摘要(yao):為提高(gao)聚乳酸(suan)(LA)薄膜的拉伸(shen)初性、透光率(lv)及其成(cheng)型加(jia)工穩定(ding)性,將(jiang)聚已二酸(suan)對苯二甲(jia)酸(suan)丁(ding)二酯(PBAT
與多元環氧擴鏈劑(ADR)預(yu)混,得到(dao)預(yu)混物PBA/ADR。再使(shi)用PBAT/ADR對PLA進行熔融共混改性(xing)和(he)咬膜成型
制(zhi)備得到PLAPBAT/ADR薄膜材料。采用旋轉(zhuan)流變儀和掃描電(dian)子顯微鏡研究ADR添(tian)加量對(dui)PLAPBATADR共混(hun)物
流(liu)變(bian)性能和微觀(guan)結構(gou)的影響。通過擠出吹(chui)膜機組、熔體流(liu)動速率測試儀、拉力試驗機、分光光度計、差式掃描量熱(re)儀
和廣(guang)角X射(she)線衍射(she)儀研(yan)究(jiu)PLAPBATADR薄膜的吹膜成型(xing)穩(wen)定性,拉伸性能(neng)、透(tou)光率以(yi)及(ji)結(jie)晶等性能(neng)。結(jie)果表明
ADR的加入起到(dao)顯著擴(kuo)鏈(lian)增(zeng)黏和反應性增(zeng)容的作用,共(gong)混物的黏度(du)(du)和熔(rong)體(ti)強度(du)(du)得到(dao)較大提升,PBAT分散(san)相也得到(dao)顯
著細化。所得PLAPBAADR(95/50.5)薄膜(mo)(mo)表現出(chu)良好(hao)的吹膜(mo)(mo)成型(xing)穩定性、高的斷裂伸長率(lv)(461.4%)以及較好(hao)的透
光性能(neng)(平均透光率(lv)為(wei)86.6%
關鍵詞:聚乳酸;薄膜;擴鏈;增容;增韌;透光率
隨(sui)著經濟的(de)(de)不(bu)斷(duan)發展,人們對(dui)(dui)塑(su)(su)料(liao)制品的(de)(de)需求也在不(bu)斷(duan)增長[1]。但隨(sui)著塑(su)(su)料(liao)碎(sui)片在地球的(de)(de)各個(ge)角(jiao)落被發現[2],人們意識到塑(su)(su)料(liao)制品廢棄后(hou)所引發的(de)(de)塑(su)(su)料(liao)污染(ran)對(dui)(dui)人類(lei)、動植物以及自(zi)然(ran)環境(jing)(jing)都有(you)巨大(da)(da)危(wei)害[3]。塑(su)(su)料(liao)污染(ran)也成(cheng)為人類(lei)不(bu)可回(hui)避的(de)(de)痛點。雖然(ran)各個(ge)國(guo)(guo)家和組織進(jin)行(xing)政策(ce)引導,聯合國(guo)(guo)環境(jing)(jing)大(da)(da)會和各國(guo)(guo)科(ke)學(xue)家也積極尋求解決(jue)方案(an)[4],但是塑(su)(su)料(liao)廢棄物對(dui)(dui)環境(jing)(jing)的(de)(de)污染(ran)仍不(bu)斷(duan)在加劇。在此(ci)背景(jing)下,可生物降解材料(liao)的(de)(de)研究和推廣應用正在成(cheng)為解決(jue)塑(su)(su)料(liao)污染(ran)的(de)(de)一種有(you)效手段,并受到各國(guo)(guo)政府和社會的(de)(de)普遍(bian)關注。
聚(ju)(ju)乳(ru)酸(suan)(PLA)是(shi)一種生(sheng)物(wu)基可(ke)生(sheng)物(wu)降(jiang)解的(de)(de)熱(re)塑性(xing)脂(zhi)肪(fang)族(zu)聚(ju)(ju)酯(zhi),其(qi)(qi)單(dan)體原料可(ke)大量從(cong)生(sheng)物(wu)質中(zhong)獲取[5-6]。PLA具有類(lei)似聚(ju)(ju)苯乙烯的(de)(de)高(gao)強度[7]、優異的(de)(de)光學性(xing)能(neng)和(he)可(ke)加(jia)工(gong)性(xing)[8-9],在(zai)生(sheng)物(wu)醫用(yong)(yong)(yong)材料[10]、包裝薄膜[11]、發泡(pao)材料[12]、紡絲(si)[13]及形狀(zhuang)記憶材料[14]等領域具有廣(guang)闊的(de)(de)應(ying)用(yong)(yong)(yong)前景。但由(you)(you)于PLA脆性(xing)大,斷裂伸長率低,限制了PLA制品的(de)(de)推廣(guang)應(ying)用(yong)(yong)(yong)。而利用(yong)(yong)(yong)其(qi)(qi)它可(ke)生(sheng)物(wu)降(jiang)解聚(ju)(ju)合物(wu)對PLA進行(xing)增(zeng)(zeng)韌(ren)(ren)(ren)改性(xing)是(shi)擴大PLA應(ying)用(yong)(yong)(yong)范圍(wei)的(de)(de)有效方法之一,例如,聚(ju)(ju)己二酸(suan)對苯二甲酸(suan)丁(ding)(ding)(ding)二酯(zhi)(PBAT)[15]、聚(ju)(ju)己內酯(zhi)(PCL)[16]、聚(ju)(ju)丁(ding)(ding)(ding)二酸(suan)丁(ding)(ding)(ding)二酯(zhi)(PBS)[17]、聚(ju)(ju)丁(ding)(ding)(ding)二酸(suan)己二酸(suan)丁(ding)(ding)(ding)二酯(zhi)(PBSA)[18]等。其(qi)(qi)中(zhong),PBAT樹脂(zhi)由(you)(you)于具有優良拉伸韌(ren)(ren)(ren)性(xing)、較好耐熱(re)性(xing)以及較高(gao)性(xing)價比等優勢(shi),在(zai)PLA增(zeng)(zeng)韌(ren)(ren)(ren)改性(xing)方面的(de)(de)應(ying)用(yong)(yong)(yong)較多。由(you)(you)于PLA與PBAT相(xiang)容(rong)性(xing)較差,常使(shi)用(yong)(yong)(yong)多元環(huan)氧擴鏈劑(ADR)作為PLA/PBAT共混體系的(de)(de)反(fan)(fan)應(ying)性(xing)增(zeng)(zeng)容(rong)劑來(lai)提高(gao)兩(liang)相(xiang)增(zeng)(zeng)容(rong)和(he)增(zeng)(zeng)韌(ren)(ren)(ren)效果,其(qi)(qi)增(zeng)(zeng)容(rong)原理是(shi)ADR的(de)(de)多環(huan)氧基團能(neng)夠和(he)PLA,PBAT大分子的(de)(de)端(duan)羧(suo)基和(he)端(duan)羥基發生(sheng)開環(huan)反(fan)(fan)應(ying),在(zai)界面生(sheng)成PLA-g-PBAT兩(liang)親性(xing)擴鏈大分子,達到界面增(zeng)(zeng)容(rong)、細化(hua)PBAT分散(san)相(xiang)顆粒(li)的(de)(de)目(mu)的(de)(de)。
