDGS OH O PBS b PDGS# G PBS P MF? ]' P, $# ] J"# 1 F 1.1 F b Q (SA)$ G,7a A 9 1,4 Q 6 (BD) W 6 (DEG) 4 (CHCl 3 ) 6 $ G,7a 0 9 Kb S (HDI),G $98%,7a@Q AlfaAe sar ; K Q S (Ti(iOPr) 4 )$ 9 M G,7 Q Sigma Aldrich 7 4 $ [ F c Q #Q 6 Q # W6 )S9Z3, ]Q Q 6S (HO PBS OH)H Q W 6 S (HO PDGS OH)H. C D,D & ( 狀 ( ) 狀 ( 6 )=1 1.2), H [18 19] ) ^, - 7 H HO PBS OH HO PDGS OH $ 4380g/ mol 4900g/mol PBS/PDGS ( & $ 93/7 86/14 Kb S(HDI) ', 0 ] PBS b PDGS 7 PBS b PDGS 14 PBS b PDGS 28,$]2, PBSH # HDI,' 0] G PBS,` 2 N@ P M b ] P [17] NR, ' (PDI) EW9! ( 犜 )F? g B_ ( 犜 m) a1 1 G PBS PBS b Table1 FundamentalparametersofneatPBSand PBS b PDGScopolymers Sample 犕 n/(10-4 g/mol) PDI 犜 / g 犜 m/ NeatPBS PBS b PDGS PBS b PDGS PBS b PDGS ;/ TA DSC Q200, \ 2 G PBS? PBS b PDGS # P, $5mg T N 2 A), N 130 B_, 5 min $,, F (20 /min 10 /min 5 /min 2.5 /min) 20,c F P M 2 '<M 2.1 N' 犇犛犆 :1 T 20 /min 10 /min 5 / min 2.5 /min BAP, T 2 P a 2 * + P, 7P ( 犜 c) :,7 PDGSO # P 9 (: 2) :16F,.,# P,, P, $ P R ),,,,,P,,P ] 2 G PBS PBS b PDGS# P Table2 CharacteristicparametersofneatPBSandits copolymersatdiferentcoolingrates Sample Coolingrate/( /min) 犜 c/ Δ 犎 c/(j/g) NeatPBS PBS b PDGS PBS b PDGS PBS b PDGS Note:Δ 犎 c heatofcrystalization

3 2884 Fig.1 :1 G PBS PBS b PDGS# T P DSC NonisothermalcrystalizationcurvesofneatPBSanditscopolymersatdiferentcoolingrates 2 :26F,T, PBS b PDGS# P ( 犜 c) PDGSO $ PDGS, ] PBS' P *,U 0 PDGS,*,2 P, S# P,P :2 G PBS PBS b PDGS# T P Fig.2 Thecrystalizationpeaktemperatureversuscooling rateforneatpbsanditscopolymers 2, (DSC) Y,,6F7 2P 犡狋, : 犜犜 0 犡狋 = d 犎犮 ( d犜 ) d 犎犮 d 犜犜 ( d犜 ) 犜 0 d 犜 (1)!": 犜 0 犜 P P 7, 犜 P V $ 狋 VP, 犎 c P V $ 狋 V P *+!(1),6F HG PBS?L# T 2P 9 ' (:3) P V ( 狋 )#P ( 犜 ) '6F $: 犜 - 犜 0 狋 = φ (2)!": 犜 P V $ 狋 VP, 犜 0 P, φ?!(1)!(2)6f7 2P V 9 ' : 4 $ G PBS? PBS b PDGS# 犡狋 #P V ': :46X, :, ] P # V Z G PBS T $ 20 /min # 1.2min8] P, U: $ 10 /min 5 /min 2.5 /minv,l] P ) # V $2.0min 3.2min 5.0min,,G PBS< P ] # V, 2aL PBS b PDGS# *F U $ 2.5 /min V,G PBS P ] # 5.0 min, PBS b PDGS 7# # 5.5min,PBS b PDGS 14# # 6.6 min,pbs b PDGS 28# # 7.2min T :,/# P ` [$:G PBS PBS b PDGS 7 PBS b PDGS 14 PBS b PDGS 28 PDGS O, < P ] # V,P # DSC F? P RS [17] 2.2 犃狏狉犪犿犻 c0 Aranmi a P M P, 2, C D Aranmi P M [20 22],L!6 $: 狀 1- 犡狋 =exp(- 犣狋 ) (3)!": 犣 P ; 狀 $ AvramiF,#?! ; 犡狋 $ ) " 狋 V 2P (`!(1) 7 )!(1)52 $: lg[-ln(1- 犡狋 )]=lg 犣 + 狀 lg 狋 (4) Flg[-ln(1- 犡狋 )]2lg 狋 :,67 Avrami, $ 狀, $lg 犣 P P $

