CN115109173B - 一种环状硅氧烷接枝聚乙烯及其制备方法 - Google Patents
一种环状硅氧烷接枝聚乙烯及其制备方法 Download PDFInfo
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- -1 Cyclic siloxane Chemical class 0.000 title claims abstract description 110
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 66
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 150000003254 radicals Chemical class 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 230000004913 activation Effects 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- 239000004700 high-density polyethylene Substances 0.000 claims description 10
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 8
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
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- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 4
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- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 claims description 2
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- HAURRGANAANPSQ-UHFFFAOYSA-N cis-2,4,6-Trimethyl-2,4,6-triphenylcyclotrisiloxane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 HAURRGANAANPSQ-UHFFFAOYSA-N 0.000 claims description 2
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
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- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 229940038384 octadecane Drugs 0.000 claims description 2
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- QKSQWQOAUQFORH-UHFFFAOYSA-N tert-butyl n-[(2-methylpropan-2-yl)oxycarbonylimino]carbamate Chemical compound CC(C)(C)OC(=O)N=NC(=O)OC(C)(C)C QKSQWQOAUQFORH-UHFFFAOYSA-N 0.000 claims description 2
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- LRRBANSQUYNJTH-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;2-ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O.CC(C)(C)OOC(C)(C)C LRRBANSQUYNJTH-UHFFFAOYSA-N 0.000 claims 1
- 125000005604 azodicarboxylate group Chemical group 0.000 claims 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