目前,PLA/PBAT改(gai)性(xing)(xing)(xing)薄(bo)(bo)膜材料(liao)的(de)(de)(de)研究主要(yao)集中(zhong)于薄(bo)(bo)膜力學(xue)性(xing)(xing)(xing)能和成(cheng)型性(xing)(xing)(xing)能等方面,對(dui)于薄(bo)(bo)膜透(tou)光率性(xing)(xing)(xing)能的(de)(de)(de)研究報道很(hen)少(shao)。而制備兼具高拉伸韌性(xing)(xing)(xing)和高透(tou)光率的(de)(de)(de)PLA/PBAT改(gai)性(xing)(xing)(xing)薄(bo)(bo)膜在對(dui)透(tou)光性(xing)(xing)(xing)能有(you)(you)較高要(yao)求的(de)(de)(de)中(zhong)高端包裝薄(bo)(bo)膜材料(liao)領域具有(you)(you)較好(hao)的(de)(de)(de)應用(yong)前景(jing)。
采用二(er)(er)步(bu)共混(hun)(hun)(hun)(hun)(hun)法(fa)制備(bei)ADR改(gai)性(xing)(xing)的(de)PLA/PBAT薄(bo)(bo)膜(mo)材(cai)料(liao)。二(er)(er)步(bu)共混(hun)(hun)(hun)(hun)(hun)法(fa)即先將ADR和PBAT進(jin)行共混(hun)(hun)(hun)(hun)(hun)得(de)到PBAT/ADR預混(hun)(hun)(hun)(hun)(hun)物(wu),再將預混(hun)(hun)(hun)(hun)(hun)物(wu)與PLA進(jin)行共混(hun)(hun)(hun)(hun)(hun)得(de)到PLA/PBAT/ADR改(gai)性(xing)(xing)料(liao),并通(tong)過擠出吹膜(mo)機得(de)到薄(bo)(bo)膜(mo)試樣。相(xiang)對于一(yi)步(bu)共混(hun)(hun)(hun)(hun)(hun)法(fa),二(er)(er)步(bu)共混(hun)(hun)(hun)(hun)(hun)法(fa)可提(ti)高PLA共混(hun)(hun)(hun)(hun)(hun)材(cai)料(liao)界(jie)面相(xiang)容性(xing)(xing)和分散相(xiang)細化效果[19-20]。研究了ADR添加(jia)量對薄(bo)(bo)膜(mo)材(cai)料(liao)的(de)成型(xing)加(jia)工穩定性(xing)(xing)、拉伸性(xing)(xing)能(neng)、透光率、結(jie)晶(jing)性(xing)(xing)能(neng)等方面的(de)影響。最終制備(bei)得(de)到拉伸韌性(xing)(xing)優良且透光性(xing)(xing)能(neng)較好(hao)的(de)PLA/PBAT薄(bo)(bo)膜(mo)材(cai)料(liao)。
1實驗部分
1.1 主要原(yuan)材料PLA:4032D,美國Nature Works公(gong)司(si)(si);PBAT:C1200,德國BASF公(gong)司(si)(si);ADR:Joncryl?ADR 4370F,德國BASF公(gong)司(si)(si)。
1.2 主要設(she)備及儀(yi)(yi)器轉(zhuan)矩流(liu)變儀(yi)(yi):XSS-300型(xing)(xing)(xing),上海(hai)科(ke)創(chuang)橡塑機(ji)(ji)(ji)械設(she)備有限(xian)公(gong)司(si)(si)(si)(si);雙螺(luo)(luo)桿(gan)擠出機(ji)(ji)(ji):SHJ-20型(xing)(xing)(xing)(螺(luo)(luo)桿(gan)直徑(jing)20 mm,長徑(jing)比(bi)40),南京(jing)杰恩特機(ji)(ji)(ji)電有限(xian)公(gong)司(si)(si)(si)(si);單螺(luo)(luo)桿(gan)擠出吹膜機(ji)(ji)(ji):LSJ-20型(xing)(xing)(xing)(螺(luo)(luo)桿(gan)直徑(jing)20mm,長徑(jing)比(bi)25),上海(hai)科(ke)創(chuang)橡塑機(ji)(ji)(ji)械設(she)備有限(xian)公(gong)司(si)(si)(si)(si);微(wei)型(xing)(xing)(xing)注塑機(ji)(ji)(ji):WZS10D型(xing)(xing)(xing),上海(hai)新(xin)碩精密儀(yi)(yi)器有限(xian)公(gong)司(si)(si)(si)(si);旋轉(zhuan)流(liu)變儀(yi)(yi):MARS60型(xing)(xing)(xing),賽默飛(fei)世爾科(ke)技(ji)有限(xian)公(gong)司(si)(si)(si)(si);熔(rong)體質量(liang)流(liu)動速率(lv)(MFR)測(ce)定儀(yi)(yi):XNR-400B型(xing)(xing)(xing),承德德盛檢測(ce)設(she)備有限(xian)公(gong)司(si)(si)(si)(si);掃(sao)(sao)描電子顯微(wei)鏡(jing)(SEM):S-3500N型(xing)(xing)(xing),日本(ben)Hitachi公(gong)司(si)(si)(si)(si);微(wei)機(ji)(ji)(ji)控制拉力試(shi)驗機(ji)(ji)(ji):WDW-1型(xing)(xing)(xing),濟南一(yi)諾世紀(ji)實驗儀(yi)(yi)器有限(xian)公(gong)司(si)(si)(si)(si);可見(jian)分光光度計:723S型(xing)(xing)(xing),上海(hai)奧(ao)析科(ke)學儀(yi)(yi)器有限(xian)公(gong)司(si)(si)(si)(si);差示量(liang)熱(re)掃(sao)(sao)描(DCS)儀(yi)(yi):DISCOVERY DSC2250型(xing)(xing)(xing),美國(guo)TA公(gong)司(si)(si)(si)(si);廣角X射線衍(yan)射(WXRD)儀(yi)(yi):D8 ADVANCE型(xing)(xing)(xing),德國(guo)Bruker D8 Advance公(gong)司(si)(si)(si)(si)。
