CN110423402A - Lower shrinkage High-impact Polypropylene and preparation method thereof - Google Patents
Lower shrinkage High-impact Polypropylene and preparation method thereof Download PDFInfo
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- CN110423402A CN110423402A CN201910565908.XA CN201910565908A CN110423402A CN 110423402 A CN110423402 A CN 110423402A CN 201910565908 A CN201910565908 A CN 201910565908A CN 110423402 A CN110423402 A CN 110423402A
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- 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
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- 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
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention belongs to technical field of polymer materials, it is related to a kind of lower shrinkage High-impact Polypropylene and preparation method thereof.It includes in parts by weight, by 60-87 parts of polypropylene, 20-36 parts of polymethyl methacrylate, 5-10 parts of expanding material, filling reinforcing agent 5-20 parts, 0.3-1 parts of lubricant, 0.01-0.5 parts of optothermal stabilizer form.The present invention reduces polyacrylic shrinking percentage using the cheap polymethyl methacrylate of density low price, and expanding material directly selects to prepare according to raw material, without separately adding elastomer or preparing monomer, is simple and efficient the compatibility for improving blend.
Description
Technical field
The invention belongs to technical field of polymer materials, it is related to a kind of lower shrinkage High-impact Polypropylene and its system
Preparation Method.
Background technique
Polypropylene is as most light general-purpose plastics, and density is small, cost performance is high.Excellent heat resistance, chemical-resistant resistance are rotten
Corrosion and it is easy to form processing and recycling characteristic, make polypropylene material become the most commonly used plastic material of purposes it
One.But PP material shrinkage is big, poor dimensional stability is easy to produce buckling deformation；Shock resistance is poor；Light aging resisting property
Difference.So the modification of polypropylene material has become the big hot spot of technical field of polymer materials one.Such as Chinese patent
[CN201110252092.9] discloses a kind of Low-shrinkage polypropylene composition and preparation method thereof, and the low-shrinkage is poly-
Propylene compositions are made of the raw material of following mass fraction: acrylic resin 35~87；Inorganic particle 10~30；Metallocene linear
Low density polyethylene (LDPE) 2~35；Toughener 1~5 and weather-proof auxiliary agent 0.05~0.3.The patent can be effectively reduced to be produced using the resin
The usage amount of inorganic filler is added when product, however the acrylic resin that uses of the patent is the mixing of two kinds of impact copolymer polypropylenes
Object and metallocene linear-low density polyethylene and elastomer, raw material restriction is more, and price is higher, and preparation method is to reaction
Device and extruder operating system high operation requirements, it is difficult to large-scale promotion application.Chinese invention patent application
[CN201610425703.8] discloses a kind of low-shrinkage modified polypropylene material, mainly by polypropylene, polystyrene and more
Kind maleic anhydride grafted polymer melt blending is made.The invention reduces the contraction of polypropylene material by the way that polystyrene is added
Rate influences the stability of product secondary operation, and polystyrene price more poly- third but the compatibility between polystyrene is poor
Alkene is high, entire polypropylene material higher cost.
Summary of the invention
Regarding the issue above, the present invention provides a kind of lower shrinkage High-impact Polypropylene.
It is another object of the present invention in view of the above-mentioned problems, providing a kind of preparation side of lower shrinkage High-impact Polypropylene
Method.
In order to achieve the above objectives, present invention employs following technical proposals:
A kind of lower shrinkage High-impact Polypropylene, which is characterized in that in parts by weight, be made of following raw material:
The polypropylene is that isotactic index is not less than 96%, and melt flow rate (MFR) is not less than the isotactic poly- third of 7g/min
Alkene.
In above-mentioned lower shrinkage High-impact Polypropylene, the expanding material is PMMA-g-AA or PMMA-g-GMA.
In above-mentioned lower shrinkage High-impact Polypropylene, the PMMA-g-AA is 100-120:8- by weight ratio
Polymethyl methacrylate, acrylic acid and the initiator triphenylphosphine composition of 15:1-1.2.
In above-mentioned lower shrinkage High-impact Polypropylene, the PMMA-g-GMA is 3-5:2-3 by weight ratio:
Polymethyl methacrylate, glycidyl methacrylate and the initiator azodiisobutyronitrile composition of 0.06-0.1.
