CN107245191A - A kind of rare earth modified plastics and preparation method thereof - Google Patents
A kind of rare earth modified plastics and preparation method thereof Download PDFInfo
- Publication number
- CN107245191A CN107245191A CN201710495800.9A CN201710495800A CN107245191A CN 107245191 A CN107245191 A CN 107245191A CN 201710495800 A CN201710495800 A CN 201710495800A CN 107245191 A CN107245191 A CN 107245191A
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- rare earth
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- modified plastics
- organic complex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The present invention relates to a kind of rare earth modified plastics and preparation method thereof.Rare earth modified plastics of the present invention, it includes following components by weight：5 10 parts of 100 parts of polypropylene, 30 40 parts of inserts, 5 10 parts of rare earth organic complex and reinforcing agent；The rare earth organic complex is the metal organic framework using cerium as core.The rare earth modified plastics of the present invention, rare earth is added by the form of rare earth organic complex, rare earth is mutually mixed by organic coordination compound with plastic basis material, the compatibility of rare earth element and polymer is improved, it is to avoid rare earth departs from phase separation that plastics are caused etc.；And the present invention introduces rare earth by the form of metal organic framework, utilize the porous of metal organic framework, macromolecular chain is set to penetrate in hole, induce the arrangement of macromolecular chain, increase the entanglement degree of macromolecular chain and rare earth organic complex, the disengaging of rare earth is further avoided, mechanical performance and the heat-resistant stabilities such as the impact strength of plastics is improved.
Description
Technical field
The present invention relates to plastics package material technology field, more particularly to a kind of rare earth modified plastics and its preparation side
Method.
Background technology
With the fast development of plastics industry, plastic products be widely used in production and people's daily life each neck
Domain.Rare earth is added in the plastic, it is possible to increase the performance of plastics, make rare earth modified plastics that there is preferable stability and mechanicalness
Can etc..
But the existing method for adding rare earth in the plastic, one is to be scattered in polymer using rare earth compound as dopant
In, the doping type rare earth polymer existed with doping way is made, two be to be present in thulium in the way of being bonded
In macromolecule, bonding type rare earth polymer is formed.But doping type rare earth polymer is mainly physical mixed, with high polymer material
Poor compatibility, be easily separated, influence material property, cause intensity impaired etc.；The preparation of bonding type rare earth polymer
Cumbersome, unfavorable use industrialized production greatly limit application of the rare earth in plastic applications.
The content of the invention
Based on this, it is an object of the present invention to provide a kind of rare earth modified plastics and preparation method thereof, described rare earth modified
The compatibility of plastics rare earth and plastics is good, and good mechanical performance.
A kind of rare earth modified plastics, it includes following components by weight：100 parts of polypropylene, 30-40 parts of inserts,
5-10 parts of 5-10 parts of rare earth organic complex and reinforcing agent；The rare earth organic complex is the organic bone of metal using cerium as core
Frame.
Relative to prior art, rare earth modified plastics of the invention add rare earth by the form of rare earth organic complex
Enter, rare earth is mutually mixed by organic coordination compound with plastic basis material, improve the compatibility of rare earth element and polymer, it is to avoid dilute
Soil departs from phase separation that plastics are caused etc.；And the present invention introduces rare earth by the form of metal organic framework, has using metal
The porous of machine skeleton, makes macromolecular chain penetrate in hole, induces the arrangement of macromolecular chain, increase macromolecular chain with rare earth is organic matches somebody with somebody
The entanglement degree of compound, further avoids the disengaging of rare earth, improves mechanical performance and the Heat-resistant stables such as the impact strength of plastics
Property.
Further, the inserts is one in talcum powder, barium sulfate, calcium carbonate, perlite, wollastonite, hydrotalcite
Plant or several mixtures.The inserts can make the plastics have good chemical resistance in use,
And improve the toughness and mechanical strength of the plastics；When wherein talcum powder is as inserts, effectively it can reduce after plastic shaping
OTR oxygen transmission rate, it is ensured that packed article is not corroded or gone bad, and with excellent humidity resistance.