1.3 試樣(yang)制(zhi)備(1)共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun)物制(zhi)備。先將(jiang)PLA,PBAT樹脂在60 °C的(de)(de)(de)真空(kong)烘箱中干(gan)燥4 h,再將(jiang)PBAT和ADR按照(zhao)一定質量(liang)比(bi)在轉(zhuan)矩流變儀中進(jin)(jin)行預(yu)混(hun)(hun)(hun)(hun),得(de)到PBAT/ADR預(yu)混(hun)(hun)(hun)(hun)物,共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun)溫度(du)(du)和共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun)轉(zhuan)速分別為(wei)160 °C和50r/min。隨后(hou),將(jiang)PBAT/ADR與PLA按照(zhao)一定質量(liang)比(bi)在轉(zhuan)矩流變儀中進(jin)(jin)行共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun),得(de)到PLA/PBAT/ADR共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun)物,其共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun)溫度(du)(du)和共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun)轉(zhuan)速分別為(wei)210 °C和50 r/min。其中,PLA/PBAT質量(liang)份(fen)數比(bi)固(gu)定為(wei)95∶5;以PLA和PBAT的(de)(de)(de)樹脂總質量(liang)為(wei)100份(fen),ADR的(de)(de)(de)加(jia)入(ru)量(liang)分別為(wei)0.25和0.5份(fen),所得(de)共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun)物記(ji)為(wei)PLA/PBAT/ADR (95/5/X) (X代表(biao)ADR添加(jia)量(liang),分別為(wei)0.25和0.5)。作為(wei)對比(bi),純PLA和PLA/PBAT (95/5)共(gong)(gong)(gong)(gong)混(hun)(hun)(hun)(hun)物也在轉(zhuan)矩流變儀中采用相同的(de)(de)(de)加(jia)工條件(jian)(210 °C和50 r/min)制(zhi)備。
(2)薄膜(mo)(mo)(mo)制(zhi)備。使(shi)用SHJ-20型雙螺(luo)(luo)(luo)(luo)(luo)桿(gan)擠出(chu)(chu)(chu)(chu)機在160 °C下將PBAT與ADR預(yu)(yu)混(hun)(hun),得到PBAT/ADR預(yu)(yu)混(hun)(hun)物,預(yu)(yu)混(hun)(hun)溫度設置(zhi)為(wei)(wei)130,160,160,160,160,150 °C,螺(luo)(luo)(luo)(luo)(luo)桿(gan)轉速(su)為(wei)(wei)100 r/min。然后,將PBAT/ADR預(yu)(yu)混(hun)(hun)物與PLA樹脂在雙螺(luo)(luo)(luo)(luo)(luo)桿(gan)擠出(chu)(chu)(chu)(chu)機中進行(xing)擠出(chu)(chu)(chu)(chu)共(gong)(gong)混(hun)(hun)及(ji)造粒(li)(li),得到PLA/PBAT/ADR質量(liang)比(bi)分別為(wei)(wei)95/5/0.25和95/5/0.5的共(gong)(gong)混(hun)(hun)物粒(li)(li)料。各(ge)區溫度設置(zhi)為(wei)(wei)130,210,210,210,210,210 °C,螺(luo)(luo)(luo)(luo)(luo)桿(gan)轉速(su)為(wei)(wei)100 r/min。作為(wei)(wei)對(dui)比(bi),純PLA和PLA/PBAT (95/5)共(gong)(gong)混(hun)(hun)物也在上述加工條件下通過雙螺(luo)(luo)(luo)(luo)(luo)桿(gan)擠出(chu)(chu)(chu)(chu)機進行(xing)熔融共(gong)(gong)混(hun)(hun)和擠出(chu)(chu)(chu)(chu)造粒(li)(li)。使(shi)用LSJ-20型單(dan)螺(luo)(luo)(luo)(luo)(luo)桿(gan)擠出(chu)(chu)(chu)(chu)吹膜(mo)(mo)(mo)機對(dui)上述粒(li)(li)料進行(xing)吹膜(mo)(mo)(mo)成型實(shi)驗,最終得到厚度為(wei)(wei)40μm左(zuo)右的薄膜(mo)(mo)(mo)試樣(yang)。其中,口(kou)模(mo)直徑(jing)為(wei)(wei)34 mm,口(kou)模(mo)間隙為(wei)(wei)0.5 mm,單(dan)螺(luo)(luo)(luo)(luo)(luo)桿(gan)各(ge)區溫度設置(zhi)為(wei)(wei)130,210,210,200 °C,螺(luo)(luo)(luo)(luo)(luo)桿(gan)轉速(su)30 r/min。
1.4 性能(neng)測試與(yu)表征