本发明涉及一种环状硅氧烷接枝聚乙烯及其制备方法。所述环状硅氧烷接枝聚乙烯如式(I)所示,R为甲基,三氟甲基丙基或苯基;x为2‑5的整数;m为20‑30000的整数;n为1‑3000的整数。本发明提供的环状硅氧烷接枝聚乙烯,具有更好流变性能、热稳定性及高反应性,在加工流变促进剂、增容剂及反应前驱体等领域具有潜在应用。所述制备方法是在一种无金属催化、无溶剂或少溶剂条件下,利用聚乙烯侧基自由基接枝或碳氢活化反应一步得到的。本发明所提供的环状硅氧烷接枝聚乙烯的制备方法,操作简单,可以在熔融或少量有机溶剂存在条件下进行,副反应可控、成本合理、实用性强。
Description
技术领域
本发明属于高分子新材料技术领域,具体涉及一种环状硅氧烷接枝聚乙烯及其制备方法。
背景技术
聚烯烃(主要为聚乙烯、聚丙烯)价格低廉、性能优异,是最大宗合成树脂产品。聚烯烃综合性能好、性价比高,是使用最为广泛的通用合成树脂,全球年产量逾2亿吨/年。聚烯烃聚合后改性一直是工业上制备功能化聚烯烃的主要方向之一。最为典型的是马来酸酐接枝聚烯烃。通过简单熔融挤出过程,优化引发剂体系和反应性挤出工艺条件,即可在聚烯烃结构中引入极性/反应性马来酸酐基团,具有很好的商业价值。聚烯烃材料性价比高,对聚烯烃进行功能化改性,其性能的提高空间很大。通过功能化反应,在聚烯烃侧基引入极性/反应性功能基团,可以得到侧基功能化聚烯烃。通过优选侧基功能基团,可以得到具有特性功能特性的侧基功能化聚烯烃,侧基功能化可以显著改善聚烯烃综合性能,拓宽聚烯烃应用领域。所述功能特性包括但不限于:反应性、极性、更佳印染性能、抗氧性能、增容特性等。
含硅功能化聚烯烃(SFPO)是聚烯烃分子结构中含有机硅功能基团或有机硅聚合物链段的一类功能化聚烯烃的统称。由于有机硅功能基团及有机硅聚合物特殊的理化性质,SFPO通常具有丰富反应性或优异性能,成为一类有代表性的功能化聚烯烃。SFPO可以作为反应性中间体,用于制备具有复杂拓扑结构的功能化聚烯烃(如星型聚合物、梳型聚合物、接枝共聚物)或聚烯烃共价键接枝改性纳米材料;SFPO还可作为功能性添加剂(如增容剂、加工助剂,表面改性剂),用于开发聚烯烃新材料。
CN201610016371.8公开了一种以低含氢硅油与长链1-烯烃之间的硅氢加成反应制备的长链烷基聚硅氧烷,在聚乙烯加工助剂方面展现出良好应用前景,但受限于加氢反应效率,其纯度不高。ZL2016110971947公开了一种聚硅氧烷接枝聚乙烯及其制备方法,可以作为聚乙烯/聚硅氧烷共混物的增容剂,但受限于其前驱体二甲氧基封端聚乙烯来源,实用性受限。ZL201910114615X公开了一种改性长链烷基聚硅氧烷及其制备方法,可以作为聚乙烯加工流动促进剂,但该制备方法需要必须在溶液中进行,且反应时间较长。总之,上述聚乙烯/聚硅氧烷杂化材料的制备步骤仍较为繁琐复杂,成本相对较高,实用性仍有待提高。
发明内容
为解决现有技术的问题,本发明提供一种环状硅氧烷接枝聚乙烯及其制备方法。
本发明通过如下技术方案实现:
一种环状硅氧烷接枝聚乙烯,其结构如式(I)所示:
其中:
R为-CH3,-CH2CH2CF3(三氟甲基丙基),-Ph(苯基)等;
x为2-5的整数;
m为20-30000的整数,优选为40-20000;
n为1-3000的整数,优选为1-1000。
根据本发明,所述的环状硅氧烷接枝聚乙烯的数均分子量为500-200000g/mol,优选为1000-100000g/mol,多分散指数为1-8,优选为1-4。
本发明还提供上述环状硅氧烷接枝聚乙烯的制备方法,其所述方法包括如下步骤:
式(III)所示的聚乙烯在有机溶剂中充分溶解后或在熔融状态下,在自由基引发剂作用下,与式(II)所示的环状硅氧烷化合物经自由基接枝或碳氢活化功能化反应,即得式(I)所示环状硅氧烷接枝聚乙烯。
其中:
R为-CH3,-CH2CH2CF3(三氟甲基丙基),-Ph(苯基)等;
x为2-5的整数;
m为20-30000的整数,优选为40-20000;
n为1-3000的整数,优选为1-1000。
根据本发明,所述引发剂为过氧化苯甲酸叔丁酯、过氧化二异丙苯、过氧化二苯甲酸、过氧化二苯甲酰、过氧化二叔丁基、过氧化(2-乙基己酸)叔丁酯、过氧化环己酮、过氧化二乙酰、过氧化二辛酰、过氧化二月桂酰、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮二甲酸二叔丁酯、偶氮二甲酸二异丙酯、偶氮二甲酰二哌啶、4,4'-偶氮二苯甲醚、偶氮二异丁腈、偶氮二环己腈、过氧化二(2,4-二氯苯甲酰)、Irgatec CR76、N-乙酰氧基琥珀酰亚胺、N-乙酰氧基邻苯二甲酰亚胺中的一种或多种。
