TWI671319B - 固態延伸的hdpe - Google Patents

固態延伸的hdpe Download PDF

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TWI671319B
TWI671319B TW104111000A TW104111000A TWI671319B TW I671319 B TWI671319 B TW I671319B TW 104111000 A TW104111000 A TW 104111000A TW 104111000 A TW104111000 A TW 104111000A TW I671319 B TWI671319 B TW I671319B
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hdpe resin
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astm
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孫陸逸
麥可 瑪里歐
約翰 亞西鮑彿
鳳奎 李
里蘭德 丹尼爾斯
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美商芬娜工業技術股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06Injection blow-moulding
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02Ethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02Combined blow-moulding and manufacture of the preform or the parison
    • B29C2049/023Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04Polymers of ethylene
    • B29K2023/06PE, i.e. polyethylene
    • B29K2023/0608PE, i.e. polyethylene characterised by its density
    • B29K2023/065HDPE, i.e. high density polyethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0094Condition, form or state of moulded material or of the material to be shaped having particular viscosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0063Density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0088Molecular weight
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/712Containers; Packaging elements or accessories, Packages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/10Applications used for bottles

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

揭露一種ISBM物件,其中該ISBM物件係由一種HDPE樹脂製得,該HDPE樹脂具有依據ASTM D-1238;190℃/2.16kg所測得之0.1至5.0dg/min的MI2,依據ASTM D792所測得之從0.940至0.970g/cc的密度,大於40,000g/mol之峰分子量,及介於15,000和250,000Pa‧sec間之零剪切黏度。

