CN109134764B - A kind of preparation method of maleic acid grafted polypropylene that helps to inhibit polypropylene degradation - Google Patents
A kind of preparation method of maleic acid grafted polypropylene that helps to inhibit polypropylene degradation Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 89
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 64
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 64
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title claims abstract description 35
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011976 maleic acid Substances 0.000 title claims abstract description 30
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 16
- 230000015556 catabolic process Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 19
- 150000002910 rare earth metals Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 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 description 5
- 238000012668 chain scission Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 150000001721 carbon Chemical group 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001723 carbon free-radicals Chemical group 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000012521 purified sample Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
本发明属于高分子材料改性领域，特别涉及一种有助于抑制聚丙烯降解的马来酸接枝聚丙烯的制备方法，首先将马来酸与可溶性稀土无机盐反应得到马来酸的配合物，然后将得到的马来酸的配合物与聚丙烯原料、抗氧剂、引发剂混合并进行熔融挤出，得到接枝后的聚丙烯。能减少聚丙烯在熔融挤出过程中的降解，也增加了对聚丙烯链的接枝率。The invention belongs to the field of polymer material modification, and particularly relates to a preparation method of maleic acid grafted polypropylene which helps to inhibit the degradation of polypropylene. Then, the obtained maleic acid complex is mixed with polypropylene raw material, antioxidant and initiator, and then melt-extruded to obtain grafted polypropylene. It can reduce the degradation of polypropylene in the process of melt extrusion, and also increase the grafting rate of polypropylene chains.
Description
技术领域technical field
本发明属于高分子材料改性领域，特别涉及一种有助于抑制聚丙烯降解的马来酸接枝聚丙烯的制备方法。The invention belongs to the field of polymer material modification, and in particular relates to a preparation method of maleic acid grafted polypropylene which helps to inhibit the degradation of polypropylene.
背景技术Background technique
聚丙烯具有优良的综合性能，是一种用途很广的通用高分子材料。但由于聚丙烯与极性材料的相容性较差，需要一些方法改善聚丙烯的极性。常见的改性方法是将某些单体接枝到聚丙烯分子链上。其中，熔融接枝法操作简单经济，适合工业化生产，是目前主要的改性方法。Polypropylene has excellent comprehensive properties and is a general-purpose polymer material with a wide range of uses. However, due to the poor compatibility of polypropylene with polar materials, some methods are needed to improve the polarity of polypropylene. A common modification method is to graft certain monomers onto polypropylene molecular chains. Among them, the melt grafting method is simple and economical to operate, suitable for industrial production, and is currently the main modification method.
熔融接枝的过程是：过氧化物引发剂分解后产生初级自由基，初级自由基再进攻聚丙烯主链，生成聚丙烯大分子自由基(主要是聚丙烯叔碳原子自由基)，该大分子自由基进一步与接枝单体反应，得到接枝聚丙烯。但由于生成的聚丙烯叔碳原子自由基在高温下同样比较容易发生β断链反应，并且断链反应的速率远大于接枝的速率，使接枝过程中伴随着严重的降解，会急剧降低聚丙烯及接枝产物的分子量及力学性能。The process of melt grafting is: after the peroxide initiator is decomposed, primary free radicals are generated, and the primary free radicals attack the main chain of polypropylene to generate polypropylene macromolecular free radicals (mainly polypropylene tertiary carbon atom free radicals). Molecular free radicals further react with grafted monomers to obtain grafted polypropylene. However, since the generated polypropylene tertiary carbon atom free radicals are also prone to beta chain scission reaction at high temperature, and the rate of chain scission reaction is much higher than the rate of grafting, the grafting process will be accompanied by serious degradation, which will decrease sharply. Molecular weight and mechanical properties of polypropylene and grafted products.