(1)動態流(liu)變(bian)性(xing)能測試(shi)。將PLA及其共混物經注塑(su)機注塑(su)成直徑為25 mm,厚(hou)度(du)(du)為1.5 mm的圓片,利(li)用旋轉流(liu)變(bian)儀(yi)對(dui)其流(liu)變(bian)行(xing)為進(jin)(jin)(jin)行(xing)測試(shi)。在平(ping)行(xing)板模式下,使用震蕩模式進(jin)(jin)(jin)行(xing)頻率(lv)掃描(miao),測試(shi)溫度(du)(du)為210 °C,角(jiao)頻率(lv)范圍在0.1~628 rad/s內,固(gu)定應變(bian)為1%。(2) SEM觀察(cha)。將共混材(cai)料切成條狀,利(li)用液氮對(dui)試(shi)樣進(jin)(jin)(jin)行(xing)冷(leng)凍脆斷(duan),并對(dui)斷(duan)面(mian)進(jin)(jin)(jin)行(xing)噴金(jin)處理后(hou),再對(dui)脆斷(duan)面(mian)進(jin)(jin)(jin)行(xing)微觀形貌觀察(cha)。放大倍數為3000倍。
(3)MFR測(ce)試(shi)(shi)。根據(ju)GB/T 3682-2018,使(shi)用MFR測(ce)定儀對試(shi)(shi)樣進行MFR測(ce)試(shi)(shi)。測(ce)試(shi)(shi)條件(jian)為溫度210 °C,載荷2.16 kg。
(4)拉(la)(la)伸(shen)(shen)性能(neng)(neng)測(ce)試。參(can)照GB/T 1040.3-2006,將薄膜沿(yan)擠出方(fang)向(MD)預先裁(cai)成(cheng)15 mm寬的長(chang)條試樣(yang)(yang),使用萬能(neng)(neng)試驗機對試樣(yang)(yang)進(jin)行拉(la)(la)伸(shen)(shen)性能(neng)(neng)測(ce)試。其中設置樣(yang)(yang)品(pin)有效(xiao)拉(la)(la)伸(shen)(shen)部分(fen)為50 mm,拉(la)(la)伸(shen)(shen)速(su)度(du)為5mm/min,獲(huo)得相關拉(la)(la)伸(shen)(shen)性能(neng)(neng)數據(ju),每個數據(ju)點由5個有效(xiao)值取(qu)平均值得到(dao)。
(5)透(tou)光率測試(shi)。根據GB/T 2410-2008,使(shi)用分(fen)光光度(du)計獲得薄膜試(shi)樣在(zai)(zai)(zai)380~780 nm范圍內的透(tou)光率曲(qu)線。對(dui)樣品(pin)在(zai)(zai)(zai)可(ke)見(jian)光范圍內透(tou)過率譜圖進行積分(fen)得到(dao)樣品(pin)在(zai)(zai)(zai)可(ke)見(jian)光范圍內的平均透(tou)光率。
(6) DSC測(ce)試(shi)。利(li)用DSC儀對薄膜試(shi)樣的熔融行為(wei)(wei)(wei)以及結(jie)(jie)晶(jing)度等熱力(li)學參數進行研究。取5~8mg樣品,在(zai)氮氣保護下(xia)進行測(ce)試(shi)。溫(wen)度從20 °C升(sheng)溫(wen)至210 °C,升(sheng)溫(wen)速(su)率(lv)為(wei)(wei)(wei)10 °C/min。記錄升(sheng)溫(wen)曲(qu)線,從曲(qu)線中(zhong)(zhong)獲(huo)得玻璃化轉變溫(wen)度(Tg)、冷(leng)(leng)結(jie)(jie)晶(jing)溫(wen)度(Tcc)、熔融溫(wen)度(Tm)、冷(leng)(leng)結(jie)(jie)晶(jing)焓(han)(han)(?Hcc)、熔融焓(han)(han)(?Hm)。并通過式(1)計算樣品中(zhong)(zhong)PLA基體結(jie)(jie)晶(jing)度。在(zai)本DSC測(ce)試(shi)中(zhong)(zhong),定義(yi)放熱焓(han)(han)為(wei)(wei)(wei)正(zheng)值。
式(shi)中(zhong):ω為(wei)試樣(yang)中(zhong)PLA所(suo)占的質量(liang)分數(shu);?H0m為(wei)PLA結晶(jing)度(du)(du)為(wei)100%時(shi)的標準熔融焓(﹣93.6 J/g)[21];Xc為(wei)PLA的結晶(jing)度(du)(du)。(7) WAXD測試。使用WXRD儀對(dui)薄膜試樣(yang)的結晶(jing)結構進行(xing)研究。其中(zhong),Cu Kα靶射(she)線波長為(wei)0.1542 nm,掃描(miao)范(fan)圍為(wei)5°~35°,掃描(miao)速度(du)(du)5 °/min。
2結果與(yu)討論2.1 共(gong)混物(wu)流變(bian)學性能(neng)圖(tu)1為(wei)PLA/PBAT/ADR (95/5/X)共(gong)混物(wu)的(de)(de)動態流變(bian)學曲(qu)(qu)線(xian)。由(you)(you)圖(tu)1a中(zhong)復數黏度(du)(η)與(yu)角頻率(lv)(ω)的(de)(de)關(guan)系曲(qu)(qu)線(xian)可知(zhi),隨(sui)著ADR添加(jia)(jia)量(liang)(liang)(liang)的(de)(de)增(zeng)大(da)(da)(da)(da),共(gong)混物(wu)的(de)(de)η-ω曲(qu)(qu)線(xian)顯著升高。這(zhe)是由(you)(you)于PBAT/ADR預混物(wu)中(zhong)原位(wei)生(sheng)(sheng)成(cheng)的(de)(de)PBAT-g-ADR以及未反應的(de)(de)ADR可以使PBAT分(fen)(fen)散相(xiang)以及PLA基(ji)體(ti)發生(sheng)(sheng)擴(kuo)鏈(lian)/支(zhi)(zhi)化(hua)反應,形成(cheng)擴(kuo)鏈(lian)及長支(zhi)(zhi)鏈(lian)聚酯大(da)(da)(da)(da)分(fen)(fen)子(zi)(zi),從而(er)使得共(gong)混物(wu)黏度(du)增(zeng)大(da)(da)(da)(da)。除此之外,隨(sui)著ADR添加(jia)(jia)量(liang)(liang)(liang)增(zeng)大(da)(da)(da)(da),試(shi)樣的(de)(de)η對(dui)剪(jian)切(qie)速率(lv)變(bian)化(hua)的(de)(de)敏感(gan)性增(zeng)大(da)(da)(da)(da),熔體(ti)假塑性不(bu)斷增(zeng)強[22]。