Further, the reinforcing agent is lignocellulosic.The lignocellulosic has excellent pliability and scattered
Property, tridimensional network can be formed by being mixed in plastics, increase the support force and endurance of plastics, improve its stability and strong
Degree.
Further, the rare earth organic complex is that cerium is coordinated the metal organic framework to be formed with 1,3,5-Benzenetricarboxylic acid.
Present invention also offers a kind of preparation method of the rare earth modified plastics, comprise the following steps：
S1：Prepare rare earth organic complex；
S2：After taking polypropylene, inserts and reinforcing agent well mixed, in high-speed mixer, heating melting stirring is obtained
Polyblend；
S3：Rare earth organic complex made from step S1 is added in polyblend made from step S2, stirring makes dilute
Native organic coordination compound is dispersed in polyblend；Then add into comminutor, plastify extruding pelletization, obtain rare earth and change
Property plastics；
Wherein, the rare earth organic complex is the metal organic framework using cerium as core.
Relative to prior art, rare earth organic complex is introduced to modeling by the present invention by way of melt-processed is blended
Expect in matrix, preparation technology is simple；Rare earth is mutually mixed by organic coordination compound with plastic basis material, improves rare earth element with polymerizeing
The compatibility of thing, it is to avoid rare earth departs from phase separation that plastics are caused etc.；And using the porous of metal organic framework, make high score
Subchain is penetrated in hole, induces the entanglement degree of the arrangement of macromolecular chain, increase macromolecular chain and rare earth organic complex, further
The disengaging of rare earth is avoided, mechanical performance and the heat-resistant stabilities such as the impact strength of plastics is improved.
Further, in step S1, comprise the following steps：
S11：1,3,5-Benzenetricarboxylic acid and six water cerous nitrates are added to the in the mixed solvent of DMF and water, in ultrasonic at 40-80 DEG C
Afterwards, centrifuge and collect solid；
S12：The solid that step S11 is obtained is washed with the mixed solvent of second alcohol and water, is dried to obtain the organic cooperation of rare earth
Thing.
Further, in the step S11, the volume ratio of DMF and water is 1:1；1,3,5-Benzenetricarboxylic acid and six water cerous nitrates
Volume ratio is 1:(1-4).
Further, in the step S12, the volume ratio of second alcohol and water is 1:1.
Further, the consumption of each component is respectively by weight：100 parts of polypropylene, 30-40 parts of inserts, rare earth
5-10 parts of 5-10 parts of organic coordination compound and reinforcing agent.
Further, the heating melting temperature in step S2 is 190-240 DEG C.
Further, in step S3, rare earth organic complex made from step S1 is added into polymerization made from step S2 mixed
In compound, 2-4h is stirred with 70-90r/min rotating speed；It is then added in comminutor, plastifies extruding pelletization, obtain rare earth and change
Property plastics.Using this mixing speed, it both can guarantee that rare earth organic complex frame was dispersed in polyblend, it is to avoid thing
Layering or reunion between material；It can guarantee that polymer chain enters in the metal organic framework of rare earth organic complex again, make metal
The arrangement of the effective induced polymer chain of organic backbone.
In order to more fully understand and implement, knot describes the present invention in detail below.
Embodiment
The invention discloses a kind of rare earth modified plastics, it includes following components by weight：100 parts of polypropylene, fill out
5-10 parts of 30-40 parts of charge, 5-10 parts of rare earth organic complex and reinforcing agent；The rare earth organic complex is using cerium as core
Metal organic framework.
Wherein, the inserts be talcum powder, barium sulfate, calcium carbonate, perlite, wollastonite, hydrotalcite in one kind or
Several mixtures；The reinforcing agent is lignocellulosic；The rare earth organic complex is cerium and 1,3,5-Benzenetricarboxylic acid coordination type
Into metal organic framework
The invention also discloses a kind of preparation method of rare earth modified plastics, comprise the following steps：
S1：Prepare rare earth organic complex；
S2：After taking polypropylene, inserts and reinforcing agent well mixed, in high-speed mixer, heating melting stirring is obtained
Polyblend；
S3：Rare earth organic complex made from step S1 is added in polyblend made from step S2, stirring makes dilute
Native organic coordination compound is dispersed in polyblend；Then add into comminutor, plastify extruding pelletization, obtain rare earth and change
Property plastics；
Wherein, the rare earth organic complex is the metal organic framework using cerium as core.
