TW201527343A - 改質聚合物之方法 - Google Patents
改質聚合物之方法 Download PDFInfo
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- TW201527343A TW201527343A TW103138586A TW103138586A TW201527343A TW 201527343 A TW201527343 A TW 201527343A TW 103138586 A TW103138586 A TW 103138586A TW 103138586 A TW103138586 A TW 103138586A TW 201527343 A TW201527343 A TW 201527343A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- IVRMZWNICZWHMI-UHFFFAOYSA-N Azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 polyethylene Polymers 0.000 claims description 25
- 150000001540 azides Chemical class 0.000 claims description 18
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
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- 239000002585 base Substances 0.000 description 2
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- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical group ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- UJVWVCLAIRDXKS-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical group C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1.C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 UJVWVCLAIRDXKS-UHFFFAOYSA-N 0.000 description 1
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- KNCZPLRYWQLPQT-UHFFFAOYSA-N 1-tert-butyl-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C(C)(C)C KNCZPLRYWQLPQT-UHFFFAOYSA-N 0.000 description 1
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- 239000005864 Sulphur Substances 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
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- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KHECLXBZYQYEGI-UHFFFAOYSA-O sulfanium azide Chemical compound [N-]=[N+]=[N-].[SH3+] KHECLXBZYQYEGI-UHFFFAOYSA-O 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/27—Compounds containing a nitrogen atom bound to two other nitrogen atoms, e.g. diazoamino-compounds
- C08K5/28—Azides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
本發明揭示在不存在元素硫的量大於0.5phr之情況下改質聚合物之方法，該方法包括以下步驟：a.在範圍80至250℃之溫度下將該聚合物與經馬來醯亞胺官能化之單疊氮化物混合，以形成官能化聚合物，及b.在範圍150至270℃之溫度下熱處理該官能化聚合物。
Description
本發明係關於一種改質聚合物而無需過氧化物或硫磺之方法。