這(zhe)是由(you)(you)于隨(sui)著ADR添加(jia)(jia)量(liang)(liang)(liang)增(zeng)大(da)(da)(da)(da),生(sheng)(sheng)成(cheng)的(de)(de)擴(kuo)鏈(lian)/支(zhi)(zhi)化(hua)大(da)(da)(da)(da)分(fen)(fen)子(zi)(zi)數量(liang)(liang)(liang)增(zeng)多,大(da)(da)(da)(da)分(fen)(fen)子(zi)(zi)解纏結行為(wei)對(dui)剪(jian)切(qie)速率(lv)變(bian)化(hua)更為(wei)敏感(gan)所致。而(er)由(you)(you)圖(tu)1b和圖(tu)1c可知(zhi),隨(sui)著ADR添加(jia)(jia)量(liang)(liang)(liang)增(zeng)大(da)(da)(da)(da),試(shi)樣的(de)(de)儲能(neng)模(mo)量(liang)(liang)(liang)(G′)與(yu)角頻率(lv)(ω)的(de)(de)關(guan)系曲(qu)(qu)線(xian)、損耗模(mo)量(liang)(liang)(liang)(G")與(yu)角頻率(lv)(ω)的(de)(de)關(guan)系曲(qu)(qu)線(xian)均不(bu)斷提高。圖(tu)1d的(de)(de)Han圖(tu)曲(qu)(qu)線(xian)隨(sui)ADR含量(liang)(liang)(liang)的(de)(de)增(zeng)加(jia)(jia),逐漸(jian)靠近等模(mo)量(liang)(liang)(liang)線(xian),共(gong)混物(wu)試(shi)樣逐漸(jian)從“類液體(ti)”流變(bian)行為(wei)轉向(xiang)為(wei)“類固體(ti)”。這(zhe)說明隨(sui)著ADR添加(jia)(jia)量(liang)(liang)(liang)的(de)(de)增(zeng)加(jia)(jia),PLA/PBAT/ADR (95/5/X)共(gong)混物(wu)中(zhong)生(sheng)(sheng)成(cheng)的(de)(de)擴(kuo)鏈(lian)/支(zhi)(zhi)化(hua)分(fen)(fen)子(zi)(zi)數量(liang)(liang)(liang)增(zeng)大(da)(da)(da)(da),其熔體(ti)模(mo)量(liang)(liang)(liang)及熔體(ti)強度(du)增(zeng)大(da)(da)(da)(da),這(zhe)有助于后(hou)續吹膜成(cheng)型時擠(ji)出膜泡穩定性的(de)(de)政(zheng)善(shan)
2.2 共(gong)(gong)混(hun)物(wu)微觀形貌圖(tu)2為PLA/PBAT(95/5)及PLA/PBAT/ADR (95/5/X)共(gong)(gong)混(hun)物(wu)脆斷(duan)面(mian)的SEM圖(tu)。由圖(tu)2可(ke)以(yi)發(fa)現(xian),在(zai)(zai)PLA/PBAT (95/5)二元共(gong)(gong)混(hun)物(wu)中(zhong)(zhong),PBAT分(fen)散(san)相(xiang)以(yi)顆(ke)粒狀分(fen)散(san)在(zai)(zai)基體(ti)中(zhong)(zhong),平均(jun)粒徑約(yue)為0.5μm,兩(liang)相(xiang)相(xiang)界(jie)(jie)面(mian)清(qing)晰,界(jie)(jie)面(mian)脫(tuo)黏現(xian)象較(jiao)明顯(xian)。這是由于PLA和PBAT組分(fen)間相(xiang)容性不佳[23],界(jie)(jie)面(mian)黏合力弱導致。而隨著ADR添加量增加,PLA/PBAT/AD共(gong)(gong)混(hun)物(wu)中(zhong)(zhong)的
PBAT分(fen)散顆粒(li)(li)(li)顯著細(xi)化,且由于PLA/PBAT兩(liang)相界(jie)面(mian)(mian)的(de)(de)黏(nian)附力(li)增強,相界(jie)面(mian)(mian)變得(de)模糊,PBAT顆粒(li)(li)(li)被包埋于PLA基體中(zhong)(zhong),界(jie)面(mian)(mian)脫(tuo)黏(nian)得(de)到(dao)(dao)顯著抑制。這(zhe)是因(yin)為在制備PBAT/ADR預混(hun)物時,ADR分(fen)子(zi)中(zhong)(zhong)的(de)(de)一部分(fen)環氧官(guan)能團與PBAT進行開環反應,生成(cheng)PBAT-ADR接枝物。而在第二步與PLA共混(hun)時,預混(hun)物中(zhong)(zhong)原(yuan)位生成(cheng)的(de)(de)PBAT-ADR和未反應ADR分(fen)子(zi)中(zhong)(zhong)的(de)(de)多元環氧基團將(jiang)富集在PBAT分(fen)散相內(nei)及PLA/PBAT兩(liang)相的(de)(de)界(jie)面(mian)(mian)上(shang)。導致在兩(liang)相界(jie)面(mian)(mian)上(shang)會原(yuan)位生成(cheng)大量PLA-ADR-PBAT接枝物,起到(dao)(dao)界(jie)面(mian)(mian)增容劑作(zuo)用,相界(jie)面(mian)(mian)的(de)(de)黏(nian)附力(li)和增容效果得(de)到(dao)(dao)強化,PBAT分(fen)散相顆粒(li)(li)(li)粒(li)(li)(li)徑進一步細(xi)化。