In above-mentioned lower shrinkage High-impact Polypropylene, the expanding material preparation step is as follows:
A, prepare above-mentioned raw materials by the parts by weight of constitutive material, polymethyl methacrylate is done under the conditions of 80-90 DEG C
It is 3-5 hours dry,
B, remaining remaining ingredient addition high-speed mixer and mixing in addition to initiator is uniform, mixture is added by major ingredient mouth
Enter in double screw extruder and melt, is 190~200 DEG C in melting temperature, under the conditions of screw speed is 30-40r/min, will cause
Agent is at the uniform velocity added twin-screw extrude from side material mouth, after melting mixing, extruding pelletization to get arrive the expanding material.
In above-mentioned lower shrinkage High-impact Polypropylene, described fills reinforcing agent by the mineral of 10-60 parts by weight
Matter additive and the modification short glass fiber of 5-40 parts by weight composition.
In above-mentioned lower shrinkage High-impact Polypropylene, the mineral additive be calcium carbonate, talcum powder or
One of glass microballoon is a variety of, and the modification short glass fiber is the alkali-free short glass fiber by size modification.
In above-mentioned lower shrinkage High-impact Polypropylene, the polymethyl methacrylate includes being not more than 30%
The polymethyl methacrylate reworked material of mass fraction.
In above-mentioned lower shrinkage High-impact Polypropylene, the optothermal stabilizer be heat stabilizer, antioxidant and
One of ultraviolet absorbing agent is a variety of, the lubricant be paraffin, stearic amide, methylene bis stearic amide, N,
One of N- ethylene bis stearic acid amide and silicone oil are a variety of.
A kind of preparation method of lower shrinkage High-impact Polypropylene, includes the following steps, A, the weight by constitutive material
Part prepares above-mentioned raw materials, and polypropylene is 2-3 hours dry under the conditions of 70~80 DEG C, by polymethyl methacrylate in 80-90
It is 3-5 hours dry under the conditions of DEG C,
B, expanding material is prepared, reinforcing agent is filled in preparation,
C, the other components in addition to polymethyl methacrylate are added, into high mixer with 900~1000rpm high-speed stirred
8~12min is uniformly mixed,
D, above-mentioned mixture is added, is added in double screw extruder by main feed opening and carries out melt blending, double
Screw extruder revolving speed is 210~480r/min, and melting temperature passes through side feed hopper at the uniform velocity to double under the conditions of being 180~250 DEG C
Polymethyl methacrylate melting refining altogether is added in screw extruder, extruding pelletization is to get the lower shrinkage high impact resistance polypropylene
Material.
Compared with prior art, the present invention has the advantages that
1, the present invention reduces polyacrylic shrinking percentage, expanding material using the cheap polymethyl methacrylate of density low price
It directly selects to prepare according to raw material, without separately adding elastomer or preparing monomer, is simple and efficient the compatibility for improving blend.
2, the present invention reduces polypropylene material shrinking percentage by mineral additive and modified glass collaboration, improves simultaneously
Polypropylene material erosion-resisting characteristics, and additive amount is greatly decreased compared with prior art ratio, it is ensured that polypropylene material when in use light
Quantization.
3, lower shrinkage High-impact Polypropylene produced by the present invention, due to the high glaze of polymethyl methacrylate and resistance to
It scrapes, more existing low-shrink polypropylene quality is more preferable, and application range is wider.
4, cost of material of the invention is low, can also utilize Resource recovery, while preparation method is simple, the synthesis of product at
This is lower, is conducive to large-scale production operation.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention
Fig. 1 is the process flow chart of one of a specific embodiment of the invention；
Fig. 2 is two process flow chart of a specific embodiment of the invention；
In figure: raw material preparation 1, polymethyl methacrylate drying 2, polypropylene drying 3, compatilizer preparation 4, filling enhancing
Agent prepares 5, mixing 6, melt blending 7, extruding pelletization 8, polymethyl methacrylate mixing 9.
Specific embodiment
Reagent and instrument as used in the following examples, are commercially available.Quantitative data in following embodiment, is respectively provided with three
Secondary to repeat to test, results are averaged.
