CN110437541A - A kind of polypropylene modified material and preparation method thereof - Google Patents
A kind of polypropylene modified material and preparation method thereof Download PDFInfo
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- CN110437541A CN110437541A CN201910768128.5A CN201910768128A CN110437541A CN 110437541 A CN110437541 A CN 110437541A CN 201910768128 A CN201910768128 A CN 201910768128A CN 110437541 A CN110437541 A CN 110437541A
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The present invention provides a kind of polypropylene modified materials, are prepared by the raw material for including following components: third 99.6~99.8wt% of fourth acrylic resin copolymer；0.1~0.3wt% of antioxidant；0.01~0.03wt% of light transmission agent；0.01~0.1wt% of halogen-absorber.Compared with prior art, the polypropylene modified material is using the third fourth acrylic resin copolymer as matrix resin, preferable interaction is realized with other certain content components, make product that there is good processing performance, mechanical property and optical property, low-molecular material is precipitated less, can satisfy the production requirement of disposable tableware.The experimental results showed that the polypropylene modified material yellow colour index is -2.4~0.2, transparency with higher；Ash content is seldom simultaneously, and oxidation induction period is 18.12~22.42min, and melt flow rate (MFR) is 12.96~13.20g/10min, has good processing performance；And bending strength is 1082~1251MPa, impact resistance with higher, preferable dimensional stability and flexibility, good mechanical properties are conducive to disposable lunch-box material and use under cryogenic, will not rupture for producing disposable lunch-box, good airproof performance.
Description
Technical field
The present invention relates to technical field of polymer materials, more specifically, be related to a kind of polypropylene modified material and its
Preparation method.
Background technique
Polypropylene has good chemical stability, processing performance and relatively cheap valence as general plastic material
Lattice, but homopolypropylene is easily formed big spherocrystal, and reflection, refraction, scattering, the product transparency can occur after passing through for light
Difference, appearance lack aesthetic feeling.Therefore it needs to be modified it, to meet the needs of Downstream Market.
Compared with general polypropylene, the transparency and glossiness greatly improve third fourth atactic copolymerized polypropene.Transparent polypropylene
Not only there is the excellent transparency and glossiness, but also heat distortion temperature with higher.It is transparent poly- due to its high performance-price ratio
Propylene compares conventional transparent material (PET, PS etc.) with wider application range and broader practice prospect.According to statistics,
The growth rate of transparent polypropylene production of articles is higher by conventional polypropylene product in recent years.
Currently, disposable tableware in the market mainly using PS/ high impact polystyrene (HIPS) blend as raw material into
Row thermoforming processing preparation, there are processing and forming hardly possible, product impact resistance, dimensional stability and flexibility are poor, low in product
The problems such as molecule object is precipitated.
Summary of the invention
In view of this, the present invention mentions the purpose of the present invention is to provide a kind of polypropylene modified material and preparation method thereof
The polypropylene modified material of confession has good processing performance, mechanical property and optical property, and few, Neng Gouman is precipitated in low-molecular material
The production requirement of sufficient disposable tableware.
The present invention provides a kind of polypropylene modified materials, are prepared by the raw material for including following components:
Third fourth acrylic resin copolymer 99.6wt%~99.8wt%；
Antioxidant 0.1wt%~0.3wt%；
Light transmission agent 0.01wt%~0.03wt%；
Halogen-absorber 0.01wt%~0.1wt%.
Preferably, the third fourth acrylic resin copolymer is randomly total in the presence of a catalyst and hydrogen by propylene and 1- butylene
It is poly- to form.
Preferably, the catalyst is II type catalyst of DQ-；The additional amount of the catalyst and the third fourth copolymer polypropylene tree
The ratio between yield of rouge is 1g:(8kg~9kg).
Preferably, the concentration of the hydrogen is 500ppm~1000ppm.
Preferably, the temperature of the random copolymerization is 60 DEG C~70 DEG C, and pressure is 2.5MPa~3.5MPa.
Preferably, the antioxidant is selected from phenolic antioxidant and/or phosphite ester antioxidant.
Preferably, the light transmission agent is selected from NA-21 and/or TMP-6.
