CN116715898A - Rare earth-based nucleating agent for polypropylene and preparation method thereof - Google Patents
Rare earth-based nucleating agent for polypropylene and preparation method thereof Download PDFInfo
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- CN116715898A CN116715898A CN202310868122.1A CN202310868122A CN116715898A CN 116715898 A CN116715898 A CN 116715898A CN 202310868122 A CN202310868122 A CN 202310868122A CN 116715898 A CN116715898 A CN 116715898A
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- polypropylene
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- nucleating agent
- based nucleating
- nitrate hexahydrate
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- -1 polypropylene Polymers 0.000 title claims abstract description 67
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 64
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 64
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 59
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 52
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 16
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229940120146 EDTMP Drugs 0.000 description 13
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The rare earth-based nucleating agent for polypropylene is characterized by comprising the following components in parts by weight: 70-85% of cerium nitrate hexahydrate; 15-30% of hexamethylenediamine tetramethylene phosphonic acid. The invention also discloses a preparation method of the rare earth-based nucleating agent for polypropylene. The rare earth-based nucleating agent can obviously improve the high-temperature stability and low-temperature toughness of polypropylene while ensuring the high strength of the polypropylene.
Description
Technical Field
The invention relates to a modified preparation of polypropylene, in particular to a nucleating agent containing rare earth, which is suitable for modification preparation of polypropylene, and also relates to a preparation method of the nucleating agent.
Background
With the rapid development of new energy automobiles, lithium ion batteries are developed in a blowout manner. However, the safety of lithium ion batteries is a high concern for the occurrence of spontaneous combustion and explosion events of new energy automobiles. In the structure of lithium batteries, the battery separator is one of the key inner layer components and is also a high-added-value material with the highest technical barrier.
The membrane is a core material for ensuring the safety of a battery system and influencing the performance of the battery, and the commercial dry-method membrane mainly adopts polypropylene because the polypropylene has the advantages of low price, excellent mechanical property, stable electrochemical property and the like. However, the polypropylene diaphragm sometimes contracts and deforms in the high-temperature charge and discharge process to cause the explosion of equipment, but is brittle in the low-temperature working condition, and is easy to be pierced by burrs, dendrites and the like to cause short circuit. The Chinese dry method diaphragm enterprises have occupied more than 60% of the global market share, but the upstream polypropylene material of the diaphragm is seriously dependent on import, which is mainly because the domestic polypropylene material cannot meet the diaphragm performance requirement.
The polypropylene lithium ion battery diaphragm can shrink and deform in the high-temperature charge and discharge process, so that the spontaneous combustion of an electric automobile and the explosion of equipment such as a mobile phone and the like are caused, and the life safety of a person is seriously endangered. Although graft polymerization, coating and other techniques can improve the thermal stability of polypropylene separators, most of the techniques are still in research stages and are not applied to large-scale commercial production.
At present, a method for adding a nucleating agent to improve the high-temperature stability and low-temperature toughness of polypropylene is mainly adopted by commercial polypropylene diaphragms. Such nucleating agents can be broadly classified into inorganic nucleating agents and organic nucleating agents in terms of chemical structure, and the inorganic nucleating agents mainly include talc, mica, calcium carbonate, silica, molecular sieves, and the like. Such nucleating agents are developed earlier, and the greatest advantage is low cost and availability. However, the inorganic powder has poor compatibility with the polypropylene resin, so that the transparency and glossiness of the product are not improved greatly, and the application of the product is further limited. The other organic nucleating agent has a plurality of kinds and good nucleating effect. Mainly comprises carboxylate, sorbitol (DBS) and aryl phosphate and abietic acid soap. Sorbitol and aryl phosphates are currently used in a large number, the former for anti-reflection and the latter for stiffening. Because of good nucleation and compatibility, organic nucleating agents are currently becoming the main development direction of polypropylene nucleating agents.
The prior art also discloses the literature of an organic nucleating agent, and is disclosed in China patent No. ZL201610513822.9, namely a rare earth polypropylene stiffening nucleating agent and a preparation method thereof (the publication No. CN 106084465B), and the patent also adopts a rare earth complex.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a rare earth-based nucleating agent for polypropylene in addition to the above state of the art.
