CN109438834A - A kind of polypropylene casting membrane material and preparation method thereof - Google Patents
A kind of polypropylene casting membrane material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/13—Phenols; Phenolates
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
The purpose of the present invention is to provide a kind of polypropylene casting membrane materials and preparation method thereof, which has high melt flow rate (MFR), and can effectively improve the stiffness, tensile strength and heat resistance of casting films, are suitble to the application demand of the casting films of multiple performance demand.The present invention discloses a kind of polypropylene casting membrane material, includes following components: acrylic resin powder: 89.9~99.76 parts, antioxidant 1010: 0.05~0.2 part, auxiliary antioxidant U626:0.03~0.1 part, halogen-absorber: 0.01~0.1 part, slipping agent A:0.05~0.2 part, slipping agent B:0.05~0.2 part, opening agent: 0.05~0.3 part, degradation agent: 0.005~0.2 part.
Description
Technical field
The present invention relates to high-molecular compound preparation field, in particular to a kind of polypropylene casting membrane material and its preparation side
Method.
Background technique
Polypropylene film can be divided into polypropylene casting film, polypropylene blown film and two-way by preparation method, performance and different purposes
Three kinds of stretched polypropene film.Polypropylene casting film (CPP film) is a kind of tensionless winkler foundation, non-that quenching production is cast by melt
The cast film of orientation.Compared with inflation film, its main feature is that speed of production is fast, yield is high, thin-film transparent, glossiness, thickness
Excellent uniformity is spent, also there is good heat sealability, oil resistivity, boiling resistance, resistance to scraping and package packing machine applicability are good, simultaneously
Due to being cast film, subsequent handling such as prints, is compound extremely convenient, thus be widely used in textile, fresh flower, food,
The packaging of daily necessities, while also being used as Tropical cooking film, compound film inner layer heat-sealable material and metallization basement membrane etc..
The production of CPP has single layer curtain coating and multi-layer co-extruded curtain coating two ways.Monolayer cast films major requirement material is low
It warms sealing property and stiffness is good.Multi-layer co-extruded casting films can be divided into hot sealing layer, supporting layer, three layers of corona layer, in the selection of material
On it is wide compared with monofilm, can individually select the material for meeting every aspect requirement, assign film different function and purposes.
Although kind is relatively single currently, the yield of domestic CPP PP Pipe Compound is high, it is mainly used for composite film heat sealing, and
Half boiling film, aluminizer, Tropical cooking film the CPP trade mark more lack, depend on import material.
Domestic CPP PP Pipe Compound on the market generally uses copolymer polypropylene as base-material now, and melt flow rate (MFR) is general
For 6.5~7.5g/10min, curtain coating property is restricted.If improving the melt flow rate (MFR) or choosing of base-material by general means
The higher polypropylene of melt flow rate (MFR) is selected as base-material, then the intensity of polymer will be affected.For ordinary circumstance, with
The raising of melt flow rate (MFR), the tensile strength of polymer, tearing strength, stress cracking resistance, heat resistance, weatherability, punching
Hit intensity and shrinking percentage can all decline therewith, thus in the presence of the possibility for leading to not meet CPP film performance requirement.
Therefore, it is necessary to research and develop a kind of CPP PP Pipe Compound, while possessing high melt flow rate (MFR), mechanical property needs full
The requirement of the various CPP films of foot.
Summary of the invention
Based on above-mentioned technical problem, the purpose of the present invention is to provide a kind of polypropylene casting membrane material and its preparation sides
Method, which has high melt flow rate (MFR), and can effectively improve the stiffness, tensile strength and heat resistance of casting films, is suitble to more
The application demand of the casting films of kind performance requirement.
The invention is realized by the following technical scheme:
A kind of polypropylene casting membrane material includes following components:
Acrylic resin powder: 89.9~99.76 parts, antioxidant 1010: 0.05~0.2 part, auxiliary antioxidant U626:0.03~
0.1 part, halogen-absorber: 0.01~0.1 part, slipping agent A:0.05~0.2 part, slipping agent B:0.05~0.2 part, opening agent:
0.05~0.3 part, degradation agent: 0.005~0.2 part.