Description

固態延伸的HDPE
本發明之具體實例大體上係關於使之適合用於射出拉伸吹製成型的聚合物。特別是,本發明之具體實例係關於使之適合用於射出拉伸吹製成型的乙烯聚合物。
數種聚合物處理技術使用固態拉伸於產生終產物。非限制性例子包含熱成型、拉伸條帶(drawn tape)、拉伸單絲、機械方向定向(MDO)薄膜、雙軸定向薄膜(例如經由雙泡處理及拉幅機拉伸)、固態擠製及射出拉伸吹製成型。傳統上,這些處理使起始物件在低於其熔融溫度的溫度下變形,將其形成最終所欲形狀。
射出拉伸吹製成型(ISBM)為固態拉伸的子集。ISBM可消除修邊及重複使用於習知擠壓吹製成型(EBM)之再磨。ISBM經常產生較精密的瓶子螺紋,因為瓶子螺紋係經由射出成型步驟形成。該固態拉伸步驟可製造具有優越頂部負載(top-load)性質及其他改良物理性質,其可容許降低規測(downgauging)/輕質,之硬瓶。此 外,表面平滑度可藉由ISBM所製造之物件改良,從而增進可印性及列印品質。另外,平滑的表面提供成型物件,例如瓶子,適當的標籤黏附性。由於ISBM瓶子係在固態拉伸,可降低或消除對熔體強度的需求。對習知EBM不很適合的樹脂對ISBM可以是相當適合的。
ISBM商業線能在1小時內生產數以千計的瓶 子。為了實現這樣的速度,典型地用於ISBM的樹脂具有優良的加工性。其他樹脂特性可包含即可拉伸性以及在拉伸和吹製步驟期間很少數的失敗率。
在本揭示之一具體實例中,揭露了一種ISBM 物件,其中該ISBM物件係由一種HDPE樹脂製得,該HDPE樹脂具有依據ASTM D-1238;190℃/2.16kg所測得之0.1至5.0dg/min的MI2,依據ASTM D792所測得之從0.940至0.970g/cc的密度,大於40,000g/mol之峰分子量,及介於15,000和250,000Pa‧sec間之零剪切黏度。
在本揭示之另一具體實例中,揭露了一種 ISBM物件,其中該ISBM物件係由一種HDPE樹脂製得,該HDPE樹脂具有依據ASTM D-1238;190℃/2.16kg所測得之0.5至8.0dg/min的MI2,從2.0至7.0之多分散性,及介於1000至50,000Pa‧sec間之零剪切黏度。該物件具有依據ASTM D523所測得之大於或等於50的45°光澤度,及依據ASTM 1003所測得之小於或等於25%的 濁度。
在本揭示之又一具體實例中,揭露了一種形 成射出拉伸吹製成型物件之方法。該方法包含提供一種HDPE樹脂,其具有依據ASTM D-1238;190℃/2.16kg所測得之0.1至5.0dg/min的MI2,依據ASTM D792所測得之從0.940至0.970g/cc的密度,由GPC所測得之小於50,000g/mol之峰分子量,及介於1000至250,000Pa‧sec間之零剪切黏度。該方法進一步包含將該HDPE樹脂射出成型成預製件及將該預製件拉伸-吹製成一物件。該方法具有小於2%之失敗率。
該圖式說明實施例所描述之聚乙烯ISBM瓶子之頂部負載強度對密度。
現在將提供詳細的描述。以下揭示包含特定具體實例、變化型及實施例,但該揭示不受這些具體實例、變化型或實施例限制,包含其等係使此項技術具有通常技術者在將本申請案之資訊與可得之資訊及技術結合時,能製造及使用該揭示。
本文中所用的各種術語係顯示於下。就使用在申請專利範圍中之術語在下文未給予定義的情況,應賦予相關技術者已給予該術語之如已發行的出版物和核發的 專利中所反映的最廣定義。再者,除非另有指明,描述於本文中之所有化合物可為經取代或未經取代,且化合物的列表包括其衍生物。
在本揭示之某些具體實例中,揭露了適合於ISBM之聚合物。在一或更多具體實例中,例如當需要低失敗率及高頂部負載強度時,可使用具有某些特性之高密度聚乙烯(HDPE)。用於這些具體實例之HDPE可具有依據ASTM D-1238;190℃/2.16kg所測得之0.1至5.0dg/min,或是從0.2至2.0dg/min或從0.4至0.7dg/min的MI2。用於這些具體實例之HDPE的密度依據ASTM D792測定,可為0.940至0.970g/cc,0.950至0.962g/cc或0.958至0.959g/cc。該峰分子量(Mp)依據GPC測定,可為大於40,000g/mol,或大於50,000g/mol。該重量平均分子量(Mw)依據GPC測定,可在介於100,000和200,000之間或介於130,000和170,000之間。在某些具體實例中,該多分散性(Mw/Mn)可在介於5和15之間,或介於8和14之間。該零剪切黏度可在介於15,000和250,000Pa.sec之間,從30,000至250,000Pa.sec,或從35,000至70,000Pa.sec。該鬆弛時間(秒)可在介於0.0010和0.010之間,或介於0.015和0.060之間。從此類樹脂經由ISBM製造之物件的失敗率可小於2%。此類樹脂之例子包含,但不限於道達爾(Total)7208,9458及BDM1 08-12。