Wherein, in step S1, comprise the following steps：
S11：1,3,5-Benzenetricarboxylic acid and six water cerous nitrates are added to the in the mixed solvent of DMF and water, in ultrasonic at 40-80 DEG C
Afterwards, centrifuge and collect solid；
S12：The solid that step S11 is obtained is washed with the mixed solvent of second alcohol and water, is dried to obtain the organic cooperation of rare earth
Thing；
Wherein, in the step S11, the volume ratio of DMF and water is 1:1；The volume of 1,3,5-Benzenetricarboxylic acid and six water cerous nitrates
Than for 1:(1-4)；In the step S12, the volume ratio of second alcohol and water is 1:1.
Wherein, the heating melting temperature in step S2 is 190-240 DEG C.In step S3, rare earth made from step S1 is had
Machine complex is added in polyblend made from step S2, and 2-4h is stirred with 70-90r/min rotating speed；It is then added to and makes
In grain machine, extruding pelletization is plastified, rare earth modified plastics are obtained.
In the preparation method, the consumption of each component is respectively by weight：100 parts of polypropylene, inserts 30-40
5-10 parts of part, 5-10 parts of rare earth organic complex and reinforcing agent.
Further illustrated with reference to specific embodiment.
Embodiment 1
Present embodiment discloses a kind of rare earth modified plastics, it includes following components by weight：100 parts of polypropylene,
8 parts of 30 parts of wollastonite, 8 parts of rare earth organic complex and lignocellulosic；The rare earth organic complex is using cerium as core
Metal organic framework.
The preparation method of the rare earth modified plastics, comprises the following steps：
S1：Rare earth organic complex is prepared, specifically：
S11：It is 1 to volume ratio:1 DMF and the in the mixed solvent of water add 1,3,5-Benzenetricarboxylic acid and six water cerous nitrates, in
At 40-80 DEG C with 120W power ultrasonics 10-20min after, centrifuge collect solid；
S12：The solid volume ratio that step S11 is obtained is 1:The mixed solvent washing of 1 second alcohol and water, is dried to obtain
Rare earth organic complex；
Wherein, the volume ratio of the 1,3,5-Benzenetricarboxylic acid and six water cerous nitrates is 1:2.
S2：After taking 8 parts of 100 parts of polypropylene, 30 parts of inserts and reinforcing agent well mixed, in high-speed mixer, heating
To 220-240 DEG C of melting stirring, polyblend is obtained.
S3：8 parts of rare earth organic complex made from step S1 is taken to add in polyblend made from step S2, stirring makes
Rare earth organic complex is dispersed in polyblend；Then add into comminutor, plastify extruding pelletization, obtain rare earth
Modified plastics.
Relative to prior art, rare earth organic complex is introduced to modeling by the present invention by way of melt-processed is blended
Expect in matrix, preparation technology is simple；Rare earth is mutually mixed by organic coordination compound with plastic basis material, improves rare earth element with polymerizeing
The compatibility of thing, it is to avoid rare earth departs from phase separation that plastics are caused etc.；And using the porous of metal organic framework, make high score
Subchain is penetrated in hole, induces the entanglement degree of the arrangement of macromolecular chain, increase macromolecular chain and rare earth organic complex, further
The disengaging of rare earth is avoided, mechanical performance and the heat-resistant stabilities such as the impact strength of plastics is improved.
Embodiment 2
Present embodiment discloses a kind of rare earth modified plastics, it includes following components by weight：100 parts of polypropylene,
10 parts of 40 parts of wollastonite, 10 parts of rare earth organic complex and lignocellulosic；The rare earth organic complex is using cerium as core
Metal organic framework.