4 xl Ａｖｍê>á?, ù Ä ù C A B D _ + & + A G ¼ ２８８５ U5 G X ３ q ＰＢＳ m ＰＢＳＰＤＧＳ 5'Ä Ê >~'( ~=5 P å=0]9^_ Ｆ３ＲｖｃｎｕｍｐｕｆｏｎＰＢＳｎｄｃｏｐｏｄｆｆｎｃｏｏｎｇｇｙｙｖｙｍ X ４ q ＰＢＳ m ＰＢＳＰＤＧＳ 5'Ä Ê >~'( å 5 P å=0]9^_ Ｆ４ＲｖｃｎｕｃｚｏｎｍｆｏｎＰＢＳｎｄｃｏｐｏｄｆｆｎｃｏｏｎｇｇｙｙｖｙｙｍ X ５ 6ð, Ａｖｍ)* q ＰＢＳ c ＰＢＳＰＤＧＳ 5 '(0ÖWPq ＰＢＳ cv5'ä0 狀 KEFÊF " å 'Ä0 ｎ１犡狋 5 狋 0 ] 9 X Ê X í ' ( ｇｇ Ø; w º 5 X í ' ( s ] n > ~ ' A ù q Z U û Ó _ Ａｖｍ) * M Ç, q ＰＢＳＰＢＳＰＤＧＳ７ＰＢＳＰＤＧＳ１４ m ＰＢＳＰＤＧＳ２８ 0 ＰＢＳ c ＰＢＳＰＤＧＳ 5'Äe90 Î ~ å Ø ; w Ａｖｍp: 狀 Kj k6 ３８３９４１ m ５２ " åz DEU 0 狀 m 犣 0 K 5 Î ~ å Ø ; w 4 0狀 úã ＰＤＧＳ 0 ]6vÊ/òÖ5'Ä0 åº m犽 0KÄ K² ô Ê P D T B C Ａｖｍ) * U 0D;w :0ÖWBp jã'zä0 åº " ３ ûr Ð M x 0 Î ~ å Ø ; w : > ~ Ò ÐMx0 å'( : 犣 K È > ~ ' ( 0 Í ÖÁôÂÌF ÊA 犣 K0D[1 ｍｎ狀 5 Ａｖｍp :狀 K ] p ) Õ 5 ' Ä 0 å $ ] + å '

5 2886 1/ 狀 ( 犽 ), 犽 = 犣,L, $ min -1, ] 狀 HY 犽 9 * F c G,I J $ Y, 犽 PDGSO, PDGS P 3 Avrami 7 G PBS PBS b PDGS# P, M Table3 NonisothermalcrystalizationparameterofneatPBSandPBS b PDGScopolyestersobtainedbytheAvramimethod Sample Coolingrate/( /min) 狀犣 /min - 狀犽 /min -1 (1/ 狋 1/2)/min -1 狋 1/2/min NeatPBS PBS b PDGS PBS b PDGS PBS b PDGS :5 G PBS PBS b PDGS# T Avrami Fig.5 AvramiplotsofforneatPBSanditscopolymersatdiferentcoolingrates P MV,6F )P 犣 c,- 4P V ( 狋 1/2)F?4P V (1/ 狋 1/2), ] P L! <$: 1 2 =1- 狀犡狋 =exp (- 犣狋 ) (5)!$: 狋 1/2= ( ln2 犽 ) 1/ 狀 (6) *+ Avrami, - 7 狀犣,6F 7 G PBS? PBS b PDGS # PDGSO 9 狋 1/2 1/ 狋 1/2 (3), ):66F

6 N Avrami \]/7# /!( ( )* ( +)*, )c/ 2887 狋 1/2 1/ 狋 1/2# ' F $ 20 / min$,g PBS PBS b PDGS 7 PBS b PDGS 14 PBS b PDGS 281/ 狋 1/2 $1.67min min min min -1, PDGS O,# 1/ 狋 1/2 I/, 狋 1/2., # P PDGSO :6 PDGSO 2 PBS b PDGS# T 狋 1/2 1/ 狋 1/2-. Fig.6 TheefectofweightfractionofPDGSon 狋 1/2and 1/ 狋 1/2ofPBS b PDGSatvariouscoolingrates 2.3 c T 3 P P M, Avrami Ozawa P,7 ^! [23 24] Avrami $!(4),Ozawa!$: lg[-ln(1- 犡狋 )]=lg 犓 ( 犜 )- 犿 lgφ (7)!": φ $ ; 犡狋 $ $ 犜 V 2P ; 犓 ( 犜 ) $ N,#! % ; 犿 $ OzawaF!(4)#!(7)P 7 T 3!: lgφ =lg 犉 ( 犜 )- 犪 lg 狋 (8)!": φ, 犉 ( 犜 )= [ 犓 ( 犜 )/ 犣 ] 1/ 犿, 犪 = 狀 / 犿, 狀 $ AvramiF, 犿 $ OzawaF 犉 ( 犜 ) P T, V < R 2P # 5 b 犉 ( 犜 )6 F c P, 犉 ( 犜 )., A ' P, 犉 ( 犜 ) /, A 'P UP V, < P # V,Flgφ 2lg 狋 :,7 R' P, $lg 犉 ( 犜 ), $- 犪 :7 5 2P $ V,G PBS?L# Flgφ 2lg 狋, R' ', T 3 c P G PBS? PBS b PDGS# P M,-/ 7 犉 ( 犜 ) 犪,2 a4 2aG PBS? PBS b PDGS#,T 3F 犪 2P..,2 9., V N 犪., PDGS L # " PBS P 2P, N 犉 ( 犜 ).,, V 7 2 :7 G PBS PBS b PDGS# T P ) "lgφ 2lg 狋 Fig.7 Plotsoflgφversuslg 狋 forneatpbsanditscopolymersduringnonisothermalcrystalization

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