2.3 吹(chui)膜(mo)(mo)穩(wen)定性(xing)(xing)(xing)(xing)圖(tu)3為PLA,PLA/PBAT (95/5),PLA/PBAT/ADR (95/5/X)粒料(liao)的吹(chui)膜(mo)(mo)成(cheng)(cheng)型照(zhao)片。純PLA和(he)PLA/PBAT (95/5)共混物經(jing)吹(chui)膜(mo)(mo)機口模擠出和(he)吹(chui)脹時(shi),由(you)于其熔(rong)體黏度和(he)熔(rong)體強(qiang)度較(jiao)低,導致其膜(mo)(mo)泡在吹(chui)脹成(cheng)(cheng)型時(shi),不斷發生破(po)膜(mo)(mo)和(he)扭(niu)轉(zhuan)現象(xiang),吹(chui)膜(mo)(mo)成(cheng)(cheng)型穩(wen)定性(xing)(xing)(xing)(xing)差。隨著(zhu)ADR的加入,PLA/PBAT/ADR (95/5/0.25)粒料(liao)的吹(chui)膜(mo)(mo)成(cheng)(cheng)型穩(wen)定性(xing)(xing)(xing)(xing)得(de)到較(jiao)大改善,破(po)膜(mo)(mo)和(he)扭(niu)轉(zhuan)現象(xiang)得(de)到較(jiao)好(hao)抑制,膜(mo)(mo)泡形狀(zhuang)和(he)尺寸穩(wen)定性(xing)(xing)(xing)(xing)較(jiao)好(hao)。而PLA/PBAT/ADR (95/5/0.5)粒料(liao)的吹(chui)膜(mo)(mo)成(cheng)(cheng)型性(xing)(xing)(xing)(xing)能進(jin)一步增強(qiang),其膜(mo)(mo)泡形狀(zhuang)和(he)尺寸穩(wen)定性(xing)(xing)(xing)(xing)保持最好(hao),可以長時(shi)間保持穩(wen)定吹(chui)膜(mo)(mo)成(cheng)(cheng)型。
表1為(wei)PLA,PLA/PBAT (95/5),PLA/PBAT/ADR (95/5/0.25)以及(ji)(95/5/0.5)粒(li)料的(de)MFR值(zhi)。由表1為(wei)PLA,PLA/PBAT (95/5),PLA/PBAT/ADR (95/5/0.25)以及(ji)(95/5/0.5)粒(li)料的(de)MFR值(zhi)。
2.4 薄膜(mo)拉伸(shen)(shen)(shen)性(xing)(xing)(xing)能表2列(lie)出(chu)了PLA,PLA/PBAT (95/5),PLA/PBAT/ADR (95/5/0.25)以及(ji)(95/5/0.5)薄膜(mo)試(shi)樣(yang)的拉伸(shen)(shen)(shen)性(xing)(xing)(xing)能數(shu)據。由(you)于柔性(xing)(xing)(xing)PBAT組分(fen)的加(jia)(jia)入,共混材料的拉伸(shen)(shen)(shen)強(qiang)度和(he)拉伸(shen)(shen)(shen)彈性(xing)(xing)(xing)模量有(you)所下降(jiang)。但(dan)純(chun)PLA薄膜(mo)試(shi)樣(yang)的斷裂伸(shen)(shen)(shen)長(chang)率(lv)(lv)僅為31.0%,而PLA/PBAT (95/5)薄膜(mo)試(shi)樣(yang)的斷裂伸(shen)(shen)(shen)長(chang)率(lv)(lv)可增大至(zhi)216.1%,PLA/PBAT/ADR (95/5/0.5)薄膜(mo)試(shi)樣(yang)的斷裂伸(shen)(shen)(shen)長(chang)率(lv)(lv)更是增大至(zhi)461.4%。顯(xian)然,PBAT和(he)PBAT/ADR的加(jia)(jia)入,可顯(xian)著改善PLA薄膜(mo)的拉伸(shen)(shen)(shen)延展性(xing)(xing)(xing)能。
2.5 薄(bo)膜(mo)(mo)(mo)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)性(xing)能圖(tu)4為(wei)(wei)PLA,PLA/PBAT (95/5),PLA/PBAT/ADR (95/5/0.25)以及(95/5/0.5)薄(bo)膜(mo)(mo)(mo)試樣(yang)的(de)(de)(de)(de)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)曲(qu)線(xian)。由(you)(you)圖(tu)4可(ke)(ke)(ke)知,純(chun)PLA薄(bo)膜(mo)(mo)(mo)在(zai)可(ke)(ke)(ke)見光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)波長范圍(380~780 nm)內的(de)(de)(de)(de)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)最高(gao)。這(zhe)是(shi)(shi)由(you)(you)于所(suo)(suo)得PLA薄(bo)膜(mo)(mo)(mo)結晶(jing)度低,可(ke)(ke)(ke)近(jin)似認為(wei)(wei)是(shi)(shi)均(jun)相(xiang)(xiang)非晶(jing)材料所(suo)(suo)致。而(er)隨著(zhu)(zhu)PBAT的(de)(de)(de)(de)加入,PLA/PBAT (95/5)薄(bo)膜(mo)(mo)(mo)的(de)(de)(de)(de)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)曲(qu)線(xian)整體(ti)顯著(zhu)(zhu)下移。這(zhe)是(shi)(shi)由(you)(you)于PLA與(yu)PBAT相(xiang)(xiang)容性(xing)較(jiao)差,PBAT分(fen)散(san)相(xiang)(xiang)顆粒(li)尺寸(cun)較(jiao)大,對(dui)入射可(ke)(ke)(ke)見光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)有較(jiao)強遮擋作用,透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)顯著(zhu)(zhu)下降(jiang)(jiang)。而(er)隨著(zhu)(zhu)PBAT/ADR預混物(wu)的(de)(de)(de)(de)加入,PLA/PBAT/ADR (95/5/0.25)和(95/5/0.5)薄(bo)膜(mo)(mo)(mo)的(de)(de)(de)(de)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)曲(qu)線(xian)整體(ti)向上移動,薄(bo)膜(mo)(mo)(mo)的(de)(de)(de)(de)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)性(xing)能得到(dao)(dao)較(jiao)大改善。