CN109134764B - Preparation method of maleic acid grafted polypropylene for inhibiting polypropylene degradation - Google Patents
Preparation method of maleic acid grafted polypropylene for inhibiting polypropylene degradation Download PDFInfo
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- CN109134764B CN109134764B CN201810939736.3A CN201810939736A CN109134764B CN 109134764 B CN109134764 B CN 109134764B CN 201810939736 A CN201810939736 A CN 201810939736A CN 109134764 B CN109134764 B CN 109134764B
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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
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- 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
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- 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
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Abstract
The invention belongs to the field of high polymer material modification, and in particular relates to a preparation method of maleic acid grafted polypropylene which is beneficial to inhibiting polypropylene degradation. Can reduce the degradation of polypropylene in the process of melt extrusion and increase the grafting rate of polypropylene chains.
Description
Technical Field
The invention belongs to the field of modification of high polymer materials, and particularly relates to a preparation method of maleic acid grafted polypropylene which is favorable for inhibiting polypropylene degradation.
Background
The polypropylene has excellent comprehensive performance and is a general polymer material with wide application range. However, because of the poor compatibility of polypropylene with polar materials, some methods are needed to improve the polarity of polypropylene. A common modification method is grafting of certain monomers onto the polypropylene molecular chain. The melt grafting method is simple and economical to operate, is suitable for industrial production, and is a main modification method at present.
The melt grafting process is: the peroxide initiator is decomposed to generate a primary free radical, the primary free radical attacks the polypropylene main chain to generate a polypropylene macromolecule free radical (mainly polypropylene tertiary carbon atom free radical), and the macromolecule free radical further reacts with the grafting monomer to obtain the grafted polypropylene. However, the beta chain scission reaction is easy to occur at high temperature due to the generated polypropylene tertiary carbon atom free radical, and the rate of the chain scission reaction is far greater than the grafting rate, so that the molecular weight and mechanical properties of polypropylene and grafted products can be drastically reduced along with serious degradation in the grafting process.
Disclosure of Invention
In order to solve the technical problem that the polypropylene has serious degradation phenomenon in the process of melt grafting other monomers, more precisely, the technical problem that the rate of the generated polypropylene tertiary carbon atom free radical chain scission degradation is obviously larger than the grafting rate, the invention provides a preparation method of maleic acid grafted polypropylene which is favorable for inhibiting the polypropylene degradation, which comprises the following specific steps:
(1) Preparation of complexes of grafting monomer maleic acid
Maleic acid reacts with soluble rare earth inorganic salt to obtain a maleic acid complex,
the method comprises dissolving maleic acid in organic solvent, dripping soluble rare earth inorganic salt solution, heating, stirring, refluxing, filtering, washing, vacuum drying,
wherein, the mole ratio of the maleic acid to the rare earth ions contained in the soluble rare earth inorganic salt is 1.6-2: 1,
the rare earth is yttrium, lanthanum, cerium, praseodymium, neodymium, erbium and the like,
the organic solvent and the solvent contained in the soluble rare earth inorganic salt solution are ethanol;
(2) Grafted polypropylene
Mixing the maleic acid complex obtained in the step (1), polypropylene raw material, antioxidant and initiator, adding into an extruder for melt extrusion, cooling,
the addition amount of the maleic acid complex, the polypropylene raw material, the antioxidant and the initiator obtained in the step (1) is 6 to 15 percent by weight: 100:0.4 to 1:0.2 to 1 percent of the total weight of the composite,
the temperature of the extruder for melt extrusion is controlled between 160 and 200 ℃.
Detailed Description
Example 1
(1) 116 parts by weight of maleic acid were dissolved in 600 parts by weight of ethanol, and a mixture of 260.4 parts by weight of cerium nitrate Ce (NO 3 ) 3 ·6H 2 Adding dropwise a salt solution formed by dispersing and dissolving O in 400 parts by weight of ethanol, heating the system to 78 ℃ after the dropwise addition is completed, stirring and refluxing the system to react and generate precipitate, filtering the reaction for 2 hours, fully washing a filter cake precipitate, and fully drying the filter cake precipitate in vacuum at 75 ℃ to obtain a maleic acid complex of rare earth cerium (and immediately used for preparation in the step (2)),
sampling from the product, and performing element analysis and infrared spectrum characterization to prove that cerium element and organic ligand exist in the product at the same time;
(2) The complex obtained in the step (1), polypropylene raw material (the name of the product is luxuriant and petrochemical, EPS 30R), antioxidant 1010 and initiator dicumyl peroxide are mixed according to the following weight ratio of 10:100:0.6: mixing in a high-speed mixer for 10 minutes at a weight ratio of 0.8, adding the obtained mixture into an extruder, performing melt extrusion at 190 ℃ (the rotating speed of the extruder is 90 rpm), and granulating to obtain a grafted polypropylene product.
Example 2
(1) As in example 1;
(2) The complex obtained in the step (1), polypropylene raw material (the name of the product is luxuriant and petrochemical, EPS 30R), antioxidant 1076 and initiator dicumyl peroxide are mixed according to a weight ratio of 12:100:0.4: mixing in a high-speed mixer for 12 minutes at a weight ratio of 0.9, adding the obtained mixture into an extruder, performing melt extrusion at 195 ℃ (the rotating speed of the extruder is 95 rpm), and granulating to obtain a grafted polypropylene product.