发明内容Contents of the invention
为解决聚丙烯熔融接枝其他单体的过程中存在严重的降解现象这一技术问题，更准确地说，是为了解决生成的聚丙烯叔碳原子自由基断链降解的速率明显大于接枝速率这一技术问题，本发明提供了一种有助于抑制聚丙烯降解的马来酸接枝聚丙烯的制备方法，具体步骤包括：In order to solve the technical problem of serious degradation phenomenon in the process of polypropylene melt grafting other monomers, more precisely, it is to solve the problem that the generated polypropylene tertiary carbon atom radical chain scission degradation rate is obviously greater than the grafting rate This technical problem, the present invention provides a kind of preparation method that helps to suppress the maleic acid grafted polypropylene of polypropylene degradation, concrete steps comprise:
(1)制备接枝单体马来酸的配合物(1) Preparation of the complex of grafted monomer maleic acid
将马来酸与可溶性稀土无机盐反应得到马来酸的配合物，Maleic acid is reacted with soluble rare earth inorganic salt to obtain the complex of maleic acid,
具体操作为，将马来酸溶解在有机溶剂中，并向其中滴加可溶性稀土无机盐溶液，滴加完成后升温进行搅拌回流反应，将反应所生成的沉淀物过滤、洗涤、真空干燥，The specific operation is that maleic acid is dissolved in an organic solvent, and a soluble rare earth inorganic salt solution is added dropwise thereto, and after the dropwise addition is completed, the temperature is raised to carry out a stirring and reflux reaction, and the precipitate generated by the reaction is filtered, washed, and vacuum-dried.
其中，马来酸与可溶性稀土无机盐中所含稀土离子的摩尔比为1.6～2：1，Among them, the molar ratio of maleic acid to the rare earth ions contained in the soluble rare earth inorganic salt is 1.6～2:1,
稀土为钇、镧、铈、镨、钕、铒等，Rare earths are yttrium, lanthanum, cerium, praseodymium, neodymium, erbium, etc.
有机溶剂及可溶性稀土无机盐溶液中所含溶剂均为乙醇；The solvent contained in the organic solvent and the soluble rare earth inorganic salt solution is ethanol;
(2)接枝聚丙烯(2) Grafted polypropylene
将包括步骤(1)中得到的马来酸的配合物、聚丙烯原料、抗氧剂、引发剂混合后，加入到挤出机中进行熔融挤出，冷却，After mixing the complex compound comprising maleic acid obtained in step (1), polypropylene raw material, antioxidant and initiator, join in the extruder and carry out melt extrusion, cooling,
步骤(1)中得到的马来酸的配合物、聚丙烯原料、抗氧剂、引发剂的加入量按重量比计算为6～15：100：0.4～1：0.2～1，The addition amount of the maleic acid complex obtained in step (1), polypropylene raw material, antioxidant, initiator is calculated as 6～15:100:0.4～1:0.2～1 by weight ratio,
挤出机熔融挤出的温度控制在160～200℃。The temperature of the extruder for melt extrusion is controlled at 160-200°C.
具体实施方式Detailed ways
实施例1Example 1
(1)将116重量份的马来酸溶解在600重量份的乙醇中，并将由260.4重量份的硝酸铈Ce(NO3)3·6H2O分散溶解于400重量份乙醇中所形成的盐溶液逐滴滴加到其中，滴加完成后将体系升温至78℃进行搅拌回流反应并由沉淀物生成，反应2小时后过滤，将滤饼沉淀物充分洗涤后于75℃下真空干燥充分，得到稀土铈的马来酸配合物(并立即用于步骤(2)中进行制备)，(1) A salt formed by dissolving 116 parts by weight of maleic acid in 600 parts by weight of ethanol and dispersing and dissolving 260.4 parts by weight of cerium nitrate Ce(NO 3 ) 3 ·6H 2 O in 400 parts by weight of ethanol The solution was added dropwise to it, and after the addition was completed, the system was heated to 78°C for stirring and reflux reaction, and the precipitate was formed. After reacting for 2 hours, it was filtered, and the filter cake precipitate was fully washed and then vacuum-dried at 75°C. Obtain the maleic acid complex of rare earth cerium (and be used in step (2) to prepare immediately),
从产物中取样，进行元素分析和红外光谱表征，证明产物中同时有铈元素和有机配体存在；Samples were taken from the product for elemental analysis and infrared spectrum characterization, which proved that both cerium and organic ligands existed in the product;
(2)将步骤(1)中得到的配合物、聚丙烯原料(茂名石化、EPS30R)、抗氧剂1010、引发剂过氧化二异丙苯按10：100：0.6：0.8的重量比于高混机内混合10分钟后，将所得的混合料加入到挤出机中于190℃下熔融挤出(挤出机的转速为90rpm)、造粒，即得到接枝后的聚丙烯产品。(2) The compound obtained in step (1), polypropylene raw material (Maoming Petrochemical, EPS30R), antioxidant 1010, initiator dicumyl peroxide are in the weight ratio of 10:100:0.6:0.8 to high After mixing in the mixer for 10 minutes, the obtained mixture was added to an extruder, melted and extruded at 190° C. (the rotational speed of the extruder was 90 rpm), and granulated to obtain a grafted polypropylene product.