The second technical problem to be solved by the present invention is to provide a method for preparing a rare earth-based nucleating agent for polypropylene in addition to the above state of the art.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the rare earth-based nucleating agent for polypropylene is characterized by comprising the following components in parts by weight:
70-85% of cerium nitrate hexahydrate;
15-30% of hexamethylenediamine tetramethylene phosphonic acid.
Optimally, the composition comprises the following components in parts by weight:
cerium nitrate hexahydrate 20%;
80% of hexamethylenediamine tetramethylene phosphonic acid.
Preferably, the purity of the cerium nitrate hexahydrate is more than or equal to 99.95%; the purity of the hexamethylenediamine tetramethylene phosphonic acid is more than or equal to 98 percent.
The invention solves the second technical problem by adopting the technical proposal that: a preparation method of a rare earth-based nucleating agent for polypropylene is characterized by comprising the following steps:
(1) dissolving hexamethylenediamine tetramethylene phosphonic acid in deionized water, and stirring at room temperature for 8-15 min until suspended substances cannot be seen by naked eyes in the deionized water to obtain an hexamethylenediamine tetramethylene phosphonic acid aqueous solution;
(2) dissolving cerium nitrate hexahydrate in deionized water to obtain cerium nitrate hexahydrate aqueous solution, and dropwise adding the cerium nitrate hexahydrate aqueous solution into the stirred hexamethylenediamine tetramethylene phosphonic acid aqueous solution;
(3) after the dripping is finished, heating is started, and the mixture reacts for 24 to 48 hours at the temperature of 70 to 90 ℃ to obtain a mixed solution;
(4) transferring the mixed solution into a high-pressure reaction kettle, and carrying out constant-temperature hydrothermal reaction for 24-72 h at the temperature of 80-100 ℃;
(5) and finally, repeatedly washing with deionized water, centrifuging, and finally obtaining the rare earth-based nucleating agent.
Preferably, the conditions for dropping the aqueous cerium nitrate hexahydrate solution in step (2) are as follows: the mixture was added dropwise via a constant pressure dropping funnel at a rate of 5 to 7 mL/min.
Preferably, the drying temperature in step (5) is 80 to 110 ℃.
The rare earth-based nucleating agent is used for preparing a polypropylene material with high temperature stability and low temperature toughness, and the preferable preparation method is as follows: the rare earth-based nucleating agent for polypropylene is melt blended with polypropylene to prepare the polypropylene material containing the rare earth-based nucleating agent and having high-temperature stability and low-temperature toughness. The rare earth-based nucleating agent for polypropylene accounts for 0.1-0.5% of the weight of the polypropylene material, and the polypropylene is one of homo-polypropylene, co-polypropylene and the like.
Compared with the prior art, the invention has the advantages that: the rare earth element cerium (Ce) in the rare earth-based nucleating agent has an empty 4f electron orbit and free radical capturing capacity, can react with a molecular chain segment of polypropylene high-temperature degradation under a high-temperature condition, prevents the free radical chain degradation reaction of polypropylene from further occurring, and further improves the high-temperature stability of the polypropylene material.
The ethylenediamine tetramethylene phosphonic acid (EDTMP) can form coordination with the rare earth element, so that the rare earth element is connected with a large number of organic groups, the dispersibility of the rare earth compound in polypropylene is improved, and the surface of the obtained rare earth-based nucleating agent has a large number of organic groups, so that the rare earth-based nucleating agent is easy to disperse in polypropylene and is not easy to generate agglomeration; in addition, the rare earth-based nucleating agent is in a nano-scale spherical form, can be used as a nano-scale nucleating agent in polypropylene, can induce the polypropylene to form a microcrystalline structure, and is not easy to generate large spherulites, thereby being beneficial to forming uniformly distributed microcrystals in the polypropylene material and ensuring the stability of performance and dimension.
The rare earth-based nucleating agent has a large number of flexible organic groups on the surface, and the nano-scale small molecular structure of the rare earth-based nucleating agent is added, so that the rare earth-based nucleating agent can enter between polypropylene macromolecular chains through melt blending with polypropylene to damage the entanglement structure of the polypropylene macromolecular chains, thereby reducing the interaction among the polypropylene macromolecules and greatly improving the low-temperature toughness of the polypropylene macromolecular chains.
Experiments prove that the rare earth-based nucleating agent can obviously improve the high-temperature stability and the low-temperature toughness of polypropylene while ensuring the high strength of the polypropylene.