根据本发明,所述有机溶剂为甲苯、苯、二甲苯、氯苯、二氯苯、三氯苯、二甲基甲酰胺、四氯乙烷、萘、十氢萘、庚烷、癸烷、环己烷、十二烷、十八烷、三十二烷中的一种或多种。所述功能化试剂为色酮或其衍生物中的一种或多种,包括氟、氯、溴、甲基、乙基、苯基或甲氧基取代色酮。
根据本发明,所述式(II)所示的环状硅氧烷化合物可以是一种或多种,包括但不限于:六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷、2,4,6-三甲基-2,4,6-三(3,3,3-三氟丙基)环三硅氧烷、2,4,6-三甲基-2,4,6-三苯基环三硅氧烷、2,4,6,8-四甲基-2,4,6,8-四(3,3,3-三氟丙基)环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四苯基环四硅氧烷。
根据本发明,所述式(III)所示的聚乙烯为聚乙烯蜡、低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯的一种或多种混合物。
根据本发明,所述式(III)所示的聚乙烯的数均分子量为400-150000g/mol,优选为600-100000g/mol,多分散指数为1-8,优选为1-4。
根据本发明,所述式(II)所示的环状硅氧烷化合物与式(III)所示的聚乙烯的质量比为1:0.1至1:25,优选为1:0.3至1:10。所述式(II)所示的环状硅氧烷化合物与引发剂的摩尔比为1:0.1至1:10,优选为1:0.2至1:4。所述式(III)所示的聚乙烯与有机溶剂的质量比为1:0至1:100,优选为1:0至1:30。
根据本发明,所述的功能化反应,当反应在有机溶剂中进行时,需在惰性气体保护下,反应温度为70-180℃,优选的反应温度为90-150℃,反应时间为0.1-30h,优选的反应时间为0.2-15h;当反应在熔融状态进行时,需在惰性气体保护下或真空条件下,在烧瓶中或螺杆挤出机中进行,反应温度为120-250℃,优选的反应温度为150-220℃,反应时间为0.1-10h,优选的反应时间为0.1-3h。
本发明提供的环状硅氧烷接枝聚乙烯,具有更好流变性能、热稳定性及高反应性,在加工流变促进剂、增容剂及反应前驱体等领域具有潜在应用。所述制备方法是在一种无金属催化、无溶剂或少溶剂条件下,利用聚乙烯侧基自由基接枝或碳氢活化反应,一步制备多功能性聚烯烃的高效方法实用性方法,操作简单,副反应可控、成本合理、实用性强。
附图说明
图1为实施例1所制备的环状硅氧烷接枝聚乙烯(D4-PE)与原始聚乙烯(PE)的红外谱图。
图2为实施例3所制备的环状硅氧烷接枝聚乙烯(3FD3-HDPE)的流变促进效果。
图3为实施例1所制备的环状硅氧烷接枝聚乙烯(D4-PE)的增容效果。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。任何熟悉本技术领域的技术人员在本发明披露的技术范围内,根据本发明的技术方案及其发明构思进行等同替换或改变均属于本发明保护范畴。
实施例1
在150ml两口瓶中,加入10g聚乙烯蜡(购买自上海共聚化工有限公司,数均分子量Mn=720g/mol,多分散系数PDI=2.5),5g八甲基环四硅氧烷(购买自阿拉丁试剂公司)及0.5g偶氮二异庚腈,加入80ml二甲苯,氮气吹扫后升温至110℃,搅拌使其充分溶解。继续搅拌反应8h,以大量酒精析出聚合物,过滤,酒精反复洗涤后,于50℃真空干燥12h,得到环状硅氧烷接枝聚乙烯(D4-PE)。
红外光谱显示,八甲基环四硅氧烷成功被接枝到聚乙烯侧基(见图1)。1H NMR表征确定,八甲基环四硅氧烷的接枝率为12.4wt%,数均分子量Mn=1260g/mol,多分散系数PDI=3.6。
实施例2
在50ml两口瓶中,加入12g聚乙烯蜡(购买自上海共聚化工有限公司,数均分子量Mn=7700g/mol,多分散系数PDI=1.4),5g 2,4,6,8-四甲基-2,4,6,8-四苯基环四硅氧烷(购买自伊诺凯试剂公司)及0.6g过氧化环己酮,加入5ml癸烷,氮气吹扫后室温搅拌混合均匀,随后升温至120℃,搅拌使聚乙烯熔融。继续搅拌反应2h,以大量酒精反复洗涤后,于50℃真空干燥12h,得到环状硅氧烷接枝聚乙烯。
1H NMR表征确定,2,4,6,8-四甲基-2,4,6,8-四苯基环四硅氧烷的接枝率为7.6wt%,数均分子量Mn=13650g/mol,多分散系数PDI=2.6。