在某些其他具體實例中,例如需要具有優異 光學性質之由ISBM所製造的物件,該HDPE可具有依據ASTM D-1238;190℃/2.16kg所測得之0.5至8.0dg/min,1.0至5.0dg/min,或1.5至3.0dg/min的MI2。 該HDPE之多分散性(Mw/Mn)可從2.0至7.0,2.5至6.5,或從3.0至6.0。
流變寬度係樹脂之鬆弛時間分佈的函數,其進而為樹脂分子結構之函數。該寬度參數係假設Cox-Merz規則,使用線性-黏彈性動態振動器頻率掃描實驗,以經修飾的Carreau-Yasuda(CY)模型,擬合所產生的流動曲線而經實驗測得。
η=ηB[1+(λγ)α](n-1α)
其中:η=黏度(Pa s);γ=剪切速率(1/s);α=流變寬度參數[CY模型參數,其描述牛頓與冪次律型(power law behavior)之間過渡區域的寬度];λ=鬆弛時間sec[CY模型參數,其描述過渡區域時間之位置];ηB=零剪切黏度(Pa s)[CY模型參數,其定義牛頓高原(Newtonian plateau)];及n=冪次律常數[CY模型參數,其定義高剪切速率區域之最終斜率]。
為了促進模型擬合度,該冪次律常數(n)係維持在一定值(n=0)。實驗係使用平行板幾何型及在頻率範 圍0.1至316.2秒(-1)之線性黏彈性區域內的應變來進行。頻率掃描係在三個溫度(170℃,200℃,及230℃)下進行,並使用已知時間-溫度疊加法將該數據轉換成在190℃形成主區線。該HPDE樹脂之零剪切黏度可在介於1000至50,000Pa‧sec之間,2000至25,000Pa‧sec之間,或2500至12,500Pa‧sec之間。
由此類樹脂製得之物件可具有依據ASTM D523所測得之大於或等於50,或大於60的45°光澤度,及依據ASTM 1003所測得之小於或等於25%,或小於15%的濁度。此類樹脂的例子包含,但不限於道達爾(Total)6410,6420及6450。
產品應用
在一具體實例中,該聚合物係被使用於射出拉伸吹製成型(ISBM)。可使用ISBM製造薄壁、高透明度瓶子。此類方法為熟習此項技術者所週知。例如,ISBM方法可包括將該聚合物射出成預製件,其接著將該預製件拉伸-吹製成瓶子。
實施例
比較數種聚乙烯樹脂在ISBM製程中之性能。該HDPE樹脂均為道達爾石化(Total Petrochemical)產品,且全部在商用反應器製造。關於該樹脂之細節係描述於表1。
表1之分子量係藉由GPC測得;密度係藉由D792測得。MI2 MI5,及HLMI係藉由ASTM D-1238;190℃/2.16kg測得。HLMI係定義為高負載熔融指數。
列於表1之該樹脂的加工性係根據下列等級分級:等級=1。只有<20%的預製件成功地形成瓶子。
等級=2。介於20%至<90%之間的預製件成功地形成瓶子。
等級=3。介於90%至<98%之間的預製件成功地形成瓶子。
等級=4。98%的預製件成功地形成瓶子。
基於此分級系統,該等HDPE評定如下:1=2285,5502
2=6410,6420,6450
4=7208,9458,BDM1 08-12
不同的HDPE樣本在拉伸性能上具有明顯的差異。與道達爾6410、6420、6450、2285及5502相較,道達爾7208、9458和BDM1 08-12具有優良的拉伸性能。
將該等瓶子的頂部負載強度列表顯示,其負載以牛頓測量:
6410:162±14牛頓
6420:159±14牛頓
6450:194牛頓(只有測試一個瓶子)
7208:178±4牛頓
9458:189±7牛頓
BDM1 08-12:176±6牛頓
頂部負載強度提供關於ISBM最終用途物件在壓碎測試條件下使用時之壓碎性質的資訊。該頂部負載強度測試之進行,係藉由將該ISBM物件置於下盤(垂直地),然後將其緩慢對著上盤升高,以測量該ISBM物件相應的負載容量。
由道達爾7208、9458製造的瓶子,及BDM 08-12瓶子具有比道達爾6410和6420高的頂部負載強度,雖然道達爾6410和6420較為緻密。此外,雙峰型(bimodal)樹脂道達爾9458瓶子展示了比具有相同密度之單峰型級別要高的頂部負載強度。因此,雙峰型級別PE 增強了加工性及瓶子頂部負載強度。圖式比較各測試樣本之頂部負載強度對密度。
由道達爾6410和6420製造的瓶子,及6450瓶子具有所測試HDPE樹脂之優良光學性質。道達爾6420尤其具有超過道達爾7208、9458或BDM1 08-12的優越的濁度及光澤度。
雖然上述係關於本揭示之具體實例,其他及進一步的具體實例可在不背離其基本範圍下設計而來,且其範圍係由隨後之申請專利範圍決定。