Preferably, the halogen-absorber is selected from zinc stearate and/or hydrotalcite.
The present invention also provides a kind of preparation method of polypropylene modified material described in above-mentioned technical proposal, including it is following
Step:
A) the third fourth acrylic resin copolymer, antioxidant, light transmission agent and halogen-absorber are mixed, carries out extruding pelletization, obtains
To polypropylene modified material.
Preferably, the temperature of extruding pelletization described in step a) is 160 DEG C~240 DEG C.
The present invention provides a kind of polypropylene modified materials, are prepared by the raw material for including following components: the third Ding Gongju
Acrylic resin 99.6wt%~99.8wt%；Antioxidant 0.1wt%~0.3wt%；Light transmission agent 0.01wt%~0.03wt%；
Halogen-absorber 0.01wt%~0.1wt%.Compared with prior art, polypropylene modified material provided by the invention is total with the third fourth
Poly- acrylic resin is matrix resin, realizes preferable interaction with other certain content components, has product good
Processing performance, mechanical property and optical property, low-molecular material are precipitated less, can satisfy the production requirement of disposable tableware.Experiment
The result shows that polypropylene modified material yellow colour index provided by the invention is -2.4~0.2, transparency with higher；Simultaneously
Ash content is seldom, and oxidation induction period is 18.12min~22.42min, and melt flow rate (MFR) is 12.96g/10min~13.20g/
10min has good processing performance；And bending strength is 1082MPa~1251MPa, impact resistance with higher, compared with
Good dimensional stability and flexibility has good mechanical property, and be conducive to disposable lunch-box material uses under cryogenic, uses
It will not be ruptured in production disposable lunch-box, good airproof performance.
In addition, preparation method simple process provided by the invention, mild condition, are suitble to large-scale industrial production, have wide
Wealthy application prospect.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of polypropylene modified materials, are prepared by the raw material for including following components:
Third fourth acrylic resin copolymer 99.6wt%~99.8wt%；
Antioxidant 0.1wt%~0.3wt%；
Light transmission agent 0.01wt%~0.03wt%；
Halogen-absorber 0.01wt%~0.1wt%.
In the present invention, the polypropylene modified material by include the third fourth acrylic resin copolymer, antioxidant, light transmission agent and
The raw material of halogen-absorber is prepared, preferably by the third fourth acrylic resin copolymer, antioxidant, light transmission agent and halogen-absorber system
It is standby to form.In the present invention, the third fourth acrylic resin copolymer is preferably existed by propylene and 1- butylene in catalyst and hydrogen
Lower random copolymerization forms.The present invention is not particularly limited the source of the propylene and 1- butylene, using those skilled in the art
Well known commercial goods or own product.
In the present invention, the catalyst is preferably II type catalyst of DQ-, major catalyst TEAL, electron donor
DONOR；The present invention is not particularly limited the source of the catalyst, is using commercial goods well known to those skilled in the art
It can.In the present invention, the ratio between yield of the additional amount of the catalyst and the third fourth acrylic resin copolymer preferably 1g:(8kg~
9kg), more preferably 1g:8.57kg.
In the present invention, the concentration of the hydrogen is preferably 500ppm~1000ppm.
The present invention is not particularly limited the device of the random copolymerization, using reaction kettle well known to those skilled in the art
.In the present invention, the process of the random copolymerization is preferably additionally added co-catalyst；Kind of the present invention to the co-catalyst
Class and source are not particularly limited, and commercially available triethyl aluminum well known to those skilled in the art such as can be used.
In the present invention, the temperature of the random copolymerization is preferably 60 DEG C~70 DEG C, more preferably 64 DEG C~66 DEG C；It is described
The pressure of random copolymerization is preferably 2.5MPa~3.5MPa, more preferably 3MPa~3.2MPa；Meanwhile the present invention preferably guarantees institute
The 1- butene concentration for stating random copolymerization is 1%~5%.
In the present invention, the polypropylene modified material includes the third fourth copolymer polypropylene tree of 99.6wt%~99.8wt%
Rouge, preferably 99.70wt%~99.76wt%.