Drawings
FIG. 1 is an infrared spectrum of the rare earth-based nucleating agent obtained in example 2.
FIG. 2 is a scanning electron microscope image of the rare earth-based nucleating agent obtained in example 2.
Fig. 3 is an optical micrograph of a polypropylene film.
FIG. 4 is an optical microscope image of the rare earth based nucleating agent of example 2 melt blended with polypropylene to produce a film.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
4.00g of EDTMP is dissolved in 100mL of deionized water, and stirring is started at room temperature for 8min;9.68g Ce (NO) 3 ·6H 2 O is dissolved in 100mL of deionized water, and is added into the stirred EDTMP water solution in a dropwise manner through a constant pressure dropping funnel at a rate of 5 mL/min; after the dripping is finished, heating is started, and the reaction is carried out for 24 hours at 90 ℃; transferring the mixed solution into a high-pressure reaction kettle, and performing constant-temperature hydrothermal reaction for 24 hours at the temperature of 100 ℃;
and finally, repeatedly washing with deionized water, centrifuging and drying to finally obtain the rare earth-based nucleating agent.
The prepared rare earth-based nucleating agent is melted and blended for 10min in an internal mixer at a melting temperature of 160 ℃ and a rotating speed of 55r/min, wherein the weight percentage of the rare earth-based nucleating agent is 0.1 percent (the rest materials are polypropylene), and the polypropylene with high-temperature stability and low-temperature toughness containing the rare earth-based nucleating agent is obtained.
Example 2:
3.15g of hexamethylenediamine tetramethylene phosphonic acid (EDTMP) are dissolved in 100mL of deionized water and stirred at room temperature for 10min; 12.60g cerium nitrate hexahydrate (Ce (NO) 3 ·6H 2 O) is dissolved in 100mL of deionized water and is added into the stirred EDTMP water solution in a dropwise manner through a constant pressure dropping funnel at a rate of 6 mL/min; after the dripping is finished, heating is started, and the reaction is carried out for 36 hours at 80 ℃; transferring the mixed solution into a high-pressure reaction kettle, and performing constant-temperature hydrothermal reaction for 48 hours at 90 ℃; and finally, repeatedly washing with deionized water, centrifuging and drying (the temperature is 80-110 ℃), and finally obtaining the rare earth-based nucleating agent.
As shown in FIG. 1, by comparing the infrared spectrograms of CeEDTMP and EDTMP, the EDTMP is easy to dissociate in aqueous solution, has strong coordination capability and can carry out coordination reaction with metal ions. EDTMP at 3409cm -1 The strong wide absorption band is the absorption peak of hydroxyl, and the absorption peak is 1658cm -1 The bending vibration peak of the water molecule is shown, which indicates that the crystal water exists in the EDTMP. 3035cm -1 And 3007cm -1 The absorption peak belonging to CH-. CeEDTMP and EDTMP at 1500-1000cm -1 The peaks of the region, which corresponds to-P (O) (OH), vary greatly 2 The characteristic peaks of (2) indicate that phosphonate and Ce react and coordinate, and indicate that CeEDTMP is synthesized.
As shown in fig. 2, ceEDTMP exhibits an approximately spherical three-dimensional structure with a particle size of about 100nm.
The prepared rare earth-based nucleating agent is melted and blended for 10min in an internal mixer at a melting temperature of 170 ℃ and a rotating speed of 60r/min, wherein the weight percentage of the rare earth-based nucleating agent is 0.3 percent (the rest is polypropylene), and the polypropylene with high-temperature stability and low-temperature toughness containing the rare earth-based nucleating agent is obtained.
As shown in figures 3 and 4, the polypropylene film forms large spherulites which are distributed sporadically, and the rare earth-based nucleating agent is fused and blended with polypropylene to prepare the film, so that a uniformly distributed microcrystalline structure is formed.