The acrylic resin powder is homopolypropylene, and melt flow rate (MFR) is 5~10g/10min.
The melt flow rate (MFR) of the polypropylene casting membrane material be 10~15g/10min, tensile yield strength be 34~
40MPa.High melt flow rate (MFR) can guarantee curtain coating when making film layer, improve the quality of production efficiency and film forming.
The antioxidant 1010 is the bis- tertiary butyl -4- hydroxycyclohexans of 3-(3,5-) propionic ester；The auxiliary antioxidant
U626 is bis- (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites.
Preferably, the halogen-absorber is calcium stearate.
Preferably, the slipping agent A is erucyl amide, and the slipping agent B is oleamide.
Preferably, the opening agent is silica.
Preferably, the degradation agent is 3,6,9- triethyl groups -3,6,9- trimethyl-Isosorbide-5-Nitrae, tri- peroxide nonane of 7-.Peroxidating
Peroxide bridge in object molecule is heated to be extremely easy in decomposition as Active Radicals Produced and oxygen, and the modification of polymer is facilitated.
A kind of preparation method of polypropylene casting membrane material comprising the steps of:
(1) propylene is under the collective effect of major catalyst, co-catalyst and external electron donor, using hydrogen as molecular-weight adjusting
Agent, the density of hydrogen that control enters reactor is 500~2000ppm, and it is 5~10g/10min that melt flow rate (MFR), which is prepared,
Acrylic resin powder；
(2) acrylic resin powder made from step (1) is uniformly mixed by formula as below:
Acrylic resin powder: 89.9~99.76 parts, antioxidant 1010: 0.05~0.2 part, auxiliary antioxidant U626:0.03~
0.1 part, halogen-absorber: 0.01~0.1 part, slipping agent A:0.05~0.2 part, slipping agent B:0.05~0.2 part, opening agent:
0.05~0.3 part, degradation agent: 0.005~0.2 part；
(3) solution flow rate is prepared through extruder extrusion in the mixture of step (2) after evenly mixing is 10~15g/
10min polypropylene casting membrane material.
Preferably, the density of hydrogen that control enters reactor in the step (1) is 500~1300ppm.It is dense through the hydrogen
Degree is lower to adjust acrylic resin powder made from molecular weight with more excellent solution flow rate and regularity.
The present invention uses Sphripol polymerization technique, by adjusting the additional amount of hydrogen in the course of the polymerization process to an ideal
Numerical value, control material melt flow rate (MFR) be prepared melt flow rate (MFR) be 5~10g/10min acrylic resin powder
Material.Acrylic resin powder is mixed with degradation agent and other auxiliary agents, further obtains melt flow rate (MFR) after extruder squeezes out
For the polypropylene casting membrane material of 10~15g/10min.
Compared with the prior art, the invention has the following beneficial effects:
1. the base-material of polypropylene casting membrane material of the present invention is, work is polymerize by common Sphripol in the prior art
On the basis of skill, the additional amount for adjusting hydrogen obtains the homopolypropylene resin powder with high melt flow rate (MFR), and homopolymerization is poly-
Propylene helps to improve the stiffness and high temperature resistance of film；
2. being squeezed out through extruder after the present invention mixes acrylic resin powder with degradation agent and other auxiliary agents, obtaining melt flow
The polypropylene casting membrane material that dynamic rate is 10~15g/10min, tensile yield strength is 34~40MPa has high melt flow
While dynamic rate improvement is cast into film property, there is high tensile yield strength, the intensity after ensure that film forming；
3. in the prior art, with the polypropylene casting membrane material of melt flow rate (MFR) suitable with the present invention, tensile yield strength
Generally only 25~32MPa, and tensile yield strength can reach the polypropylene casting membrane material of 34~40MPa, melt flows speed
For rate generally between 8~9g/10min, the present invention all has excellent property in terms of melt flow rate (MFR) and tensile yield strength
Can, adapt to the performance requirement of the casting films of various different applications.