In following embodiment,
PP-1, the permanent big PPH-XD-045 in Heze, melt flow rate (MFR) 7.5g/min, isotactic index are close not less than 96%
Degree is not more than 0.4g/m3；
PP-2, the permanent big PPH-XD-300 in Heze, melt flow rate (MFR) 26g/min, isotactic index are not less than 97%, density
No more than 0.46g/m3；
PMMA, Zhangjiagang China auspicious 304, melt flow rate (MFR) 2g/min, density 1.18g/m3, molding shrinkage is little
In 0.5, ball indentation hardness is not less than 130N/mm2, light transmittance is greater than 91；
PMMA reworked material, the rich outstanding plastics in Yuyao, melt flow rate (MFR) 1.5g/min, density 1.16g/m3, molding receipts
Shrinkage is not more than 0.5, and ball indentation hardness is not less than 120N/mm2, light transmittance is greater than 91；
Acrylic acid, triphenylphosphine and azodiisobutyronitrile, Solution on Chemical Reagents in Shanghai factory；
Glycidyl methacrylate, Suzhou Chemical Co., Ltd., South Airways；
PMMA-g-AA-1, self-control, polymethyl methacrylate, acrylic acid and triphenylphosphine weight ratio are 100:8:1；
PMMA-g-AA-2, self-control, polymethyl methacrylate, acrylic acid and triphenylphosphine weight ratio are 120:15:1.2；
PMMA-g-GMA-1, self-control, methyl methacrylate, glycidyl methacrylate and azodiisobutyronitrile weight
Amount compares 3:2:0.06；
PMMA-g-GMA-2, self-control, methyl methacrylate, glycidyl methacrylate and azodiisobutyronitrile weight
Amount compares 5:3:0.1；
Alkali-free short glass fiber, megalith glass 306A；
Size is self-control, and raw material forms parts by weight: coupling agent KH55000.4, polyurethane finishing agent 7,0.1 and of ammonium chloride
Methyl stearate 0.06；
Calcium carbonate, talcum powder and the glass microballoon of mineral additive need to be nanoscale master batch, and need to be carried out with coupling agent
It is activated, embodiment selects the transparent master batch of nanometer calcium carbonate, and Yuyao speeds to create SZ5428；
The modification short glass fiber and mineral additive for filling reinforcing agent can be formed according to 0.5-3:1-3.Embodiment filling
Reinforcing agent selects modified short glass fiber and the transparent master batch of mineral additive nanometer calcium carbonate to form by weight 3:2；
Lubricant selects stearic amide, methylene bis stearic amide and N, N- ethylene bis stearic acid amide by weight 1:
1:1 composition；
Heat stabilizer in optothermal stabilizer can be calcium-zinc composite stabilizing agent；Antioxidant can be antioxidant 1076, resist
One or more of oxygen agent 2246 and antioxidant DSTP；Ultraviolet absorbing agent can be benzophenone class ultraviolet absorbing agent, benzene
And at least one of imidazoles ultraviolet absorbing agent and triazine-based ultraviolet absorbent；
Embodiment optothermal stabilizer selects calcium-zinc composite stabilizing agent and benzophenone class ultraviolet absorbing agent by weight 2:3 group
At.
Embodiment 1-5
The component proportion of embodiment 1-5 is shown in Table 1.
1 embodiment 1-5 of table and comparative example 1-2 component proportion
As shown in connection with fig. 1, steps are as follows for the preparation method of embodiment 1-5:
A, raw material preparation 1 is to prepare above-mentioned raw materials by the parts by weight of constitutive material；Polymethyl methacrylate dry 2 will
Polymethyl methacrylate is 3-5 hours dry under the conditions of 80-90 DEG C；Polypropylene dry 3 is i.e. by polypropylene in 70~80 DEG C of items
It is 2-3 hours dry under part；
B, compatilizer preparation 4 is i.e. uniform by raw material mixed at high speed according to the ratio, on the twin screw extruder extruding pelletization,
In, melting temperature is 190~200 DEG C, screw speed 30-40r/min, and extrusion temperature is no more than 190 DEG C；The reinforcing agent system of filling
Standby 5, alkali-free short glass fiber is passed through into size modification, mineral additive is activated with silane coupling agent, then will
Modified short glass fiber and mineral additive are uniformly mixed the preparation for completing filling reinforcing agent；
C, mixing 6: the other components in addition to polymethyl methacrylate are added, into high mixer with 900~1000rpm high
Speed 8~12min of stirring, is uniformly mixed；
D, melt blending 7: above-mentioned mixture is added, and is added in double screw extruder and is melted by main feed opening
It is blended, is 210~480r/min in double screw extruder revolving speed, melting temperature passes through side feed hopper under the conditions of being 180~250 DEG C
Polymethyl methacrylate melting refining altogether is added at the uniform velocity into double screw extruder, extruding pelletization 8 is to get the lower shrinkage highly resistance
Rush polypropylene material.
Embodiment 6-10
The component proportion of embodiment 6-10 is shown in Table 2.