Comparative example 1
The grafting monomer maleic acid with corresponding proportion is directly added into the polypropylene matrix for melt extrusion, the rare earth ion is not introduced to prepare the complex, and the rest components and the operation are the same as in example 1:
maleic acid, polypropylene raw materials (Mao-name petrochemical, EPS 30R), an antioxidant 1010 and an initiator dicumyl peroxide are mixed according to a ratio of 6.24:100:0.6: mixing in a high-speed mixer for 10 minutes at a weight ratio of 0.8, adding the obtained mixture into an extruder, performing melt extrusion at 190 ℃ (the rotating speed of the extruder is 90 rpm), and granulating to obtain a grafted polypropylene product.
Comparative example 2
Instead of forming a complex of maleic acid and rare earth ions in advance, maleic acid and rare earth ions are added into a polypropylene matrix independently for melt extrusion, and the rest components and operations are the same as in example 1:
maleic acid, ce (NO) 3 ) 3 ·6H 2 O, polypropylene raw material (luxury petrochemical industry, EPS 30R), antioxidant 1010 and initiator dicumyl peroxide according to the proportion of 6.24:11.67:100:0.6: mixing in a high-speed mixer for 10 minutes at a weight ratio of 0.8, adding the obtained mixture into an extruder, performing melt extrusion at 190 ℃ (the rotating speed of the extruder is 90 rpm), and granulating to obtain a grafted polypropylene product.
Comparative example 3
The method is based on maleic acid and cerium ions, but a complex with better complexing stability than that in the step (1) of the example 1 is prepared in advance, and a maleic acid graft with corresponding proportion is added into a polypropylene matrix in the form of the complex for melt extrusion, and the rest components and operations are the same as those in the example 1, and the specific steps are as follows:
(1) Dissolving 230 parts by weight of maleic anhydride in 650 parts by weight of acetonitrile to obtain maleic anhydride solution, dissolving 60 parts by weight of ethylenediamine in 300 parts by weight of acetonitrile to obtain ethylenediamine solution, dropwise adding the maleic anhydride solution into the ethylenediamine solution under ice bath condition, fully stirring for reaction until complete precipitation, filtering, fully washing a filter cake with absolute ethyl alcohol, vacuum drying at 70 ℃ to obtain ethylenediamine bismaleimide acid,
taking the fact that ethylenediamine bismaleimide acid is insoluble in ethanol, adding 128 parts by weight of the obtained ethylenediamine bismaleimide acid and 40 parts by weight of sodium hydroxide into 600 parts by weight of ethanol, and reacting fully to obtain an ethanol solution of ethylenediamine bismaleimide acid salt;
(2) Will be composed of 260.4 parts by weight of cerium nitrate Ce (NO 3 ) 3 ·6H 2 Dispersing and dissolving O into 400 parts by weight of ethanol to form a salt solution, dropwise adding the salt solution into the ethanol solution of ethylenediamine bismaleimide acid salt prepared in the step (1), heating a system to 78 ℃ after the dropwise adding is completed, stirring and refluxing the system to react, generating a precipitate, filtering the precipitate after 2 hours of reaction, fully washing a filter cake precipitate, and fully drying the filter cake precipitate in vacuum at 75 ℃ to obtain ethylenediamine bismaleimide acid rare earth complex;
(3) The complex obtained in the step (2), polypropylene raw material (the name of the product is luxuriant and petrochemical, EPS 30R), antioxidant 1010 and initiator dicumyl peroxide are mixed according to the weight ratio of 12.11:100:0.6: mixing in a high-speed mixer for 10 minutes at a weight ratio of 0.8, adding the obtained mixture into an extruder, performing melt extrusion at 190 ℃ (the rotating speed of the extruder is 90 rpm), and granulating to obtain a grafted polypropylene product.
Respectively weighing equal amounts of the grafted polypropylene products prepared in the examples and the comparative examples, and measuring the melt flow rate;
adding each sample into dimethylbenzene, boiling and dissolving, pouring the solution into excessive acetone while the solution is hot to separate out, filtering, drying to obtain purified samples, weighing the purified samples of equal amount, adding the purified samples into dimethylbenzene for dissolving, respectively adding excessive alkali to neutralize maleic acid (anhydride) grafted on a polypropylene macromolecular chain in the samples, and then back-titrating the excessive alkali with acid to calculate the grafting rate of each product, wherein the specific grafting rate is shown in the following table:
as can be seen from the table, the grafting rate of the grafted polypropylene prepared by the scheme is obviously improved, the melt flow rate is obviously reduced, i.e. the degradation degree of polypropylene macromolecules is obviously reduced.