Specific embodiment
Below by way of specific embodiment, the present invention will be further elaborated:
Halogen-absorber described in the embodiment of the present invention and comparative example is calcium stearate, and the slipping agent A is erucyl amide,
The slipping agent B is oleamide, and the opening agent is silica, and the degradation agent is 3,6,9- triethyl group -3,
Three peroxide nonane of 6,9- trimethyl -1,4,7-.
Polypropylene casting membrane material described in the embodiment of the present invention is prepared by following preparation method:
(1) propylene is under the collective effect of major catalyst, co-catalyst and external electron donor, using hydrogen as molecular-weight adjusting
Agent, the density of hydrogen that control enters reactor is 500~2000ppm, and it is 5~10g/10min that melt flow rate (MFR), which is prepared,
Acrylic resin powder；
(2) acrylic resin powder made from step (1) is uniformly mixed by formula as below:
Acrylic resin powder: 89.9~99.76 parts, antioxidant 1010: 0.05~0.2 part, auxiliary antioxidant U626:0.03~
0.1 part, halogen-absorber: 0.01~0.1 part, slipping agent A:0.05~0.2 part, slipping agent B:0.05~0.2 part, opening agent:
0.05~0.3 part, degradation agent: 0.005~0.2 part；
(3) solution flow rate is prepared through extruder extrusion in the mixture of step (2) after evenly mixing is 10~15g/
10min polypropylene casting membrane material.
Embodiment 1
In Sphripol polymerisation process, the density of hydrogen that control enters reactor is 800ppm, and melt flows speed is made
Rate is the acrylic resin powder of 5.5g/10min.
Specific formula in step (2) is as follows: acrylic resin powder: 99.38 parts, antioxidant 1010: 0.1 part, auxiliary
U626:0.06 parts of antioxidant, halogen-absorber: 0.04 part, A:0.15 parts of slipping agent, B:0.06 parts of slipping agent, opening agent: 0.2
Part, degradation agent: 0.01 part；
It is 12.5g/10min polypropylene casting membrane material, property that solution flow rate, which is prepared, through extruder extrusion in step (3)
It can test and be shown in Table -2.
Embodiment 2
In Sphripol polymerisation process, the density of hydrogen that control enters reactor is 1000ppm, and melt flows speed is made
Rate is the acrylic resin powder of 6.7g/10min.
Specific formula in step (2) is as follows: acrylic resin powder: 99.26 parts, antioxidant 1010: 0.1 part, auxiliary
U626:0.08 parts of antioxidant, halogen-absorber: 0.05 part, A:0.12 parts of slipping agent, B:0.1 parts of slipping agent, opening agent: 0.2
Part, degradation agent: 0.009 part；
It is 13.2g/10min polypropylene casting membrane material, property that solution flow rate, which is prepared, through extruder extrusion in step (3)
It can test and be shown in Table -2.
Embodiment 3
In Sphripol polymerisation process, the density of hydrogen that control enters reactor is 1300ppm, and melt flows speed is made
Rate is the acrylic resin powder of 8.2g/10min.
Specific formula in step (2) is as follows: acrylic resin powder: 99.27 parts, antioxidant 1010: 0.1 part, auxiliary
U626:0.08 parts of antioxidant, halogen-absorber: 0.05 part, A:0.12 parts of slipping agent, B:0.12 parts of slipping agent, opening agent: 0.18
Part, degradation agent: 0.008 part；
It is 13.4g/10min polypropylene casting membrane material, property that solution flow rate, which is prepared, through extruder extrusion in step (3)
It can test and be shown in Table -2.