2 embodiment 6-10 of table and comparative example 3-4 component proportion
A, raw material preparation 1 is to prepare above-mentioned raw materials by the parts by weight of constitutive material；Polymethyl methacrylate mixing 9, i.e.,
By polymethyl methacrylate reworked material and polymethyl methacrylate in the revolving speed of 1000~1200r/min in high mixer
3~5min of lower stirring is uniformly mixed；Polymethyl methacrylate dry 2 is i.e. by polymethyl methacrylate mixture in 80-90
It is 3-5 hours dry under the conditions of DEG C；Polypropylene dry 3 is i.e. 2-3 hours dry under the conditions of 70~80 DEG C by polypropylene；
B, compatilizer preparation 4 is i.e. uniform by raw material mixed at high speed according to the ratio, on the twin screw extruder extruding pelletization,
In, melting temperature is 190~200 DEG C, screw speed 30-40r/min, and extrusion temperature is no more than 190 DEG C；The reinforcing agent system of filling
Standby 5, alkali-free short glass fiber is passed through into size modification, mineral additive is activated with silane coupling agent, then will
Modified short glass fiber and mineral additive stir 3~5min, mixing in high mixer under the revolving speed of 800~1000r/min
Uniformly, it is uniformly mixed the preparation for completing filling reinforcing agent；
C, mixing 6: the other components in addition to polymethyl methacrylate are added, into high mixer with 900~1000rpm high
Speed 8~12min of stirring, is uniformly mixed；
D, melt blending 7: above-mentioned mixture is added, and is added in double screw extruder and is melted by main feed opening
It is blended, is 210~480r/min in double screw extruder revolving speed, melting temperature passes through side feed hopper under the conditions of being 180~250 DEG C
Polymethyl methacrylate melting refining altogether is added at the uniform velocity into double screw extruder, extruding pelletization 8 is to get the lower shrinkage highly resistance
Rush polypropylene material.
Comparative example 1-2
The component proportion of comparative example 1-2 is shown in Table 1.
The preparation method is the same as that of Example 1-5 by comparative example 1-2.
Comparative example 3-4
The component proportion of comparative example 3-4 is shown in Table 2.
The preparation method of comparative example 3-4 is the same as embodiment 6-10.
Test case
Embodiment 1-10 and comparative example the 1-4 polypropylene material being prepared are molded by injection molding machine, prepare test sample,
It is tested for the property；
Testing standard is as follows:
Density: it is tested according to ISO 1183；
Melt flow rate (MFR): testing according to ISO 1183, and experimental condition is 230 DEG C, 2.16kg；
Shrinking percentage: it is tested according to ISO 294-4；
Hardness: it is tested according to ISO 868；
Tensile strength: it is tested according to ISO 527-2；
Bending modulus: it is tested according to ISO 178；
IZOD notch impact strength is tested according to ISO 180, and experimental condition is 0 DEG C；
IZOD notch impact strength is tested according to ISO 180, and experimental condition is 23 DEG C；
Heat distortion temperature is tested according to ISO75-2/A, test-strips peace and quiet 1.80MPa.
Embodiment 1-5 and comparative example 1-2 test performance the results are shown in Table 3.
3 embodiment 1-5 of table and comparative example 1-2 test performance result
As shown in Table 3, embodiment 1-5 shrinking percentage is respectively less than 0.9%, even uses polypropylene material prepared by the present invention,
Finished size formed after injection molding is almost consistent with desired size.The properties of embodiment 1-5 are still more excellent simultaneously, simultaneously
Density is also maintained at compared with low water-mark.Obviously it can be seen that the difference of expanding material and embodiment, comparative example 1-2 properties are bright
It is aobvious to be lower than embodiment 1-5.
Embodiment 6-10 and comparative example 3-4 test performance the results are shown in Table 4.
4 embodiment 6-10 of table and comparative example 3-4 test performance result
As shown in Table 4, embodiment 6-10 shrinking percentage is still maintained at the level less than 1%, i.e., the present invention is regenerated using PMMA
Material can still prepare low-shrink polypropylene material.Embodiment 6-10 properties and embodiment 1-5 are compared simultaneously, and difference is little,
It is still maintained at high levels.Due to the difference of expanding material and embodiment, the properties of comparative example 3-4 are significantly lower than embodiment 6-
10。
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. a kind of lower shrinkage High-impact Polypropylene, which is characterized in that in parts by weight, be made of following raw material:
The polypropylene is that isotactic index is not less than 96%, and melt flow rate (MFR) is not less than the isotactic polypropylene of 7g/min.
2. lower shrinkage High-impact Polypropylene according to claim 1, which is characterized in that the expanding material is
PMMA-g-AA or PMMA-g-GMA.