In the present invention, the antioxidant is preferably selected from phenolic antioxidant and/or phosphite ester antioxidant, more preferably
Phenolic antioxidant and phosphite ester antioxidant.The present invention is not particularly limited the source of the antioxidant, using this field
The commercial goods of above-mentioned phenolic antioxidant and phosphite ester antioxidant known to technical staff.In currently preferred reality
It applies in example, the antioxidant is phenolic antioxidant 1010 and phosphite ester antioxidant 168；The phenolic antioxidant 1010 and Asia
The mass ratio of phosphoric acid ester irgasfos 168 is preferably (1~1.5): 1.In the present invention, the polypropylene modified material includes
The antioxidant of 0.1wt%~0.3wt%, preferably 0.2wt%~0.24wt%.
In the present invention, the light transmission agent is preferably selected from NA-21 and/or TMP-6.Source of the present invention to the light transmission agent
It is not particularly limited, using commercial goods well known to those skilled in the art.In the present invention, the polypropylene modification material
Material includes the light transmission agent of 0.01wt%~0.03wt%, preferably 0.02wt%.
In the present invention, the halogen-absorber is preferably selected from zinc stearate and/or hydrotalcite.The present invention is to the halogen
The source of absorbent is not particularly limited, using commercial goods well known to those skilled in the art.Currently preferred
In embodiment, the halogen-absorber is zinc stearate and hydrotalcite；The mass ratio of the zinc stearate and hydrotalcite is preferably
1:(1~1.2), more preferably 1:1.In the present invention, the polypropylene modified material includes the halogen of 0.01wt%~0.1wt%
Plain absorbent, preferably 0.02wt%~0.08wt%.
Polypropylene modified material provided by the invention specific contains using the third fourth acrylic resin copolymer as matrix resin with other
It measures component and realizes preferable interaction, make product that there is good processing performance, mechanical property and optical property, low-molecular material
It is precipitated less, can satisfy the production requirement of disposable tableware.
The present invention also provides a kind of preparation method of polypropylene modified material described in above-mentioned technical proposal, including it is following
Step:
A) the third fourth acrylic resin copolymer, antioxidant, light transmission agent and halogen-absorber are mixed, carries out extruding pelletization, obtains
To polypropylene modified material.
The present invention mixes the third fourth acrylic resin copolymer, antioxidant, light transmission agent and halogen-absorber, squeeze out and makes
Grain, obtains polypropylene modified material.In the present invention, the third fourth acrylic resin copolymer, antioxidant, light transmission agent and halogen are inhaled
Receive agent with it is as described in the above technical scheme identical, details are not described herein.
The present invention is not particularly limited the mixed device, mixed using high-speed stirred well known to those skilled in the art
Conjunction machine；The present invention is not particularly limited the mixed temperature, pressure simultaneously, using known to those skilled in the art
Normal temperature and pressure.In the present invention, the mixed revolving speed is preferably 15r/min~30r/min, more preferably 20r/
min；The mixed time is preferably 1min~10min, more preferably 5min~6min.
In the present invention, the temperature of the extruding pelletization is preferably 160 DEG C~240 DEG C, more preferably 200 DEG C~220 DEG C；
The present invention is not particularly limited the device of the extruding pelletization, using extruding granulator well known to those skilled in the art, protects
It demonstrate,proves each zone temperatures and realizes melt blending within the scope of above-mentioned restriction.
Preparation method simple process provided by the invention, mild condition are suitble to large-scale industrial production, have wide answer
Use prospect.
The present invention provides a kind of polypropylene modified materials, are prepared by the raw material for including following components: the third Ding Gongju
Acrylic resin 99.6wt%~99.8wt%；Antioxidant 0.1wt%~0.3wt%；Light transmission agent 0.01wt%~0.03wt%；
Halogen-absorber 0.01wt%~0.1wt%.Compared with prior art, polypropylene modified material provided by the invention is total with the third fourth
Poly- acrylic resin is matrix resin, realizes preferable interaction with other certain content components, has product good
Processing performance, mechanical property and optical property, low-molecular material are precipitated less, can satisfy the production requirement of disposable tableware.Experiment
The result shows that polypropylene modified material yellow colour index provided by the invention is -2.4~0.2, transparency with higher；Simultaneously
Ash content is seldom, and oxidation induction period is 18.12min~22.42min, and melt flow rate (MFR) is 12.96g/10min~13.20g/
10min has good processing performance；And bending strength is 1082MPa~1251MPa, impact resistance with higher, compared with
Good dimensional stability and flexibility has good mechanical property, and be conducive to disposable lunch-box material uses under cryogenic, uses
It will not be ruptured in production disposable lunch-box, good airproof performance.