習知地，彈性體係藉由使用與若干硫磺硫化促進劑結合之元素硫而交聯的。然而，在過去的幾年，以過氧化物交聯得到更多之應用。與硫磺交聯系統相比，過氧化物交聯之優勢為更好的耐返原性、更好的耐熱性及耐化學性及更好的壓縮形變。
聚烯烴例如聚乙烯一般以過氧化物固化。基於硫磺之固化系統一般不用於聚烯烴，因為其處理溫度接近或超過硫磺固化包之固化起始值。另外，在聚烯烴應用中，最不希望出現由添加劑引起的變色及硫磺組分之氣味。
然而，已知聚丙烯在過氧化物處理後降解，且無法經硫磺交聯，因為在聚合物中不存在不飽和。
過氧化物係藉由創造長鏈分支而用以增強聚丙烯之熔融強度。
硫磺-及過氧化物處理共有的又一劣勢為在過程中會形成有機揮發物。另外，該等固化系統之組分(即硫磺、促進劑、過氧化物及其分解產物)通常趨向於遷移至經處理之聚合物物件之表面(此稱為「起霜」)，此可對皮膚或其他表面造成非所欲的接觸污染。
因此，需要提供一種改質聚合物而無需過氧化物及硫磺或含硫化合物之方法。
較佳地，該方法亦避免有機揮發物的釋放及起霜現象。
可藉由本發明之方法達成此目的，該方法不需要使用過氧化物、硫磺或硫化促進劑，且其中氮氣可為唯一形成之揮發組分。
該方法涉及聚合物主鏈之官能化。在此官功能化過程中，釋放氮氣。該方法之第二步涉及熱處理，在該過程中，無需釋放任何額外的揮發物。
本發明之方法係關於一種在不存在元素硫的量大於0.5phr之情況下改質聚合物之方法，該方法包括以下步驟：a.在範圍80至250℃之溫度下將該聚合物與經馬來醯亞胺官能化之單疊氮化物混合，以形成官能化聚合物，及b.在範圍150至270℃之溫度下熱處理該官能化聚合物。
可藉由該方法合適地改質之聚合物包括彈性體、鏈飽和之聚合物及聚酯。
彈性體之實例為天然橡膠(NR)、苯乙烯丁二烯橡膠(SBR)、丁二烯橡膠(BR)、丁基橡膠(IIR)、乙烯丙烯共聚物彈性體(EPM)、乙烯丙烯二烯三元共聚物彈性體(EPDM)及乙烯乙酸乙烯酯共聚物(EVA)。
鏈飽和之聚合物包括聚烯烴。合適之聚烯烴為聚苯乙烯、聚乙烯(LDPE、LLDPE、HDPE)及聚丙烯(PP)、及其均聚物及共聚物。該等共聚物之實例為基於聚乙烯-辛烯或丁烷共聚物之聚烯烴彈性體(POE)。
聚酯之實例為聚乳酸(即聚乳交酯PLA)及聚(羥基烷酸酯)例如聚(羥基丁酸酯)、聚(丁烯琥珀酸酯)、聚乙交酯及聚(ε-己內酯)。
可用於本發明之方法中之經馬來醯亞胺官能化之單疊氮化物較佳具有下式：
其中Y為：
m為0或1，n為0或1，n+m=1或2，較佳地為1，及X為具有1至12個碳原子之直鏈或分支鏈脂族或芳香族烴部分，其可視情況含有雜原子。
當X含有雜原子時，其較佳地具有以下結構中之一者：
其中Z、Q及P為範圍從1至6之整數，及R選自由H、烷基、芳基、苯基及經取代之苯基組成之群。
特別佳的單疊氮化物為4-(2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯疊氮：
官能化步驟a)可在可於80至250℃範圍之溫度下混合聚合物之任何合適之設備中實施。該設備之實例為內部分批混合機(通常稱為班伯里(Banbury)混合機)、雙輥軸研磨機(當可加熱輥軸時)、擠壓機及類似者。官能化之結果為含有馬來醯亞胺官能基之聚合物。
聚合物及馬來醯亞胺官能性疊氮化物較佳以0.01至20phr、更佳0.05至10phr，且最佳0.1至5phr之重量比率混合。術語「phr」指：重量份/100重量份聚合物。
除聚合物及馬來醯亞胺官能性疊氮化物以外，亦可向混合物中加入自由基清除劑及抗氧化劑。自由基清除劑之實例為第三丁基氫醌(TBHQ)、2,2,6,6-四甲基哌啶氧(TEMPO)及4-羥基-2,2,6,6-四甲基哌啶-1-氧基(OH-TEMPO)。合適之抗氧化劑之實例為空間位阻多核苯酚(例如Vulkanox® SKF、Vulkanox® DS、Vulkanox BKF、Irganox 1010)、胺類抗氧化劑(例如Flectol TMQ)、基於二苯基二胺之抗氧化劑(例如Santonox 6PPD)及亞磷酸酯(例如Weston TNPP)。
官能化係在範圍80至250℃，較佳90至230℃，更佳100至200℃，及最佳110至180℃之溫度下實施。溫度選擇取決於聚合物之類型及疊氮化物之類型。磺醯基疊氮化物(疊氮基磺酸酯)一般在130℃左右開始分解成反應性氮烯部分，在180℃左右達到峰值；疊氮甲酸酯在超過110℃時開始分解，在160℃達到峰值。所形成之氮烯部分會與聚合物反應，從而導致氮烯接枝於聚合物上。
其中疊氮化物可與不飽和聚合物反應之另一機制係經由所謂的「點擊」機制，其可在低於疊氮化物之分解溫度下發生。在完全飽和之聚合物上，該「點擊」機制將不會發生。
較佳之反應時間為1至120分鐘，更佳1至60分鐘，且最佳2至30分鐘。
在該官能化步驟期間或之後，聚合物可成形為所需形式。該成
形可在模具(壓縮、注射或轉移模塑)、擠壓機(其中成形模具可安置於擠壓機頭上)、或壓光機(為將聚合物熔體處理成薄片或薄膜)中實施。同樣，可使用所謂熱成形方法以從聚烯烴之箔或薄片形成形狀。
隨後，該官能化聚合物在範圍150至270℃，較佳160至250℃，最佳170至220℃之溫度下經熱處理。因為本發明之方法之兩個步驟均為利用自由基機制之熱方法，該等兩個步驟可作為一個整體實施，換言之：無需在兩者不同步驟之間分開。