实施例3
在250ml两口瓶中,加入50g高密度聚乙烯(购买自兰州石化,数均分子量Mn=54000g/mol,多分散系数PDI=2.2),8g的2,4,6-三甲基-2,4,6-三(3,3,3-三氟丙基)环三硅氧烷(购买自伊诺凯试剂公司)及3g Irgatec CR76(巴斯夫),氮气吹扫后室温搅拌混合均匀,随后升温至150℃,搅拌使聚乙烯熔融。继续搅拌反应0.5h,以大量酒精反复洗涤后,于50℃真空干燥12h,得到环状硅氧烷接枝聚乙烯(3FD3-HDPE)。
1H NMR表征确定,2,4,6-三甲基-2,4,6-三(3,3,3-三氟丙基)环三硅氧烷的接枝率为1.6wt%,数均分子量Mn=89000g/mol,多分散系数PDI=4.0。
实施例4
500g线性低密度聚乙烯(购买自燕山石化,LLDPE,数均分子量Mn=162000g/mol,多分散系数PDI=3.7),35g六甲基环三硅氧烷(购买自伊诺凯试剂公司)及12g N-乙酰氧基琥珀酰亚胺,室温搅拌混合均匀,随后在真空条件下使用双螺杆挤出机挤出,挤出机温度190℃,螺杆转速为30转/分钟,挤出时间12分钟,挤出样条经水冷、切粒后,以大量酒精反复洗涤后,于50℃真空干燥12h,得到环状硅氧烷接枝聚乙烯(D6-LLDPE)。
1H NMR表征确定,六甲基环三硅氧烷的接枝率为1.6wt%,数均分子量Mn=227000g/mol,多分散系数PDI=5.2。表1展示了原料线性低密度聚乙烯(LLDPE)与所得环状硅氧烷接枝聚乙烯(D6-LLDPE)的热失重温度,可以看出,D6-LLDPE与LLDPE相比热稳定性明显提高。测试条件:30-700℃,空气气氛,升温速率20℃/分钟。
表1
实施例5
所制备的环状硅氧烷接枝聚乙烯的促进流变效果按照如下方案进行鉴定。将实施例3所得环状硅氧烷接枝聚乙烯(3FD3-HDPE)及对应原料高密度聚乙烯(HDPE)的进行流变分析。结果显示3FD3-HDPE与HDPE相比,在相同条件下,复数黏度明显降低,说明环状硅氧烷接枝接枝后,能够显著提高聚乙烯的加工流变性能(见图2)。
实施例6
所制备的环状硅氧烷接枝聚乙烯的增容效果按照如下方案进行鉴定。将实施例1所得环状硅氧烷接枝聚乙烯(D4-PE)作为线性低密度聚乙烯(LLDPE)与聚二甲基硅氧烷(PDMS)共混体系的增容剂,分别制备出LLDPE/PDMS/D4-PE(质量比95/5/5)及LLDPE/PDMS(质量比95/5)两种共混物。共混物制备过程为:小型密炼机中,聚合物总重量为45克,按比例加入后,190℃密炼10分钟,转速为15转/分钟。扫描电镜结果显示,LLDPE/PDMS/D4-PE共混物脆断断面中PDMS的分散相尺寸显著降低。证明D4-PE与能够增容线性低密度聚乙烯(LLDPE)与聚二甲基硅氧烷(PDMS)共混体系(见图3)。
Claims (10)
1.一种环状硅氧烷接枝聚乙烯,其特征在于,其结构如式(I)所示:
其中:
R为甲基,三氟甲基丙基或苯基;
x为2-5的整数;
m为20-30000的整数;
n为1-3000的整数。
2.根据权利要求1所述的环状硅氧烷接枝聚乙烯,其特征在于,其数均分子量为500-200000g/mol,多分散指数为1-8。
3.一种制备权利要求1所述的环状硅氧烷接枝聚乙烯的方法,其特征在于,所述方法包括如下步骤:
式(III)所示的聚乙烯在有机溶剂中溶解后或在熔融状态下,在引发剂作用下,与式(II)所示的环状硅氧烷化合物进行自由基接枝或碳氢活化反应,即得式(I)所示环状硅氧烷接枝聚乙烯,
其中:
R为甲基,三氟甲基丙基或苯基;
x为2-5的整数;
m为20-30000的整数;
n为1-3000的整数。
4.根据权利要求3所述的方法,其特征在于,所述引发剂为过氧化苯甲酸叔丁酯、过氧化二异丙苯、过氧化二苯甲酸、过氧化二苯甲酰、过氧化二叔丁基、过氧化(2-乙基己酸)叔丁酯、过氧化环己酮、过氧化二乙酰、过氧化二辛酰、过氧化二月桂酰、偶氮二异庚腈、偶氮二异丁酸二甲酯、偶氮二甲酸二叔丁酯、偶氮二甲酸二异丙酯、偶氮二甲酰二哌啶、4,4'-偶氮二苯甲醚、偶氮二异丁腈、偶氮二环己腈、过氧化二(2,4-二氯苯甲酰)、Irgatec CR76、N-乙酰氧基琥珀酰亚胺、N-乙酰氧基邻苯二甲酰亚胺中的一种或多种。
5.根据权利要求3所述的方法,其特征在于,所述有机溶剂为甲苯、苯、二甲苯、氯苯、二氯苯、三氯苯、二甲基甲酰胺、四氯乙烷、萘、十氢萘、庚烷、癸烷、环己烷、十二烷、十八烷、三十二烷中的一种或多种。
