CN109134764A - A kind of preparation method for the maleic acid graft polypropylene helping to inhibit degradation of polypropylene - Google Patents
A kind of preparation method for the maleic acid graft polypropylene helping to inhibit degradation of polypropylene Download PDFInfo
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- CN109134764A CN109134764A CN201810939736.3A CN201810939736A CN109134764A CN 109134764 A CN109134764 A CN 109134764A CN 201810939736 A CN201810939736 A CN 201810939736A CN 109134764 A CN109134764 A CN 109134764A
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- polypropylene
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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
- 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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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention belongs to polymer modification fields, in particular to a kind of preparation method for the maleic acid graft polypropylene for helping to inhibit degradation of polypropylene, first maleic acid is reacted to obtain the complex of maleic acid with soluble inorganic salt of rare earth, then the complex of obtained maleic acid is mixed with pp material, antioxidant, initiator and carries out melting extrusion, the polypropylene after being grafted.It can be reduced the degradation of polypropylene during melt extrusion, also increase the grafting rate to polypropylene chains.
Description
Technical field
The invention belongs to polymer modification field, in particular to a kind of maleic acid for helping to inhibit degradation of polypropylene
The preparation method of graft polypropylene.
Background technique
Polypropylene has excellent comprehensive performance, is a kind of commodity polymer material having many uses.But due to polypropylene
It is poor with the compatibility of polar material, need certain methods to improve polyacrylic polarity.Common method of modifying is by certain lists
Body is grafted in polypropylene molecular chain.Wherein, melt grafting economy easy to operate is suitble to industrialized production, is main at present
Method of modifying.
The process of fusion-grafting is: peroxide initiator generates primary group of free radicals, primary group of free radicals attack again after decomposing
Polypropylene backbone generates polypropylene macromolecular radical (mainly polypropylene tertiary carbon atom free radical), the macromolecular radical
It is further reacted with grafted monomers, obtains graft polypropylene.But at high temperature due to the polypropylene tertiary carbon atom free radical of generation
It is equally easier that β chain-breaking reaction occurs, and the rate of chain-breaking reaction makes adjoint in grafting process much larger than the rate of grafting
Serious degradation, the molecular weight and mechanical property of polypropylene and graft product can be drastically reduced.
Summary of the invention
There are this technical problems of serious signs of degradation during to solve polypropylene fusion graft other monomers, more
Precisely, be in order to solve generate polypropylene tertiary carbon atom free radical chain-scission degradation rate be significantly greater than grafting rate this
One technical problem, the present invention provides it is a kind of facilitate inhibit degradation of polypropylene maleic acid graft polypropylene preparation method,
Specific steps include:
(1) complex of grafted monomers maleic acid is prepared
Maleic acid is reacted to obtain the complex of maleic acid with soluble inorganic salt of rare earth,
Concrete operations are in organic solvent by maleic acid dissolution, and soluble inorganic salt of rare earth solution to be added dropwise thereto,
Heating is stirred back flow reaction after being added dropwise to complete, and will react sediment generated and is filtered, washed, is dried in vacuo,
Wherein, the molar ratio of maleic acid and contained rare earth ion in soluble inorganic salt of rare earth is 1.6~2:1,
Rare earth is yttrium, lanthanum, cerium, praseodymium, neodymium, erbium etc.,
Contained solvent is ethyl alcohol in organic solvent and soluble inorganic salt of rare earth solution；
(2) graft polypropylene
After complex including maleic acid obtained in step (1), pp material, antioxidant, initiator are mixed, add
Enter into extruder to carry out melting extrusion, it is cooling,
The complex of maleic acid obtained in step (1), pp material, antioxidant, initiator additional amount by weight
Than being calculated as 6~15:100:0.4~1:0.2~1,
The temperature of extruder melting extrusion is controlled at 160~200 DEG C.
Specific embodiment
Embodiment 1
(1) maleic acid of 116 parts by weight is dissolved in the ethyl alcohol of 600 parts by weight, and will be by the nitric acid of 260.4 parts by weight
Cerium Ce (NO3)3·6H2O dispersing and dissolving salting liquid formed in 400 parts by weight of ethanol is added drop-wise to wherein dropwise, is added dropwise to complete
System is warming up to 78 DEG C afterwards to be stirred back flow reaction and generated by sediment, reaction is filtered after 2 hours, by filter cake sediment
Sufficiently washing after at 75 DEG C be dried in vacuo sufficiently, obtain cerium maleic acid complex (and be immediately available in step (2) into
Row preparation),
It is sampled from product, carries out elemental analysis and infrared spectrum characterization, it was demonstrated that have Ce elements and organic in product simultaneously
Ligand exists；
(2) by complex obtained in step (1), pp material (Maoming Petrochemical, EPS30R), antioxidant 1010, draw
Agent cumyl peroxide is sent out by the weight ratio of 10:100:0.6:0.8 in mixing in high mixer after ten minutes, by resulting mixing
Material is added in extruder the melting extrusion (revolving speed of extruder is 90rpm) at 190 DEG C, is granulated to get poly- to after being grafted
Propylene product.