The preparation method of the rare earth modified plastics, comprises the following steps：
S1：Rare earth organic complex is prepared, specifically：
S11：It is 1 to volume ratio:1 DMF and the in the mixed solvent of water add 1,3,5-Benzenetricarboxylic acid and six water cerous nitrates, in
At 40-80 DEG C with 120W power ultrasonics 10-20min after, centrifuge collect solid；
S12：The solid volume ratio that step S11 is obtained is 1:The mixed solvent washing of 1 second alcohol and water, is dried to obtain
Rare earth organic complex；
Wherein, the volume ratio of the 1,3,5-Benzenetricarboxylic acid and six water cerous nitrates is 1:4.
S2：After taking 10 parts of 100 parts of polypropylene, 40 parts of inserts and reinforcing agent well mixed, in high-speed mixer, heating
To 190-220 DEG C of melting stirring, polyblend is obtained.
S3：10 parts of rare earth organic complex made from step S1 is taken to add in polyblend made from step S2, stirring
Rare earth organic complex is set to be dispersed in polyblend；Then add into comminutor, plastify extruding pelletization, obtain dilute
Native modified plastics.
Embodiment 3
Present embodiment discloses a kind of rare earth modified plastics, it includes following components by weight：100 parts of polypropylene,
5 parts of 36 parts of wollastonite, 5 parts of rare earth organic complex and lignocellulosic；The rare earth organic complex is using cerium as core
Metal organic framework.
The preparation method of the rare earth modified plastics, comprises the following steps：
S1：Rare earth organic complex is prepared, specifically：
S11：It is 1 to volume ratio:1 DMF and the in the mixed solvent of water add 1,3,5-Benzenetricarboxylic acid and six water cerous nitrates, in
At 40-80 DEG C with 120W power ultrasonics 10-20min after, centrifuge collect solid；
S12：The solid volume ratio that step S11 is obtained is 1:The mixed solvent washing of 1 second alcohol and water, is dried to obtain
Rare earth organic complex；
Wherein, the volume ratio of the 1,3,5-Benzenetricarboxylic acid and six water cerous nitrates is 1:1.
S2：After taking 5 parts of 100 parts of polypropylene, 36 parts of inserts and reinforcing agent well mixed, in high-speed mixer, heating
To 190-220 DEG C of melting stirring, polyblend is obtained.
S3：5 parts of rare earth organic complex made from step S1 is taken to add in polyblend made from step S2, stirring makes
Rare earth organic complex is dispersed in polyblend；Then add into comminutor, plastify extruding pelletization, obtain rare earth
Modified plastics.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.
Claims (10)
1. a kind of rare earth modified plastics, it is characterised in that：It includes following components by weight：100 parts of polypropylene, inserts
5-10 parts of 30-40 parts, 5-10 parts of rare earth organic complex and reinforcing agent；The rare earth organic complex is the gold using cerium as core
Belong to organic backbone.
2. rare earth modified plastics according to claim 1, it is characterised in that：The inserts is talcum powder, barium sulfate, carbon
One or more of mixtures in sour calcium, perlite, wollastonite, hydrotalcite.
3. rare earth modified plastics according to claim 1, it is characterised in that：The reinforcing agent is lignocellulosic.
4. rare earth modified plastics according to claim 1, it is characterised in that：The rare earth organic complex is cerium and isophthalic
Tricarboxylic acid is coordinated the metal organic framework to be formed.
5. a kind of preparation method of rare earth modified plastics, it is characterised in that：Comprise the following steps：
S1：Prepare rare earth organic complex；
S2：After taking polypropylene, inserts and reinforcing agent well mixed, in high-speed mixer, heating melting stirring is polymerize
Mixture；
S3：Rare earth organic complex made from step S1 is added in polyblend made from step S2, stirring has rare earth
Machine complex is dispersed in polyblend；Then add into comminutor, plastify extruding pelletization, obtain rare earth modified modeling
Material；
Wherein, the rare earth organic complex is the metal organic framework using cerium as core.