In addition, preparation method simple process provided by the invention, mild condition, are suitble to large-scale industrial production, have wide
Wealthy application prospect.
In order to further illustrate the present invention, it is described in detail below by following embodiment.Following embodiment of the present invention
The preparation method of third fourth acrylic resin copolymer used specifically:
Propylene and 1- butylene are added in reaction kettle, and catalyst DQ- II type (major catalyst TEAL, electron donor is added
DONOR it) is stirred evenly with co-catalyst (triethyl aluminum)；
Catalyst is added according to yield 8.57kg/g catalyst, and TEAL/Ti (Ti element in catalyst)=64:1, Ti/ is mono-
Body (C3)=2.45:1, TEAL/DONOR=3.18:1；
Control temperature of reactor be 65 ± 1 DEG C, reaction pressure be 3.0MPa~3.2MPa, density of hydrogen be 500ppm~
1000ppm, 1- butene concentration are 1%~5%, and reaction obtains the third fourth acrylic resin copolymer.
Propylene used is polymerization-grade propylene, and design parameter index ginseng is shown in Table 1；
The design parameter achievement data of propylene used in 1 embodiment of the present invention of table
| Project | Unit | Index |
| Purity | % | 99.6 |
| Water | ppm | ≤10 |
| Sulphur | ppm | ≤1 |
| CO | ppm | ≤5 |
| CO2 | ppm | ≤10 |
| O2 | ppm | ≤10 |
| Alkadienes, alkynes | ppm | ≤5 |
| Propane | ppm | ≤300 |
| C4 | mL/m3 | ≤5 |
The design parameter index ginseng of comonomer 1- butylene used is shown in Table 2；
The design parameter achievement data of comonomer 1- butylene used in 2 embodiment of the present invention of table
The design parameter index ginseng of hydrogen used is shown in Table 3；
The design parameter achievement data of hydrogen used in 3 embodiment of the present invention of table
| Project | Unit | Con trolling index |
| Purity | % | > 99.99 |
| Oxygen content | ppm | < 10 |
| CO+CO2 | ppm | < 10 |
| Water content | ppm | < 5 |
The properties for the third fourth acrylic resin copolymer being prepared are tested, as a result ginseng is shown in Table 4；
The properties data for the third fourth acrylic resin copolymer that 4 embodiment of the present invention of table is prepared
Examples 1 to 7
According to mass percent shown in table 5 match, by the third fourth acrylic resin copolymer, antioxidant, halogen-absorber and
Light transmission agent is added in 15L high-speed stirring mixer, and under 20r/min revolving speed, then normal temperature and pressure mixing 5min~6min is used
Grand extruding granulator carries out melt blending extruding pelletization again for section, and each zone temperatures control obtains one between 200 DEG C~220 DEG C
Secondary property cutlery box polypropylene modified material.