這(zhe)是(shi)(shi)由(you)(you)于PBAT/ADR預混物(wu)對(dui)兩相(xiang)(xiang)界面較(jiao)強的(de)(de)(de)(de)界面增容作用,使(shi)得PLA/PBAT/ADR薄(bo)膜(mo)(mo)(mo)中PBAT分(fen)散(san)相(xiang)(xiang)顆粒(li)尺寸(cun)得到(dao)(dao)顯著(zhu)(zhu)細(xi)化,允許更多的(de)(de)(de)(de)可(ke)(ke)(ke)見光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)透(tou)(tou)(tou)(tou)(tou)(tou)過所(suo)(suo)致。此外,將透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)曲(qu)線(xian)在(zai)可(ke)(ke)(ke)見光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)范圍內進行積分(fen),得到(dao)(dao)其(qi)(qi)在(zai)可(ke)(ke)(ke)見光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)波長范圍內的(de)(de)(de)(de)平(ping)(ping)均(jun)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)值,見表3,其(qi)(qi)數(shu)值變(bian)化趨勢與(yu)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)曲(qu)線(xian)結果一致。純(chun)PLA薄(bo)膜(mo)(mo)(mo)的(de)(de)(de)(de)可(ke)(ke)(ke)見光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)平(ping)(ping)均(jun)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)高(gao)達91.6%,但由(you)(you)于PLA與(yu)PBAT相(xiang)(xiang)容性(xing)差,PBAT分(fen)散(san)相(xiang)(xiang)尺寸(cun)較(jiao)大,PLA/PBAT (95/5)薄(bo)膜(mo)(mo)(mo)的(de)(de)(de)(de)平(ping)(ping)均(jun)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)下降(jiang)(jiang)至(zhi)76.9%。而(er)隨著(zhu)(zhu)ADR的(de)(de)(de)(de)加入,PLA/PBAT/ADR薄(bo)膜(mo)(mo)(mo)的(de)(de)(de)(de)平(ping)(ping)均(jun)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)不斷增大,特別是(shi)(shi)PLA/PBAT/ADR (95/5/0.5)薄(bo)膜(mo)(mo)(mo)的(de)(de)(de)(de)平(ping)(ping)均(jun)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)可(ke)(ke)(ke)增大至(zhi)86.6%,接近(jin)于純(chun)PLA的(de)(de)(de)(de)平(ping)(ping)均(jun)透(tou)(tou)(tou)(tou)(tou)(tou)光(guang)(guang)(guang)(guang)(guang)(guang)(guang)(guang)率(lv)(lv)(lv)(91.6%)
由(you)上(shang)述試(shi)(shi)驗結(jie)果對比(bi)可(ke)知,相(xiang)對于(yu)純(chun)PLA和PLA/PBAT (95/5)薄(bo)膜(mo)試(shi)(shi)樣,PLA/PBAT/ADR (95/5/0.5)薄(bo)膜(mo)在(zai)拉(la)伸韌(ren)性(xing)(xing)和透(tou)(tou)光(guang)率之間取得了(le)較(jiao)(jiao)好平衡。2.6 結(jie)晶(jing)(jing)(jing)(jing)(jing)性(xing)(xing)能(neng)除了(le)PBAT分散(san)相(xiang)可(ke)以顯(xian)(xian)著影響(xiang)PLA/PBAT/ADR薄(bo)膜(mo)試(shi)(shi)樣的(de)(de)(de)透(tou)(tou)光(guang)性(xing)(xing)能(neng)外,PLA基體(ti)的(de)(de)(de)結(jie)晶(jing)(jing)(jing)(jing)(jing)度(du)及結(jie)晶(jing)(jing)(jing)(jing)(jing)結(jie)構(gou)(gou)也(ye)可(ke)能(neng)會(hui)對薄(bo)膜(mo)透(tou)(tou)光(guang)率產生(sheng)較(jiao)(jiao)為(wei)(wei)明(ming)顯(xian)(xian)的(de)(de)(de)作用(yong)(yong)。通(tong)常情況下,聚合物基體(ti)的(de)(de)(de)結(jie)晶(jing)(jing)(jing)(jing)(jing)度(du)越(yue)高(gao),晶(jing)(jing)(jing)(jing)(jing)體(ti)尺寸越(yue)大,對透(tou)(tou)射光(guang)的(de)(de)(de)遮擋(dang)作用(yong)(yong)越(yue)強,其材料的(de)(de)(de)透(tou)(tou)光(guang)率也(ye)會(hui)出(chu)(chu)現(xian)(xian)較(jiao)(jiao)明(ming)顯(xian)(xian)的(de)(de)(de)減弱(ruo)趨(qu)勢(shi)。采(cai)用(yong)(yong)DSC和WAXD測試(shi)(shi)來表征(zheng)薄(bo)膜(mo)試(shi)(shi)樣的(de)(de)(de)結(jie)晶(jing)(jing)(jing)(jing)(jing)度(du)及其結(jie)晶(jing)(jing)(jing)(jing)(jing)結(jie)構(gou)(gou)。