6.根据权利要求3所述的方法,其特征在于,所述式(II)所示的环状硅氧烷化合物为六甲基环三硅氧烷、八甲基环四硅氧烷、十甲基环五硅氧烷、2,4,6-三甲基-2,4,6-三(3,3,3-三氟丙基)环三硅氧烷、、2,4,6-三甲基-2,4,6-三苯基环三硅氧烷、2,4,6,8-四甲基-2,4,6,8-四(3,3,3-三氟丙基)环四硅氧烷、2,4,6,8-四甲基-2,4,6,8-四苯基环四硅氧烷中的一种或多种。
7.根据权利要求3所述的方法,其特征在于,所述式(III)所示聚乙烯为聚乙烯蜡、低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯的一种或多种混合物。
8.根据权利要求3所述的方法,其特征在于,所述式(III)所示的聚乙烯的数均分子量为400-150000g/mol,多分散指数为1-8。
9.根据权利要求3所述的方法,其特征在于,所述式(II)所示的环状硅氧烷化合物与式(III)所示的聚乙烯的质量比为1:0.1至1:25;所述式(II)所示的环状硅氧烷化合物与引发剂的摩尔比为1:0.1至1:10;所述式(III)所示的聚乙烯与有机溶剂的质量比为1:0至1:100。
10.根据权利要求3所述的方法,其特征在于,当反应在有机溶剂中进行时,在惰性气体保护下反应,反应温度为70-180℃,反应时间为0.1-30h;当反应在熔融状态进行时,在惰性气体保护下或真空条件下,在烧瓶中或螺杆挤出机中进行,反应温度为120-250℃反应时间为0.1-10h。
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WO1996039459A1 (en) * | 1995-06-06 | 1996-12-12 | Shell Internationale Research Maatschappij B.V. | Anionically polymerized block copolymers of ethylene and cyclic siloxane monomers |
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CN102216372A (zh) * | 2008-08-01 | 2011-10-12 | 联合碳化化学及塑料技术有限责任公司 | 有机硅-热塑性聚合物反应性共混物和共聚产物 |
CN106957396A (zh) * | 2017-04-10 | 2017-07-18 | 广东优科艾迪高分子材料有限公司 | 一种自清洁耐磨型有机硅增韧剂及其制备方法与应用 |
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WO1996039459A1 (en) * | 1995-06-06 | 1996-12-12 | Shell Internationale Research Maatschappij B.V. | Anionically polymerized block copolymers of ethylene and cyclic siloxane monomers |
US5618903A (en) * | 1995-06-06 | 1997-04-08 | Shell Oil Company | Anionically polymerized block copolymers of ethylene and cyclic siloxane monomers |
US6160045A (en) * | 1998-05-08 | 2000-12-12 | Shell Oil Company | Oil gel formulations containing polyethylene-polydimethylsiloxane block copolymers dissolved in polydimethylsiloxane |
JP2005075996A (ja) * | 2003-09-03 | 2005-03-24 | Kaneka Corp | ポリオレフィン系グラフト共重合体およびその製造方法 |
CN102216372A (zh) * | 2008-08-01 | 2011-10-12 | 联合碳化化学及塑料技术有限责任公司 | 有机硅-热塑性聚合物反应性共混物和共聚产物 |
CN106957396A (zh) * | 2017-04-10 | 2017-07-18 | 广东优科艾迪高分子材料有限公司 | 一种自清洁耐磨型有机硅增韧剂及其制备方法与应用 |
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