Embodiment 2
(1) with embodiment 1；
(2) by complex obtained in step (1), pp material (Maoming Petrochemical, EPS30R), antioxidant 1076, draw
Agent cumyl peroxide is sent out by the weight ratio of 12:100:0.4:0.9 after mixing 12 minutes in high mixer, by resulting mixing
Material is added in extruder the melting extrusion (revolving speed of extruder is 95rpm) at 195 DEG C, is granulated to get poly- to after being grafted
Propylene product.
Comparative example 1
The grafted monomers maleic acid accordingly matched is added directly into polypropylene matrix and carries out melting extrusion, is not introduced into dilute
Native ion prepares complex, remaining component and operation are with embodiment 1:
By maleic acid, pp material (Maoming Petrochemical, EPS30R), antioxidant 1010, initiator cumyl peroxide
Resulting mixture is added in extruder by the weight ratio by 6.24:100:0.6:0.8 in mixing in high mixer after ten minutes
Melting extrusion (revolving speed of extruder is 90rpm), granulation are at 190 DEG C to get the polypropylene product to after being grafted.
Comparative example 2
It is not previously formed the complex of maleic acid and rare earth ion, but maleic acid and rare earth ion are separately added
Enter into polypropylene matrix and carry out melting extrusion, remaining component and operation are with embodiment 1:
By maleic acid, Ce (NO3)3·6H2O, pp material (Maoming Petrochemical, EPS30R), antioxidant 1010, initiator
Cumyl peroxide by the weight ratio of 6.24:11.67:100:0.6:0.8 in being mixed in high mixer after ten minutes, will be resulting
Mixture is added in extruder the melting extrusion (revolving speed of extruder is 90rpm) at 190 DEG C, is granulated to get to after being grafted
Polypropylene product.
Comparative example 3
It is again based on maleic acid and cerium ion, but prepares stablize compared to complexing in 1 step of embodiment (1) in advance
The better complex of property, the maleic acid graft accordingly matched, which is added in polypropylene matrix by way of the complex, to carry out
Melting extrusion, remaining component and operation are the same as embodiment 1, specific steps are as follows:
(1) maleic anhydride of 230 parts by weight is dissolved in the acetonitrile of 650 parts by weight and obtains maleic anhydride solution, by 60
The ethylenediamine of parts by weight is dissolved in the acetonitrile of 300 parts by weight and obtains ethylenediamine solution, under condition of ice bath that maleic anhydride is molten
Liquid is added drop-wise in ethylenediamine solution dropwise, and reaction is sufficiently stirred and precipitates to complete, and filtering, filter cake is sufficiently washed through dehydrated alcohol,
70 DEG C of vacuum drying obtain the double maleamic acids of ethylenediamine,
In view of the double maleamic acids of ethylenediamine do not dissolve in ethyl alcohol, therefore first take the double maleamic acids of resulting ethylenediamine
128 parts by weight are added in the ethyl alcohol of 600 parts by weight with the sodium hydroxide of 40 parts by weight and react sufficiently, obtain ethylenediamine span
The ethanol solution of amide hydrochlorate；
It (2) will be by the cerous nitrate Ce (NO of 260.4 parts by weight3)3·6H2O dispersing and dissolving institute's shape in 400 parts by weight of ethanol
At salting liquid be added drop-wise in the ethanol solution of the double maleamic acid salt of ethylenediamine prepared by step (1) dropwise, be added dropwise to complete
System is warming up to 78 DEG C afterwards to be stirred back flow reaction and generated by sediment, reaction is filtered after 2 hours, by filter cake sediment
It is sufficiently dried in vacuo sufficiently at 75 DEG C after washing, obtains the double maleamic acid root rare earth compoundings of ethylenediamine；
(3) by complex obtained in step (2), pp material (Maoming Petrochemical, EPS30R), antioxidant 1010, draw
Send out agent cumyl peroxide by the weight ratio of 12.11:100:0.6:0.8 in being mixed in high mixer after ten minutes, will be resulting
Mixture is added in extruder the melting extrusion (revolving speed of extruder is 90rpm) at 190 DEG C, is granulated to get to after being grafted
Polypropylene product.
Polypropylene product after weighing the various embodiments described above of equivalent, the grafting of comparative example preparation respectively, is melted
The measurement of body flow rate；
And each sample is added in dimethylbenzene and boils dissolution, then solution is poured into excessive propanone be precipitated while hot, it filters, does
Dry obtained purification of samples, each group, which weighs equivalent purification of samples and is added in dimethylbenzene, to be dissolved, then is separately added into excessive alkali neutralization sample
The maleic acid (acid anhydride) on polypropylene macromolecular chain is grafted in product, then with the excessive alkali of sour back titration, calculates connecing for each product
Branch rate, shown in table specific as follows:
As can be seen from the above table, the grafting rate of the graft polypropylene of this programme preparation is significantly improved, melt flows speed
Rate is substantially reduced, i.e. the palliating degradation degree of polypropylene macromolecular significantly reduces.