6. the preparation method of rare earth modified plastics according to claim 5, it is characterised in that：In step S1, including it is following
Step：
S11：1,3,5-Benzenetricarboxylic acid and six water cerous nitrates are added to the in the mixed solvent of DMF and water, in after ultrasound at 40-80 DEG C, from
The heart separates and collects solid；
S12：The solid that step S11 is obtained is washed with the mixed solvent of second alcohol and water, is dried to obtain rare earth organic complex.
7. the preparation method of rare earth modified plastics according to claim 6, it is characterised in that：In the step S11, DMF
Volume ratio with water is 1:1, the volume ratio of 1,3,5-Benzenetricarboxylic acid and six water cerous nitrates is 1:(1-4)；In the step S12, ethanol
Volume ratio with water is 1:1.
8. the preparation method of rare earth modified plastics according to claim 5, it is characterised in that：The consumption of each component is by weight
Number is respectively：5-10 parts of 100 parts of polypropylene, 30-40 parts of inserts, 5-10 parts of rare earth organic complex and reinforcing agent.
9. the preparation method of rare earth modified plastics according to claim 5, it is characterised in that：Heating melting in step S2
Temperature is 190-240 DEG C.
10. the preparation method of rare earth modified plastics according to claim 5, it is characterised in that：In step S3, by step S1
Obtained rare earth organic complex is added in polyblend made from step S2, and 2-4h is stirred with 70-90r/min rotating speed；
It is then added in comminutor, plastifies extruding pelletization, obtain rare earth modified plastics.
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| CN201710495800.9A CN107245191A (en) | 2017-06-26 | 2017-06-26 | A kind of rare earth modified plastics and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108912463A (en) * | 2018-08-06 | 2018-11-30 | 中国科学院合肥物质科学研究院 | A kind of gadolinium Base Metal organic backbone composite shielding material and preparation method |
| CN109096723A (en) * | 2018-06-22 | 2018-12-28 | 宁波帅特龙集团有限公司 | Spanner is opened in one kind |
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| CN102652035A (en) * | 2009-12-15 | 2012-08-29 | 环球油品公司 | Metal organic framework polymer mixed matrix membranes |
| CN104312000A (en) * | 2014-11-03 | 2015-01-28 | 华东理工大学 | Wood-plastic composite with flame-retardation effect and preparation method |
| CN104324761A (en) * | 2014-10-09 | 2015-02-04 | 济南大学 | Preparation and applications of porous rare earth organic complex base catalyst |
| CN105061810A (en) * | 2015-07-20 | 2015-11-18 | 广西中烟工业有限责任公司 | Anti-bacterial electronic cigarette appearance material as well as preparation method and application thereof |
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2017
- 2017-06-26 CN CN201710495800.9A patent/CN107245191A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102652035A (en) * | 2009-12-15 | 2012-08-29 | 环球油品公司 | Metal organic framework polymer mixed matrix membranes |
| CN104324761A (en) * | 2014-10-09 | 2015-02-04 | 济南大学 | Preparation and applications of porous rare earth organic complex base catalyst |
| CN104312000A (en) * | 2014-11-03 | 2015-01-28 | 华东理工大学 | Wood-plastic composite with flame-retardation effect and preparation method |
| CN105061810A (en) * | 2015-07-20 | 2015-11-18 | 广西中烟工业有限责任公司 | Anti-bacterial electronic cigarette appearance material as well as preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096723A (en) * | 2018-06-22 | 2018-12-28 | 宁波帅特龙集团有限公司 | Spanner is opened in one kind |
| CN108912463A (en) * | 2018-08-06 | 2018-11-30 | 中国科学院合肥物质科学研究院 | A kind of gadolinium Base Metal organic backbone composite shielding material and preparation method |
| CN108912463B (en) * | 2018-08-06 | 2021-04-27 | 中国科学院合肥物质科学研究院 | Gadolinium-based metal organic framework composite shielding material and preparation method thereof |
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