The addition of rare earth ions is also involved in comparative examples 2 and 3, and particularly in comparative example 3, the grafting monomer and rare earth ions are added to the polypropylene matrix in the form of a complex, but the effect of inhibiting the degradation of polypropylene is very limited, and there is a significant difference from the complex prepared in this scheme. For this, the applicant speculates that:
in the scheme, maleic acid is directly used for complexing with cerium ions to form a complex, the complex is unstable, after being blended with polypropylene, a new complexing point is sought in a mixed system to maintain the self coordination structure, so that the complex is likely to have a trend of approaching to a polypropylene molecular chain (particularly, the activity of the complex and the polypropylene chain is increased when the temperature is raised and melted), and a new complexing point or a closed structure is sought to be found on the polypropylene chain; meanwhile, along with the attack of primary free radicals generated by the decomposition of the peroxide initiator on the polypropylene main chain, a plurality of main chains generate polypropylene macromolecule free radicals (mainly polypropylene tertiary carbon atom free radicals), and the polypropylene tertiary carbon atom free radicals are subjected to chain scission degradation reaction at high temperature, but because the complex is close to the polypropylene chain and is provided with a maleic acid structure, the attack of the polypropylene tertiary carbon atom free radicals on a maleic acid structure can be more conveniently completed, so that a considerable part of polypropylene tertiary carbon atom free radicals which are subjected to chain scission degradation can be combined with the maleic acid structure on the complex to realize grafting, and the degradation of the polypropylene tertiary carbon atom free radicals is naturally avoided after the grafting is completed. Thus, overall, the degradation of polypropylene during melt extrusion is greatly reduced, and the grafting rate to the polypropylene chain is increased.
In comparative example 2, no complex is formed between the rare earth ion and the maleic acid structure, so that the effect of approaching the grafting monomer to the polypropylene chain does not exist; in contrast, in comparative example 3, a complex containing a maleic acid structure was obtained in advance, but the complex had good stability, and after mixing with polypropylene, there was no case where a new complexing point was found to maintain the self-coordination structure, and therefore the maleic acid structure was not driven to approach the polypropylene chain actively. The applicant speculates that these are responsible for such differences between the results in the above tables.
Claims (3)
1. A preparation method of maleic acid grafted polypropylene for inhibiting polypropylene degradation is characterized by comprising the following steps: the specific steps of the preparation method comprise,
(1) Preparation of complexes of grafting monomer maleic acid
Maleic acid reacts with soluble rare earth inorganic salt to obtain a maleic acid complex;
(2) Grafted polypropylene
Mixing the maleic acid complex obtained in the step (1), a polypropylene raw material, an antioxidant and an initiator, adding the mixture into an extruder for melt extrusion, and cooling;
the rare earth is cerium;
the specific operation of the step (1) is that,
dissolving maleic acid in an organic solvent, dropwise adding a soluble rare earth inorganic salt solution into the organic solvent, heating the mixture after the dropwise adding is finished, stirring and refluxing the mixture for reaction, and filtering, washing and vacuum drying a precipitate generated by the reaction;
in the step (1), the mole ratio of the maleic acid to the rare earth ions contained in the soluble rare earth inorganic salt is 1.6-2: 1, a step of;
the organic solvent and the solvent contained in the soluble rare earth inorganic salt solution are ethanol.
2. The method for preparing maleic acid grafted polypropylene which helps to inhibit the degradation of polypropylene according to claim 1, wherein: in the step (2), the addition amount of the complex of the maleic acid, the polypropylene raw material, the antioxidant and the initiator is 6 to 15 percent by weight: 100:0.4 to 1:0.2 to 1.
3. The method for preparing maleic acid grafted polypropylene which helps to inhibit the degradation of polypropylene according to claim 1, wherein: in the step (2), the temperature of the melt extrusion of the extruder is controlled between 160 and 200 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0718018A (en) * | 1993-06-30 | 1995-01-20 | Mitsubishi Chem Corp | Production of modified polypropylene |
| WO2002018463A1 (en) * | 2000-08-29 | 2002-03-07 | Dupont Canada Inc. | High melt flow, highly-grafted polypropylene |
| CN1401730A (en) * | 2002-09-23 | 2003-03-12 | 中国科学院广州化学研究所 | Photoluminescence rareearth polymer material and synthesis process thereof |
| CN1693329A (en) * | 2005-06-03 | 2005-11-09 | 中国科学院长春应用化学研究所 | Process for preparing functional polyolefins resin mixed with rare earth compound |
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- 2018-08-17 CN CN201810939736.3A patent/CN109134764B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0718018A (en) * | 1993-06-30 | 1995-01-20 | Mitsubishi Chem Corp | Production of modified polypropylene |
| WO2002018463A1 (en) * | 2000-08-29 | 2002-03-07 | Dupont Canada Inc. | High melt flow, highly-grafted polypropylene |
| CN1401730A (en) * | 2002-09-23 | 2003-03-12 | 中国科学院广州化学研究所 | Photoluminescence rareearth polymer material and synthesis process thereof |
| CN1693329A (en) * | 2005-06-03 | 2005-11-09 | 中国科学院长春应用化学研究所 | Process for preparing functional polyolefins resin mixed with rare earth compound |
Non-Patent Citations (1)
| Title |
|---|
| 朱连超等.《朱连超等》.《高等学校化学学报》.2006,第27卷(第5期),第971页. * |
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