It is also related in comparative example 2 and comparative example 3 in the addition of rare earth ion, especially comparative example 3
It is equally grafted monomers and rare earth ion to be added in polypropylene matrix in the form of complex, but inhibiting degradation of polypropylene
Effect on it is extremely limited, with this programme preparation complex there are apparent differences.In this regard, applicant speculates:
It directly is complexed to form complex using maleic acid and cerium ion in this programme, this complex is simultaneously unstable, and poly-
Propylene can attempt to search out coordination structure of the new hapto to be maintained itself in mixed system after being blended, therefore complex
Be likely that there are to the close trend of polypropylene molecular chain (especially when starting to warm up melting, complex and polypropylene chains
Activity all increases), it is intended to new hapto or enclosed construction are found in polypropylene chains；Simultaneously with this, as peroxide draws
It sends out agent and decomposes attack of the primary group of free radicals generated to polypropylene backbone, generate polypropylene macromolecular radical on many main chains
(mainly polypropylene tertiary carbon atom free radical), this polypropylene tertiary carbon atom free radical was chain rupture to be occurred originally at high temperature
Degradation reaction, but since complex is to the close of polypropylene chains, the structure of maleic acid is had on complex, this promotes poly-
Propylene tertiary carbon atom free radical can complete the attack to the carbon-carbon double bond in maleic acid structure more conveniently, to make suitable one
The polypropylene tertiary carbon atom free radical that chain-scission degradation should occur for part can be combined first with the maleic acid structure on complex
It realizes grafting, avoids the degradation of this polypropylene segment tertiary carbon atom free radical after the completion of grafting naturally.Therefore, on the whole
From the point of view of, the degradation of polypropylene during melt extrusion is greatly reduced, also increases the grafting rate to polypropylene chains.
Rare earth ion and maleic acid structure are not formed into complex in comparative example 2, thus there is no grafted monomers to
The close effect of polypropylene chains；And although the complex of the structure containing maleic acid is also obtained in comparative example 3 in advance, should
Complexes stability is preferable, and also there is no will search out new hapto to maintain itself coordination structure after mixing with polypropylene
Situation, therefore it is actively close to polypropylene chains not will drive maleic acid structure.Applicant speculates that these are all to cause to tie in table
There is the reason of such difference between fruit.
Claims (7)
1. a kind of preparation method for the maleic acid graft polypropylene for helping to inhibit degradation of polypropylene, it is characterised in that: the system
The specific steps of Preparation Method include,
(1) complex of grafted monomers maleic acid is prepared
Maleic acid is reacted to obtain the complex of maleic acid with soluble inorganic salt of rare earth；
(2) graft polypropylene
After complex including maleic acid obtained in step (1), pp material, antioxidant, initiator are mixed, it is added to
Melting extrusion is carried out in extruder, it is cooling.
2. facilitate the preparation method of the maleic acid graft polypropylene of inhibition degradation of polypropylene as described in claim 1, it is special
Sign is: the concrete operations of step (1) are,
In organic solvent by maleic acid dissolution, and thereto soluble inorganic salt of rare earth solution is added dropwise, heats up after being added dropwise to complete
It is stirred back flow reaction, sediment generated will be reacted and be filtered, washed, be dried in vacuo.
3. facilitate the preparation method of the maleic acid graft polypropylene of inhibition degradation of polypropylene as claimed in claim 2, it is special
Sign is: in step (1), the molar ratio of contained rare earth ion is 1.6~2:1 in maleic acid and soluble inorganic salt of rare earth.
4. facilitate the preparation method of the maleic acid graft polypropylene of inhibition degradation of polypropylene as claimed in claim 2, it is special
Sign is: the rare earth is the combination of one or more of yttrium, lanthanum, cerium, praseodymium, neodymium, erbium.
5. facilitate the preparation method of the maleic acid graft polypropylene of inhibition degradation of polypropylene as claimed in claim 2, it is special
Sign is: contained solvent is ethyl alcohol in the organic solvent and the soluble inorganic salt of rare earth solution.
6. facilitate the preparation method of the maleic acid graft polypropylene of inhibition degradation of polypropylene as described in claim 1, it is special
Sign is: in step (2), the additional amount calculating by weight of the complex, pp material, antioxidant, initiator of maleic acid
For 6~15:100:0.4~1:0.2~1.
7. facilitate the preparation method of the maleic acid graft polypropylene of inhibition degradation of polypropylene as described in claim 1, it is special
Sign is: in step (2), the temperature of extruder melting extrusion is controlled at 160~200 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810939736.3A CN109134764B (en) | 2018-08-17 | 2018-08-17 | Preparation method of maleic acid grafted polypropylene for inhibiting polypropylene degradation |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810939736.3A CN109134764B (en) | 2018-08-17 | 2018-08-17 | Preparation method of maleic acid grafted polypropylene for inhibiting polypropylene degradation |
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| CN109134764A true CN109134764A (en) | 2019-01-04 |
| CN109134764B CN109134764B (en) | 2023-05-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861610A (en) * | 2021-08-30 | 2021-12-31 | 济南大学 | Preparation method and application of novel weather-resistant composite waterproof material |
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 |
-
2018
- 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》" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113861610A (en) * | 2021-08-30 | 2021-12-31 | 济南大学 | Preparation method and application of novel weather-resistant composite waterproof material |
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