实施例2Example 2
(1)同实施例1；(1) with embodiment 1;
(2)将步骤(1)中得到的配合物、聚丙烯原料(茂名石化、EPS30R)、抗氧剂1076、引发剂过氧化二异丙苯按12：100：0.4：0.9的重量比于高混机内混合12分钟后，将所得的混合料加入到挤出机中于195℃下熔融挤出(挤出机的转速为95rpm)、造粒，即得到接枝后的聚丙烯产品。(2) The compound obtained in step (1), polypropylene raw material (Maoming Petrochemical, EPS30R), antioxidant 1076, initiator dicumyl peroxide are in the weight ratio of 12:100:0.4:0.9 to high After mixing in the mixer for 12 minutes, the obtained mixture was added to an extruder, melted and extruded at 195° C. (the rotational speed of the extruder was 95 rpm), and granulated to obtain a grafted polypropylene product.
对比实施例1Comparative Example 1
将相应配比的接枝单体马来酸直接加入到聚丙烯基体中进行熔融挤出，未引入稀土离子制备配合物，其余组分及操作均同实施例1：The grafted monomer maleic acid of the corresponding ratio is directly added to the polypropylene matrix for melt extrusion, and the rare earth ion is not introduced to prepare the complex, and the remaining components and operations are the same as in Example 1:
将马来酸、聚丙烯原料(茂名石化、EPS30R)、抗氧剂1010、引发剂过氧化二异丙苯按6.24：100：0.6：0.8的重量比于高混机内混合10分钟后，将所得的混合料加入到挤出机中于190℃下熔融挤出(挤出机的转速为90rpm)、造粒，即得到接枝后的聚丙烯产品。Mix maleic acid, polypropylene raw material (Maoming Petrochemical, EPS30R), antioxidant 1010, and initiator dicumyl peroxide in a high mixer at a weight ratio of 6.24:100:0.6:0.8 for 10 minutes. The obtained mixture was put into an extruder, melted and extruded at 190° C. (the rotational speed of the extruder was 90 rpm), and granulated to obtain a grafted polypropylene product.
对比实施例2Comparative Example 2
未事先形成马来酸与稀土离子的配合物，而是将马来酸和稀土离子分别独立地加入到聚丙烯基体中进行熔融挤出，其余组分及操作均同实施例1：A complex of maleic acid and rare earth ions was not formed in advance, but maleic acid and rare earth ions were independently added to the polypropylene matrix for melt extrusion, and the remaining components and operations were the same as in Example 1:
将马来酸、Ce(NO3)3·6H2O、聚丙烯原料(茂名石化、EPS30R)、抗氧剂1010、引发剂过氧化二异丙苯按6.24：11.67：100：0.6：0.8的重量比于高混机内混合10分钟后，将所得的混合料加入到挤出机中于190℃下熔融挤出(挤出机的转速为90rpm)、造粒，即得到接枝后的聚丙烯产品。Maleic acid, Ce(NO 3 ) 3 6H 2 O, polypropylene raw material (Maoming Petrochemical, EPS30R), antioxidant 1010, initiator dicumyl peroxide according to the ratio of 6.24:11.67:100:0.6:0.8 After mixing in the high mixer for 10 minutes by weight, the resulting mixture was added to the extruder, melted and extruded at 190°C (the rotating speed of the extruder was 90rpm), and granulated to obtain the grafted polymer. Propylene products.