Embodiment 4
In Sphripol polymerisation process, the density of hydrogen that control enters reactor is 500ppm, and melt flows speed is made
Rate is the acrylic resin powder of 5g/10min.
Specific formula in step (2) is as follows: acrylic resin powder: 93.73 parts, antioxidant 1010: 0.2 part, auxiliary
U626:0.04 parts of antioxidant, halogen-absorber: 0.07 part, A:0.08 parts of slipping agent, B:0.16 parts of slipping agent, opening agent: 0.25
Part, degradation agent: 0.005 part；
It is 10.1g/10min polypropylene casting membrane material, property that solution flow rate, which is prepared, through extruder extrusion in step (3)
It can test and be shown in Table -2.
Embodiment 5
In Sphripol polymerisation process, the density of hydrogen that control enters reactor is 1800ppm, and melt flows speed is made
Rate is the acrylic resin powder of 9.3g/10min.
Specific formula in step (2) is as follows: acrylic resin powder: 95.81 parts, antioxidant 1010: 0.05 part, auxiliary
U626:0.03 parts of antioxidant, halogen-absorber: 0.08 part, A:0.05 parts of slipping agent, B:0.05 parts of slipping agent, opening agent: 0.08
Part, degradation agent: 0.07 part；
It is 14.1g/10min polypropylene casting membrane material, property that solution flow rate, which is prepared, through extruder extrusion in step (3)
It can test and be shown in Table -2.
Embodiment 6
In Sphripol polymerisation process, the density of hydrogen that control enters reactor is 2000ppm, and melt flows speed is made
Rate is the acrylic resin powder of 10g/10min.
Specific formula in step (2) is as follows: acrylic resin powder: 99.76 parts, antioxidant 1010: 0.15 part, auxiliary
U626:0.1 parts of antioxidant, halogen-absorber: 0.1 part, A:0.2 parts of slipping agent, B:0.2 parts of slipping agent, opening agent: 0.3 part, drop
Solution agent: 0.2 part；
It is 15g/10min polypropylene casting membrane material, performance that solution flow rate, which is prepared, through extruder extrusion in step (3)
Test is shown in Table -2.
Embodiment 7
In Sphripol polymerisation process, the density of hydrogen that control enters reactor is 1500ppm, and melt flows speed is made
Rate is the acrylic resin powder of 8.9g/10min.
Specific formula in step (2) is as follows: acrylic resin powder: 89.9 parts, antioxidant 1010: 0.08 part, auxiliary
U626:0.05 parts of antioxidant, halogen-absorber: 0.01 part, A:0.1 parts of slipping agent, B:0.07 parts of slipping agent, opening agent: 0.05
Part, degradation agent: 0.1 part；
It is 13.6g/10min polypropylene casting membrane material, property that solution flow rate, which is prepared, through extruder extrusion in step (3)
It can test and be shown in Table -2.
Comparative example 1
Comparative example 1 is casting films base resin F800ET common in the market, and polymer type is random copolymerization polymer, melt
Flow rate is 8.0g/10min, and the performance test results are shown in Table -2.
Comparative example 2
Comparative example 2 is casting films base resin F850EA common in the market, and polymer type is homopolymer polymer, melt flows
Rate is 8.5g/10min, and the performance test results are shown in Table -2.
The formula of the various embodiments described above and comparative example indicates in table -1.