圖(tu)5為(wei)(wei)PLA,PLA/PBAT (95/5),PLA/PBAT/ADR (95/5/0.25)以及(95/5/0.5)薄(bo)膜(mo)試(shi)(shi)樣的(de)(de)(de)升溫DSC曲(qu)(qu)線,由(you)DSC曲(qu)(qu)線獲得的(de)(de)(de)相(xiang)關熱(re)力學參數列于(yu)表4中。純(chun)PLA在(zai)102.3 °C時出(chu)(chu)現(xian)(xian)顯(xian)(xian)著放熱(re)峰(feng),這(zhe)是PLA非(fei)晶(jing)(jing)(jing)(jing)(jing)組分在(zai)升溫過(guo)程(cheng)中發(fa)生(sheng)冷(leng)結(jie)晶(jing)(jing)(jing)(jing)(jing)所(suo)致。而(er)繼(ji)續升溫至167.9 °C時,出(chu)(chu)現(xian)(xian)明(ming)顯(xian)(xian)吸熱(re)峰(feng),其對應(ying)區間為(wei)(wei)PLA結(jie)晶(jing)(jing)(jing)(jing)(jing)組分的(de)(de)(de)熔融過(guo)程(cheng)。隨著PBAT和PBAT/ADR預(yu)混(hun)物的(de)(de)(de)加入(ru),能(neng)夠發(fa)現(xian)(xian)Tcc有(you)明(ming)顯(xian)(xian)降低趨(qu)勢(shi),這(zhe)說明(ming)柔性(xing)(xing)PBAT組分的(de)(de)(de)引入(ru)能(neng)夠提高(gao)PLA基體(ti)的(de)(de)(de)冷(leng)結(jie)晶(jing)(jing)(jing)(jing)(jing)能(neng)力。需要特(te)別指出(chu)(chu)的(de)(de)(de)是,純(chun)PLA薄(bo)膜(mo)的(de)(de)(de)結(jie)晶(jing)(jing)(jing)(jing)(jing)度(du)僅(jin)為(wei)(wei)8.0%,而(er)PLA共混(hun)薄(bo)膜(mo)的(de)(de)(de)結(jie)晶(jing)(jing)(jing)(jing)(jing)度(du)雖略(lve)有(you)提升,但結(jie)晶(jing)(jing)(jing)(jing)(jing)度(du)仍均不(bu)(bu)高(gao)于(yu)13.0%。這(zhe)是由(you)于(yu)PLA熔體(ti)的(de)(de)(de)結(jie)晶(jing)(jing)(jing)(jing)(jing)速(su)度(du)緩慢,遠遠跟不(bu)(bu)上(shang)薄(bo)膜(mo)吹脹后冷(leng)卻(que)定(ding)型(xing)速(su)度(du)所(suo)致。圖(tu)6為(wei)(wei)上(shang)述四(si)種(zhong)薄(bo)膜(mo)的(de)(de)(de)WAXD譜(pu)圖(tu)。觀察發(fa)現(xian)(xian)其WAXD譜(pu)圖(tu)中均呈現(xian)(xian)出(chu)(chu)典型(xing)的(de)(de)(de)非(fei)晶(jing)(jing)(jing)(jing)(jing)結(jie)構(gou)(gou)衍(yan)射特(te)征(zheng),未發(fa)現(xian)(xian)明(ming)顯(xian)(xian)的(de)(de)(de)PLA結(jie)晶(jing)(jing)(jing)(jing)(jing)結(jie)構(gou)(gou)特(te)征(zheng)衍(yan)射峰(feng)。這(zhe)可(ke)能(neng)是由(you)于(yu)薄(bo)膜(mo)中生(sheng)成的(de)(de)(de)晶(jing)(jing)(jing)(jing)(jing)體(ti)數量少,且結(jie)晶(jing)(jing)(jing)(jing)(jing)結(jie)構(gou)(gou)發(fa)育不(bu)(bu)完善,不(bu)(bu)能(neng)產生(sheng)顯(xian)(xian)著的(de)(de)(de)X射線衍(yan)射效應(ying)所(suo)致。
綜合上述(shu)測試和結果(guo)分析可(ke)知,PLA,PLA/PBAT (95/5),PLA/PBAT/ADR (95/5/0.25)以及PLA/PBAT/ADR (95/5/0.5)薄(bo)(bo)膜(mo)結晶度低,接近非(fei)晶態,因此其結晶結構對薄(bo)(bo)膜(mo)的物理性能(neng)以及透(tou)光率影(ying)響很小。
3結論
(1)通(tong)過(guo)兩步共(gong)混(hun)法成功制(zhi)備了PLA/PBAT/ADR共(gong)混(hun)物(wu)薄膜。流(liu)變學結果顯(xian)示,隨著PBAT/ADR預混(hun)物(wu)中(zhong)ADR添加量的增大(da),PLA/PBAT/ADR共(gong)混(hun)物(wu)黏度(du)和熔(rong)體強度(du)顯(xian)著增大(da)。同時(shi),由SEM觀察可知,共(gong)混(hun)物(wu)界面增容作用顯(xian)著,PBAT分散(san)相粒徑得到明顯(xian)細化。
(2)吹膜成型(xing)實(shi)驗表明,相對(dui)于PLA/PBAT (95/5)粒料(liao),PLA/PBAT/ADR (95/5/0.5)粒料(liao)在加工過程中表現出更(geng)高的(de)熔體強度和吹膜成型(xing)穩定性。
(3)拉伸測(ce)試(shi)和透(tou)光率測(ce)試(shi)表明,純(chun)PLA的(de)平(ping)均(jun)透(tou)光率可(ke)達91.6%,但斷(duan)裂(lie)伸長(chang)率僅(jin)為(wei)(wei)31.0%,而隨著柔(rou)性PBAT加入,PLA/PBAT (95/5)薄膜材(cai)料的(de)斷(duan)裂(lie)伸長(chang)率可(ke)增大至(zhi)216.1%,但平(ping)均(jun)透(tou)光率卻跌至(zhi)76.9%。作(zuo)為(wei)(wei)對(dui)比,PLA/PBAT/ADR (95/5/0.5)薄膜的(de)斷(duan)裂(lie)伸長(chang)率和平(ping)均(jun)透(tou)光率則分別達到461.4%和86.6%,在獲得(de)了高拉伸韌(ren)性的(de)同(tong)時,兼具較(jiao)好的(de)透(tou)光性能。
摘要:工(gong)程(cheng)塑料(liao)應用
咨詢電話
微信掃碼咨詢