然而，若需在兩者步驟之間分開，則此可藉由在不同溫度下實施各步驟，或藉由在步驟a)中加入自由基清除劑及/或抗氧化劑及/或在步驟b)中加入陰離子聚合觸媒、C-C引發劑或過氧化物而實現。
自由基清除劑及抗氧化劑之實例已於上列出。陰離子聚合觸媒之實例為三乙二胺(DABCO)、聚合性1,2-二氫-2,2,4-三甲基喹啉(抗氧化劑TMQ)及1,8-二氮雜二環[5.4.0]十一碳-7-烯(DBU)。抗氧化劑TMQ(1,2-二氫-2,2,4-三甲基喹啉)可作為自由基清除劑及陰離子聚合觸媒。
合適之過氧化物之實例為第三丁基過氧化異丙苯、3,6,9-三乙基-3,6,9-三甲基-1,4,7-三過氧壬烷、過氧化二異丙苯、二(第三丁基過氧化異丙基)苯及2,5-二甲基-2,5-二(第三丁基過氧)己烷。
合適之C-C引發劑為苯頻哪醇(1,1,2,2-四苯基-1,2-乙二醇)。
發明之方法導致聚合物之流變性變化。所得之經改質聚合物可經完全交聯或經流變性改質。流變性改質意指聚合物之流變學性質例如熔體流動指數被改變。
對於聚丙烯，所需之流變性改質可為藉由創造分支使熔體流動指數降低。在需要高熔融強度之聚丙烯之應用(諸如熱成形方法)中使用分支聚丙烯。官能化聚合物係經流變性改質還係經交聯主要取決於聚合物之類型。一般而言，聚丙烯係經分支及乙烯丙烯共聚物係經交聯。
儘管本發明之方法不排除過氧化物之存在，但該存在係非所需。較佳地，本發明之方法係在不存在過氧化物之情況下實施。
本發明之方法亦不排除硫磺硫化促進劑(即習知地用於加速硫固化之化合物)之存在。然而，該存在係非所需。較佳地，本發明之方法係在不存在硫磺硫化促進劑之情況下實施。
本發明之方法亦不需要使用元素硫。然而，允許添加一些硫，只要其不超過0.5phr，較佳不超過0.2phr，甚至更佳不超過0.1phr即可。最佳地，在反應過程中不存在元素硫。
實例
實例1
在該實例中使用包含表1中所列成分之基於天然橡膠之化合物。該橡膠化合物適用於卡車輪胎胎面化合物。
在雙輥軸研磨機上將47公克該化合物與0.93公克馬來醯亞胺磺醯疊氮(4-(2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯疊氮)混合。此相當於3.2phr疊氮化物。於120℃之溫度下，在具有50mL內部體積之班伯里類型混合機中，熱處理混合物持續30分鐘以使該疊氮化物接枝於NR橡膠上。
在該疊氮化物接枝於天然橡膠上後，藉由在170℃下熱處理固化該化合物。在該熱處理過程中，馬來醯亞胺官能基彼此反應並形成網
狀物，藉以使橡膠交聯。
作為對比，於超過50℃之溫度下，在雙輥軸研磨機中將相同之NR橡膠與2.9phr過氧化二異丙苯混合；足以熔化過氧化物。藉由在170℃下之熱處理固化所得之化合物。在該熱處理過程中，過氧化物分解為自由基，其與聚合物鏈反應，藉以形成網狀物並使橡膠交聯。
表2列出所得之經改質聚合物之性質。列出的為焦化時間(ts2；從曲線最小值增加0.2Nm扭矩所需要之時間)及t50與t90(即於流變儀中測量，分別達到最終之最大交聯密度之50%及90%所需之時間)。在流變儀中測得之△扭矩(△S)係用作交聯密度之指示。結果顯示經3.2phr疊氮化物改質之天然橡膠化合物之交聯行為係與經2.9phr過氧化二異丙苯改質者相似。
最終交聯水平(用MH表示)對於兩個固化系統而言係相當。同樣地，機械性質(用拉伸強度及斷裂伸長率表示)對於兩個固化系統而言係相似。
該等結果指示，本發明之方法得到令人滿意之交聯行為，而不產生除氮氣之外的揮發物。
實例2
於170℃之溫度下，在班伯里混合機中將聚丙烯均聚物(Moplen HP500N)與馬來醯亞胺磺醯疊氮混合，並在此溫度下反應持續20分鐘。在此反應過程中，該疊氮化物接枝於聚丙烯上。在溫度升高至200℃並在200℃下混合2至3分鐘後，聚合物上之馬來醯亞胺基團開始反應並產生分支並交聯，從表3中下降之熔體流動指數(MFI)可明顯看出。
該表顯示加入之疊氮化物之量(以phr計)之作用。使用之疊氮化物越多，MFI越小，且交聯水平越高。
Irganox® 1010係經添加作為聚丙烯之穩定劑，並阻止馬來醯亞胺基團在170℃下之聚合。Irganox® 1010影響馬來醯亞胺基團之間的交聯反應，此可從表3中倒數第二個條目觀測，其中Irganox® 1010濃度之增高導致MFI之增高，此最可能係由自由基清除干擾馬來醯亞胺交聯所致。
藉由對已在170℃下混合之樣本測量在200℃時之扭矩增加來觀測交聯。該等樣本顯示在170℃下無交聯，僅在流變儀中曝露於200℃後其才開始交聯。扭矩增加列於表3中。
實例3
在該實例中使用包含表4所列成分之基於SBR之化合物。此橡膠化合物適用於卡車輪胎胎面化合物。
在雙輥軸研磨機上將47公克該化合物與0.93公克馬來醯亞胺磺醯疊氮(4-(2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯疊氮)混合。此相當於3.2phr疊氮化物。於120℃之溫度下，在具有50mL內部體積之班伯里類型之混合機中，熱處理混合物持續20分鐘以使該疊氮化物接枝於SBR橡膠上。