Table -1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Polymer type | Homopolymerization | Homopolymerization | Homopolymerization | Homopolymerization | Homopolymerization | Homopolymerization | Homopolymerization |
| Powder melt flow rate (MFR) g/10min | 5.5 | 6.7 | 8.2 | 5 | 9.3 | 10 | 8.9 |
| Acrylic resin powder/part | 99.38 | 99.26 | 99.27 | 93.73 | 95.81 | 99.76 | 89.9 |
| Antioxidant 1010/part | 0.1 | 0.1 | 0.1 | 0.2 | 0.05 | 0.15 | 0.08 |
| U626/ parts of auxiliary antioxidant | 0.06 | 0.08 | 0.08 | 0.04 | 0.03 | 0.1 | 0.05 |
| Halogen-absorber/part | 0.04 | 0.05 | 0.05 | 0.07 | 0.08 | 0.1 | 0.01 |
| A/ parts of slipping agent | 0.15 | 0.12 | 0.12 | 0.08 | 0.05 | 0.2 | 0.1 |
| B/ parts of slipping agent | 0.06 | 0.1 | 0.12 | 0.16 | 0.05 | 0.2 | 0.07 |
| Opening agent/part | 0.2 | 0.2 | 0.18 | 0.25 | 0.08 | 0.3 | 0.05 |
| Degradation agent/part | 12.5 | 13.2 | 13.4 | 10.1 | 14.1 | 15 | 13.6 |
The various embodiments described above and the preparation-obtained material properties test result of comparative example are as shown in following table -2:
Table -2
The melt flow rate (MFR) that can be seen that polypropylene casting membrane material of the present invention from the test result of table -2 is much larger than
Common polypropylene casting film resin in the market, and there is excellent melt flow rate (MFR), improve polypropylene in the prior art
The defect that curtain coating membrane material can not get both in this two performances.It should be pointed out that the above-mentioned specific embodiment of the present invention is only
It is to further explanation of the invention rather than limits.For those skilled in the art, this is not being departed from
Under the premise of inventive principle, several improvements and modifications can also be made, these improvements and modifications also should be regarded as protection of the invention
Range.
Claims (7)
1. a kind of polypropylene casting membrane material includes following components:
Acrylic resin powder: 89.9~99.76 parts, antioxidant 1010: 0.05~0.2 part, auxiliary antioxidant U626:0.03~
0.1 part, halogen-absorber: 0.01~0.1 part, slipping agent A:0.05~0.2 part, slipping agent B:0.05~0.2 part, opening agent:
0.05~0.3 part, degradation agent: 0.005~0.2 part；
The acrylic resin powder is homopolypropylene, and melt flow rate (MFR) is 5~10g/10min；
The melt flow rate (MFR) of the polypropylene casting membrane material be 10~15g/10min, tensile yield strength be 34~
40MPa。
2. polypropylene casting membrane material according to claim 1, which is characterized in that the halogen-absorber is stearic acid
Calcium.
3. polypropylene casting membrane material according to claim 1, which is characterized in that the slipping agent A is erucyl amide, institute
Stating slipping agent B is oleamide.
4. polypropylene casting membrane material according to claim 1, which is characterized in that the opening agent is silica.
5. polypropylene casting membrane material according to claim 1, which is characterized in that the degradation agent is 3,6,9- tri- second
Three peroxide nonane of base -3,6,9- trimethyl -1,4,7-.
6. a kind of preparation method of polypropylene casting membrane material, which is characterized in that comprise the steps of:
(1) propylene is under the collective effect of major catalyst, co-catalyst and external electron donor, using hydrogen as molecular-weight adjusting
Agent, the density of hydrogen that control enters reactor is 500~2000ppm, and it is 5~10g/10min that melt flow rate (MFR), which is prepared,
Acrylic resin powder；
(2) acrylic resin powder made from step (1) is uniformly mixed by formula as below:
Acrylic resin powder: 89.9~99.76 parts, antioxidant 1010: 0.05~0.2 part, auxiliary antioxidant U626:0.03~
0.1 part, halogen-absorber: 0.01~0.1 part, slipping agent A:0.05~0.2 part, slipping agent B:0.05~0.2 part, opening agent:
0.05~0.3 part, degradation agent: 0.005~0.2 part；
(3) solution flow rate is prepared through extruder extrusion in the mixture of step (2) after evenly mixing is 10~15g/
10min polypropylene casting membrane material.
7. the preparation method of polypropylene casting membrane material according to claim 6, which is characterized in that in the step (1)
The density of hydrogen that control enters reactor is 500~1300ppm.
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