Claims (21)

  1. 一種射出拉伸吹製成型(ISBM)物件,其包括:一種HDPE樹脂,其具有依據ASTM D-1238;190℃/2.16kg所測得之0.1至5.0dg/min的MI2,依據ASTM D792所測得之從0.940至0.970g/cc的密度,大於40,000g/mol之峰分子量,及介於15,000和250,000Pa˙sec間之零剪切黏度。
  2. 如申請專利範圍第1項之物件,其中該HDPE樹脂具有依據ASTM D-1238;190℃/2.16kg所測得之從0.25至1.0dg/min的MI2。
  3. 如申請專利範圍第1項之物件,其中該HDPE樹脂具有依據ASTM D792所測得之從0.953至0.959g/cc的密度。
  4. 如申請專利範圍第1項之物件,其中該HDPE樹脂具有大於50,000g/mol之峰分子量。
  5. 如申請專利範圍第1項之物件,其中該HDPE樹脂具有介於35,000至70,000Pa˙sec之零剪切黏度。
  6. 如申請專利範圍第1項之物件,其中該HDPE樹脂係雙峰型(bimodal)。
  7. 如申請專利範圍第1項之物件,其中該HDPE樹脂之MI2係介於0.4和0.7之間。
  8. 如申請專利範圍第1項之物件,其中該HDPE樹脂之Mw係介於130,000和170,000之間。
  9. 如申請專利範圍第1項之物件,其中該HDPE樹脂之密度係介於0.958和0.959之間。
  10. 如申請專利範圍第1項之物件,其中該HDPE樹脂之鬆弛時間係介於0.015和0.060之間。
  11. 一種ISBM物件,其包括:一種HDPE樹脂,其具有依據ASTM D-1238;190℃/2.16kg所測得之0.5至8.0dg/min的MI2,從2.0至7.0之多分散性(Mw/Mn),及介於1000至50,000Pa˙sec間之零剪切黏度;且該物件具有依據ASTM D523所測得之大於或等於50的45°光澤度,及依據ASTM 1003所測得之小於或等於25%的濁度。
  12. 如申請專利範圍第11項之物件,其中該HDPE樹脂具有依據ASTM D-1238;190℃/2.16kg所測得之1.5至3.0dg/min的MI2。
  13. 如申請專利範圍第11項之物件,其中該HDPE樹脂具有從3.0至6.0之多分散性(Mw/Mn)。
  14. 如申請專利範圍第11項之物件,其中該HDPE樹脂具有從2500至12,500Pa˙sec之零剪切黏度。
  15. 如申請專利範圍第11項之物件,其具有依據ASTM D523所測得之大於60的45°光澤度。
  16. 如申請專利範圍第11項之物件,其具有依據ASTM 1003所測得之小於15%的濁度。
  17. 一種形成射出拉伸吹製成型物件之方法,其包括:提供一種HDPE樹脂,其具有依據ASTM D-1238;190℃/2.16kg所測得之0.1至5.0dg/min的MI2,依據ASTM D792所測得之從0.940至0.970g/cc的密度,大於40,000g/mol之峰分子量,及介於15,000至250,000Pa˙sec間之零剪切黏度;將該HDPE樹脂射出成型成預製件;及將該預製件拉伸-吹製成一物件。
  18. 如申請專利範圍第17項之方法,其中該方法具有10%或更小之失敗率。
  19. 如申請專利範圍第18項之方法,其中該方法具有小於2%之失敗率。
  20. 一種形成射出拉伸吹製成型物件之方法,其包括:提供一種HDPE樹脂,其具有依據ASTM D-1238;190℃/2.16kg所測得之0.5至8.0dg/min的MI2,從2.0至7.0之多分散性(Mw/Mn),及介於1000至50,000Pa˙sec間之零剪切黏度;且該物件具有依據ASTM D523所測得之大於或等於50的45°光澤度及依據ASTM 1003所測得之小於或等於25%的濁度;將該HDPE樹脂射出成型成預製件;及將該預製件拉伸-吹製成一物件。
  21. 一種射出拉伸吹製成型(ISBM)物件,其包括:一種HDPE樹脂,其具有依據ASTM D-1238;190℃/2.16kg所測得之0.4至0.7dg/min的MI2,依據ASTM D792所測得之從0.958至0.959g/cc的密度,大於40,000g/mol之峰分子量,及介於0.015和0.060間之鬆弛時間。
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