在疊氮化物接枝於SBR橡膠上後，藉由在170℃或180℃下之熱處理固化該化合物。
該等實驗顯示，在經馬來醯亞胺磺醯疊氮改質後，SBR可經熱交聯。表4顯示，在將溫度從170℃升高至180℃後，交聯速度增加而交聯密度(MH)亦改善。
Claims (7)
- 一種用於在不存在元素硫的量大於0.5phr之情況下改質聚合物之方法，該方法包括以下步驟：a.在範圍80至250℃之溫度下將該聚合物與經馬來醯亞胺官能化之單疊氮化物混合，以形成官能化聚合物，及b.在範圍150至270℃之溫度下熱處理該官能化聚合物。
- 如請求項1之方法，其中該聚合物為彈性體。
- 如請求項2之方法，其中該彈性體係選自由天然橡膠(NR)、苯乙烯丁二烯橡膠(SBR)、丁二烯橡膠(BR)、丁基橡膠(IIR)、乙烯丙烯共聚物彈性體(EPM)、乙烯丙烯二烯三元共聚物彈性體(EPDM)及乙烯乙酸乙烯酯共聚物(EVA)組成之群。
- 如請求項1之方法，其中該聚合物為聚烯烴。
- 如請求項4之方法，其中該聚烯烴係選自由聚苯乙烯、聚乙烯、聚丙烯、及乙烯及/或丙烯之共聚物組成之群。
- 如請求項1之方法，其中該聚合物為聚乳酸。
- 如請求項1至6中任一項之方法，其中該經馬來醯亞胺官能化之疊氮化物具有以下結構：
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| KR20170134719A (ko) * | 2015-04-24 | 2017-12-06 | 아크조 노벨 케미칼즈 인터내셔널 비.브이. | 중합체의 관능화 방법 |
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| FR3051792B1 (fr) | 2016-05-30 | 2020-01-24 | Ecole Superieure De Physique Et De Chimie Industrielles De La Ville De Paris | Nouveaux composes, derives de dioxoborolane ou de dioxaborinane fonctionnalises, leur procede de preparation et leurs utilisations |
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- 2014-10-31 MX MX2016005601A patent/MX2016005601A/es unknown
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- 2014-11-06 AR ARP140104184A patent/AR098336A1/es unknown
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2016
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|---|---|
| ZA201602431B (en) | 2017-07-26 |
| TWI622601B (zh) | 2018-05-01 |
| EP3066152A1 (en) | 2016-09-14 |
| WO2015067531A1 (en) | 2015-05-14 |
| AR098335A1 (es) | 2016-05-26 |
| MX2016005601A (es) | 2016-07-21 |
| RU2662006C2 (ru) | 2018-07-23 |
| CN105705564A (zh) | 2016-06-22 |
| US20160264688A1 (en) | 2016-09-15 |
| JP6232132B2 (ja) | 2017-11-15 |
| CN105705564B (zh) | 2018-02-23 |
| ES2660495T3 (es) | 2018-03-22 |
| CA2927994A1 (en) | 2015-05-14 |
| EP3066152B1 (en) | 2017-12-06 |
| JP2016535137A (ja) | 2016-11-10 |
| RU2016121147A (ru) | 2017-12-12 |
| AR098336A1 (es) | 2016-05-26 |
| SA516371024B1 (ar) | 2017-09-28 |
| RU2016121147A3 (zh) | 2018-05-23 |
| US9683057B2 (en) | 2017-06-20 |
| TR201802165T4 (tr) | 2018-03-21 |
| KR20160084383A (ko) | 2016-07-13 |
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