Example 3:
2.00g of EDTMP is dissolved in 100mL of deionized water, and stirring is started at room temperature for 15min; 11.33g of Ce (NO) 3 ·6H 2 O is dissolved in 100mL of deionized water, and is added into the stirred EDTMP water solution in a dropwise manner through a constant pressure dropping funnel at a rate of 7 mL/min; after the dripping is finished, heating is started, and the reaction is carried out for 72 hours at 70 ℃; transferring the mixed solution into a high-pressure reaction kettle, and performing constant-temperature hydrothermal reaction for 72 hours at the temperature of 80 ℃; finally, repeatedly washing with deionized water, centrifuging and drying (the temperature is 80-110 ℃), and finally obtaining the rare earth-based nucleating agent;
the prepared rare earth-based nucleating agent is melted and blended for 10min in an internal mixer at a melting temperature of 160 ℃ and a rotating speed of 50r/min, wherein the weight percentage of the rare earth-based nucleating agent is 0.5 percent (the rest materials are polypropylene), and the polypropylene with high-temperature stability and low-temperature toughness containing the rare earth-based nucleating agent is obtained.
The test results of the high temperature stability and low temperature toughness test (test conditions: impact test was conducted according to GB1043-93 standard, sample size was 70X 6X 4mm, notch 2mm, tensile test was conducted according to GB1040-89 standard, sample was made into dumbbell shape, gauge length was 25mm, tensile rate was 25mm/min, heat deformation test was conducted according to GB/T1633 standard, span size was 64mm, and heating rate was 5 ℃/min.) are shown in Table 1. As can be seen from the table, the notch impact strength and the tensile strength of the polypropylene at low temperature are obviously improved after the rare earth-based nucleating agent is added, and the mechanical properties of the polypropylene at room temperature are not greatly different; in addition, the thermal deformation temperature of the polypropylene is greatly improved after the rare earth-based nucleating agent is added, and can reach 180 ℃ at maximum, so that the polypropylene can maintain good stability at high temperature.
TABLE 1 results of Performance test of examples
Claims (6)
1. The rare earth-based nucleating agent for polypropylene is characterized by comprising the following components in parts by weight:
70-85% of cerium nitrate hexahydrate;
15-30% of hexamethylenediamine tetramethylene phosphonic acid.
2. The rare earth-based nucleating agent for polypropylene according to claim 1, which is characterized by comprising the following components in parts by weight:
cerium nitrate hexahydrate 20%;
80% of hexamethylenediamine tetramethylene phosphonic acid.
3. The rare earth-based nucleating agent for polypropylene according to claim 1, wherein the purity of cerium nitrate hexahydrate is not less than 99.95%; the purity of the hexamethylenediamine tetramethylene phosphonic acid is more than or equal to 98 percent.
4. A process for the preparation of a rare earth based nucleating agent for polypropylene as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
(1) dissolving hexamethylenediamine tetramethylene phosphonic acid in deionized water, and stirring at room temperature until suspended substances cannot be seen by eyes in the deionized water to obtain an hexamethylenediamine tetramethylene phosphonic acid aqueous solution;
(2) dissolving cerium nitrate hexahydrate in deionized water to obtain cerium nitrate hexahydrate aqueous solution, and dropwise adding the cerium nitrate hexahydrate aqueous solution into the stirred hexamethylenediamine tetramethylene phosphonic acid aqueous solution;
(3) after the dripping is finished, heating is started, and the mixture reacts for 24 to 48 hours at the temperature of 70 to 90 ℃ to obtain a mixed solution;
(4) transferring the mixed solution into a high-pressure reaction kettle, and carrying out constant-temperature hydrothermal reaction for 24-72 h at the temperature of 80-100 ℃;
(5) and finally, repeatedly washing with deionized water, centrifuging, and finally obtaining the rare earth-based nucleating agent.
5. The process according to claim 4, wherein the conditions for dropping the aqueous cerium nitrate hexahydrate solution in the step (2) are as follows: the mixture was added dropwise via a constant pressure dropping funnel at a rate of 5 to 7 mL/min.
6. The process according to claim 4, wherein the drying temperature in the step (5) is 80 to 110 ℃.
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| CN116855206A (en) * | 2023-07-31 | 2023-10-10 | 重庆索梦得新材料科技有限公司 | Waterproof flame-retardant plant fiber polymer adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116855206A (en) * | 2023-07-31 | 2023-10-10 | 重庆索梦得新材料科技有限公司 | Waterproof flame-retardant plant fiber polymer adhesive |
| CN116855206B (en) * | 2023-07-31 | 2024-02-02 | 重庆索梦得新材料科技有限公司 | Waterproof flame-retardant plant fiber polymer adhesive |
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