对比实施例3Comparative Example 3
同样是基于马来酸和铈离子，但是事先制备出相比于实施例1步骤(1)中络合稳定性更好的配合物，相应配比的马来酸接枝物通过该配合物的形式加入到聚丙烯基体中进行熔融挤出，其余组分及操作均同实施例1，具体步骤为：It is also based on maleic acid and cerium ion, but prepares in advance compared with the compound compound with better complexation stability in the step (1) of embodiment 1, the maleic acid graft of corresponding proportion passes through the compound of this compound Form joins in the polypropylene matrix and carries out melt extruding, and all the other components and operation are all the same as embodiment 1, and concrete steps are:
(1)将230重量份的马来酸酐溶解在650重量份的乙腈中得到马来酸酐溶液，将60重量份的乙二胺溶解在300重量份的乙腈中得到乙二胺溶液，在冰浴条件下将马来酸酐溶液逐滴滴加到乙二胺溶液中，充分搅拌反应至完全沉淀，过滤，滤饼经无水乙醇充分洗涤，70℃真空干燥，得乙二胺双马来酰胺酸，(1) the maleic anhydride of 230 weight parts is dissolved in the acetonitrile of 650 weight parts to obtain maleic anhydride solution, the ethylenediamine of 60 weight parts is dissolved in the acetonitrile of 300 weight parts to obtain ethylenediamine solution, in ice bath Add the maleic anhydride solution dropwise to the ethylenediamine solution under certain conditions, stir the reaction until complete precipitation, filter, wash the filter cake thoroughly with absolute ethanol, and dry it in vacuum at 70°C to obtain ethylenediamine bismaleamic acid ,
考虑到乙二胺双马来酰胺酸不溶于乙醇，因此先取所得的乙二胺双马来酰胺酸128重量份与40重量份的氢氧化钠加入到600重量份的乙醇中并反应充分，得乙二胺双马来酰胺酸盐的乙醇溶液；Considering that ethylenediamine bismaleamic acid is insoluble in ethanol, therefore get 128 weight parts of gained ethylenediamine bismaleamic acid and the sodium hydroxide of 40 weight parts to join in the ethanol of 600 weight parts and fully react, obtain Ethanol solution of ethylenediamine bismaleamic acid salt;
(2)将由260.4重量份的硝酸铈Ce(NO3)3·6H2O分散溶解于400重量份乙醇中所形成的盐溶液逐滴滴加到步骤(1)所制备的乙二胺双马来酰胺酸盐的乙醇溶液中，滴加完成后将体系升温至78℃进行搅拌回流反应并由沉淀物生成，反应2小时后过滤，将滤饼沉淀物充分洗涤后于75℃下真空干燥充分，得到乙二胺双马来酰胺酸根稀土配合物；(2) The salt solution formed by dispersing and dissolving 260.4 parts by weight of cerium nitrate Ce(NO 3 ) 3 ·6H 2 O in 400 parts by weight of ethanol is added dropwise to the ethylenediamine bismaline prepared in step (1). In the ethanol solution of lyamic acid salt, after the dropwise addition is completed, the system is heated to 78°C for stirring and reflux reaction, and the precipitate is formed. After reacting for 2 hours, filter, and the filter cake precipitate is fully washed and then vacuum-dried at 75°C. , to obtain ethylenediamine bismaleamic acid radical rare earth complex;
(3)将步骤(2)中得到的配合物、聚丙烯原料(茂名石化、EPS30R)、抗氧剂1010、引发剂过氧化二异丙苯按12.11：100：0.6：0.8的重量比于高混机内混合10分钟后，将所得的混合料加入到挤出机中于190℃下熔融挤出(挤出机的转速为90rpm)、造粒，即得到接枝后的聚丙烯产品。(3) The compound obtained in step (2), polypropylene raw material (Maoming Petrochemical, EPS30R), antioxidant 1010, initiator dicumyl peroxide are in the weight ratio of 12.11:100:0.6:0.8 to high After mixing in the mixer for 10 minutes, the obtained mixture was added to an extruder, melted and extruded at 190° C. (the rotational speed of the extruder was 90 rpm), and granulated to obtain a grafted polypropylene product.
分别称取等量的上述各实施例、对比实施例制备的接枝后的聚丙烯产品，进行熔体流动速率的测定；Respectively take equivalent above-mentioned each embodiment, the polypropylene product after the grafting that comparative example prepares, carry out the mensuration of melt flow rate;
并将各样品加入二甲苯中煮沸溶解，再趁热将溶液倒入过量丙酮中析出，过滤，干燥制得纯化样品，各组称取等量纯化样品加入二甲苯中溶解，再分别加入过量的碱中和样品中接枝于聚丙烯大分子链上的马来酸(酐)，然后用酸反滴定过量的碱，计算各产品的接枝率，具体如下表所示：Add each sample to xylene and boil to dissolve, then pour the solution into excess acetone to precipitate while it is hot, filter, and dry to obtain a purified sample. Each group weighs an equal amount of purified sample and adds it to dissolve in xylene, and then adds excess acetone. Alkali neutralizes the maleic acid (anhydride) grafted on the polypropylene macromolecular chain in the sample, and then uses acid back titration to excess alkali to calculate the grafting rate of each product, as shown in the following table:
从上表中可以看出，本方案制备的接枝聚丙烯的接枝率有明显提高，熔体流动速率明显降低，即聚丙烯大分子的降解程度明显减少。It can be seen from the above table that the grafting rate of the grafted polypropylene prepared by this scheme is obviously increased, and the melt flow rate is obviously reduced, that is, the degree of degradation of the polypropylene macromolecule is obviously reduced.