Each material quality percentage proportion in 5 embodiment of the present invention 1~7 of table
The properties for the polypropylene modified material that the embodiment of the present invention 1~7 is prepared respectively are tested, as a result
Ginseng is shown in Table 6；
The properties data for the polypropylene modified material that 6 embodiment of the present invention 1~7 of table is prepared
As shown in Table 6, the yellow colour index for the polypropylene modified material that the embodiment of the present invention 1~7 is prepared meets primary
Property cutlery box material optical property requirement (translucency requirement), yellow colour index be -2.4~0.2, transparency with higher,
Make to be made cutlery box material with good transparent appearance；Simultaneously because not adding slipping agent, ash content is seldom in material, and ash content meets
The processing performance requirement of disposable lunch-box material；Also, the matrix resin of the polypropylene modified material is the third fourth copolymer polypropylene tree
Rouge replaces ethylene as comonomer using 1- butylene, and low molecule content is low, can be excessive to avoid n-hexane extract in product
The problem of, the quality that low molecular weight surfactant migrates and causes surface tension influence of fading cutlery box material is reduced, while avoiding disposably eating
Low-molecular material is precipitated in box material, meets the requirement of disposable lunch-box material, and control third fourth by adjusting density of hydrogen
There is acrylic resin copolymer good fluidity of molten to be avoided in process with enhancing the processing performance of matrix resin
The additives such as slipping agent are added, the low-molecular material reduced in disposable lunch-box material is precipitated；In addition, by polypropylene modified material
In component and each component content control, be both able to maintain certain rigidity, played a supporting role to disposable lunch-box material, and energy
The bending strength for improving product, enhances the mechanical property of product, especially shock resistance is improved, and meets disposable lunch-box
The mechanical property of material, and be conducive to disposable lunch-box material and use under cryogenic.
The above description of the disclosed embodiments, enables those skilled in the art to implement or use the present invention.It is right
A variety of modifications of these embodiments will be readily apparent to those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein
Widest scope.
Claims (10)
1. a kind of polypropylene modified material is prepared by the raw material for including following components:
Third fourth acrylic resin copolymer 99.6wt%~99.8wt%；
Antioxidant 0.1wt%~0.3wt%；
Light transmission agent 0.01wt%~0.03wt%；
Halogen-absorber 0.01wt%~0.1wt%.
2. polypropylene modified material according to claim 1, which is characterized in that the third fourth acrylic resin copolymer is by third
Random copolymerization forms in the presence of a catalyst and hydrogen for alkene and 1- butylene.
3. polypropylene modified material according to claim 2, which is characterized in that the catalyst is II type catalyst of DQ-；
The ratio between yield of the additional amount of the catalyst and the third fourth acrylic resin copolymer is 1g:(8kg~9kg).
4. polypropylene modified material according to claim 2, which is characterized in that the concentration of the hydrogen be 500ppm~
1000ppm。
5. polypropylene modified material according to claim 2, which is characterized in that the temperature of the random copolymerization be 60 DEG C~
70 DEG C, pressure is 2.5MPa~3.5MPa.
6. polypropylene modified material according to claim 1, which is characterized in that the antioxidant is selected from phenolic antioxidant
And/or phosphite ester antioxidant.
7. polypropylene modified material according to claim 1, which is characterized in that the light transmission agent be selected from NA-21 and/or
TMP-6。
8. polypropylene modified material according to claim 1, which is characterized in that the halogen-absorber is selected from zinc stearate
And/or hydrotalcite.
9. a kind of preparation method of polypropylene modified material according to any one of claims 1 to 8, comprising the following steps:
A) the third fourth acrylic resin copolymer, antioxidant, light transmission agent and halogen-absorber are mixed, carries out extruding pelletization, is gathered
Propylene modified material.
10. preparation method according to claim 9, which is characterized in that the temperature of extruding pelletization described in step a) is 160
DEG C~240 DEG C.
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| CN102453282A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
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| CN107417836A (en) * | 2017-04-13 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of clear acrylic of low n-hexane dissolution |
-
2019
- 2019-08-20 CN CN201910768128.5A patent/CN110437541A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453282A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| CN103087418A (en) * | 2011-10-29 | 2013-05-08 | 中国石油化工股份有限公司 | Food packaging container and its making method |
| CN104479228A (en) * | 2014-11-20 | 2015-04-01 | 中国石油化工股份有限公司 | Aluminum-plated propylene and butylene co-polypropylene tape casting membrane material and preparation method thereof |
| CN107099097A (en) * | 2017-04-13 | 2017-08-29 | 中国石油化工股份有限公司 | A kind of COPP biaxially oriented film material and its industrial process |
| CN107163403A (en) * | 2017-04-13 | 2017-09-15 | 中国石油化工股份有限公司 | A kind of preparation method of the clear acrylic of low n-hexane dissolution |
| CN107417836A (en) * | 2017-04-13 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of clear acrylic of low n-hexane dissolution |
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