对比实施例2和对比实施例3中也涉及到稀土离子的加入，特别是对比实施例3中同样是以配合物的形式将接枝单体与稀土离子加入到聚丙烯基体中，但在抑制聚丙烯降解的效果上却十分有限，与本方案制备的配合物存在明显的差异。对此，申请人推测：The addition of rare earth ions is also involved in comparative example 2 and comparative example 3, especially in comparative example 3, the graft monomer and rare earth ions are also added to the polypropylene matrix in the form of complexes, but in the inhibition However, the degradation effect of polypropylene is very limited, which is obviously different from the complex prepared by this scheme. In this regard, the applicant speculates that:
本方案中直接使用马来酸与铈离子络合形成配合物，这种配合物并不稳定，与聚丙烯共混后会试图在混合体系中寻找到新的络合点以维持住自身的配位结构，因此配合物很可能存在向聚丙烯分子链靠近的趋势(特别是在开始升温熔融时，配合物及聚丙烯链的活性都增加)，试图在聚丙烯链上找到新的络合点或封闭结构；以此同时，随着过氧化物引发剂分解产生的初级自由基对聚丙烯主链的进攻，很多主链上生成了聚丙烯大分子自由基(主要是聚丙烯叔碳原子自由基)，这种聚丙烯叔碳原子自由基在高温下本来是要发生断链降解反应的，但由于配合物对聚丙烯链的靠近，配合物上带有马来酸的结构，这就促使了聚丙烯叔碳原子自由基能更为方便地完成对马来酸结构上的碳碳双键的进攻，从而使相当一部分本应该发生断链降解的聚丙烯叔碳原子自由基能先与配合物上的马来酸结构相结合实现接枝，接枝完成后自然就避免了这部分聚丙烯叔碳原子自由基的降解。因此，从总体上来看，大幅减少了聚丙烯在熔融挤出过程中的降解，也增加了对聚丙烯链的接枝率。In this scheme, maleic acid is directly used to complex with cerium ions to form a complex. This complex is not stable. After blending with polypropylene, it will try to find a new complex point in the mixed system to maintain its own coordination. Therefore, the complex is likely to have a tendency to approach the polypropylene molecular chain (especially when the temperature rises and melts, the activity of the complex and the polypropylene chain increases), trying to find a new complex point on the polypropylene chain Or closed structure; at the same time, with the attack of the primary free radicals generated by the decomposition of the peroxide initiator to the main chain of polypropylene, many main chains generate polypropylene macromolecular free radicals (mainly polypropylene tertiary carbon atom free radicals) radical), this kind of polypropylene tertiary carbon atom free radical would have undergone a chain scission degradation reaction at high temperature, but due to the proximity of the complex to the polypropylene chain, the complex has a maleic acid structure, which promotes The polypropylene tertiary carbon free radicals can more conveniently complete the attack on the carbon-carbon double bond on the maleic acid structure, so that a considerable part of the polypropylene tertiary carbon free radicals that should be degraded by chain scission can first cooperate with the The maleic acid structure on the material is combined to achieve grafting. After the grafting is completed, the degradation of this part of polypropylene tertiary carbon atom free radicals is naturally avoided. Therefore, overall, the degradation of polypropylene during melt extrusion is greatly reduced, and the grafting ratio of polypropylene chains is also increased.
对比实施例2中未将稀土离子与马来酸结构形成配合物，因此不存在接枝单体向聚丙烯链靠近的效应；而对比实施例3中虽然也事先获得了含马来酸结构的配合物，但是该配合物稳定性较好，与聚丙烯混合后也不存在要寻找到新的络合点以维持自身配位结构的情况，因此不会带动马来酸结构主动向聚丙烯链靠近。申请人推测，这些都是导致上表中结果之间有如此差异的原因。Rare earth ion and maleic acid structure are not formed complex in comparative example 2, therefore there is no effect that grafting monomer approaches to polypropylene chain; complex, but the complex has good stability, and there is no need to find new complexation points to maintain its own coordination structure after mixing with polypropylene, so it will not drive the maleic acid structure to actively move to the polypropylene chain. near. Applicants speculate that these are the reasons for such discrepancies between the results in the table above.
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