3. lower shrinkage High-impact Polypropylene according to claim 2, which is characterized in that the PMMA-g-AA by
Polymethyl methacrylate, acrylic acid and initiator the triphenylphosphine composition that weight ratio is 100-120:8-15:1-1.2.
4. lower shrinkage High-impact Polypropylene according to claim 2, which is characterized in that the PMMA-g-GMA by
Weight ratio is polymethyl methacrylate, glycidyl methacrylate and the initiator azo two of 3-5:2-3:0.06-0.1
Isobutyronitrile composition.
5. the lower shrinkage High-impact Polypropylene according to any one of claim 3-4, which is characterized in that the increasing
It is as follows to hold agent preparation step:
A, prepare above-mentioned raw materials by the parts by weight of constitutive material, polymethyl methacrylate is dried into 3-5 under the conditions of 80-90 DEG C
Hour,
B, remaining remaining ingredient addition high-speed mixer and mixing in addition to initiator is uniform, mixture is double by the addition of major ingredient mouth
Melted in screw extruder, melting temperature be 190~200 DEG C, screw speed be 30-40r/min under the conditions of, by initiator from
Side material mouth at the uniform velocity adds twin-screw extrude, after melting mixing, extruding pelletization to get arrive the expanding material.
6. lower shrinkage High-impact Polypropylene according to claim 1, which is characterized in that the filling reinforcing agent by
The mineral additive of 10-60 parts by weight and the modification short glass fiber composition of 5-40 parts by weight.
7. lower shrinkage High-impact Polypropylene according to claim 6, which is characterized in that the mineral additive
For one of calcium carbonate, talcum powder or glass microballoon or a variety of, the modification short glass fiber is by size modification
Alkali-free short glass fiber.
8. lower shrinkage High-impact Polypropylene according to claim 1, which is characterized in that the polymethylacrylic acid
Methyl esters includes the polymethyl methacrylate reworked material no more than 30% mass fraction.
9. lower shrinkage High-impact Polypropylene according to claim 1, which is characterized in that the optothermal stabilizer is
One of heat stabilizer, antioxidant and ultraviolet absorbing agent are a variety of, and the lubricant is paraffin, stearic amide, first
Support double stearic amides, N, one of N- ethylene bis stearic acid amide and silicone oil or a variety of.
10. a kind of preparation method of lower shrinkage High-impact Polypropylene, which is characterized in that include the following steps,
A, prepare above-mentioned raw materials by the parts by weight of constitutive material, polypropylene is 2-3 hours dry under the conditions of 70~80 DEG C, it will gather
Methyl methacrylate is 3-5 hours dry under the conditions of 80-90 DEG C,
B, expanding material is prepared, reinforcing agent is filled in preparation,
C, other components in addition to polymethyl methacrylate are added into high mixer, with 900~1000rpm high-speed stirred 8~
12min is uniformly mixed,
D, above-mentioned mixture is added, is added in double screw extruder by main feed opening and carries out melt blending, in twin-screw
Extruder revolving speed is 210~480r/min, and melting temperature passes through side feed hopper at the uniform velocity to twin-screw under the conditions of being 180~250 DEG C
Polymethyl methacrylate melting refining altogether is added in extruder, extruding pelletization is to get the lower shrinkage High-impact Polypropylene.
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Cited By (4)
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| CN111518338A (en) * | 2020-06-15 | 2020-08-11 | 南京市天祥塑胶有限公司 | Polypropylene resin composite material for household appliance shell |
| CN112778634A (en) * | 2020-12-29 | 2021-05-11 | 成都金发科技新材料有限公司 | Rigid-tough balance low-density polypropylene composite material and preparation method and application thereof |
| CN115094533A (en) * | 2022-08-26 | 2022-09-23 | 汕头市超越织造有限公司 | Nano-modified high-strength polypropylene fiber filament and preparation method and application thereof |
| WO2024032433A1 (en) * | 2022-08-11 | 2024-02-15 | 上海金发科技发展有限公司 | Low post-shrinkage polypropylene material and preparation method therefor |
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| CN111518338A (en) * | 2020-06-15 | 2020-08-11 | 南京市天祥塑胶有限公司 | Polypropylene resin composite material for household appliance shell |
| CN112778634A (en) * | 2020-12-29 | 2021-05-11 | 成都金发科技新材料有限公司 | Rigid-tough balance low-density polypropylene composite material and preparation method and application thereof |
| WO2024032433A1 (en) * | 2022-08-11 | 2024-02-15 | 上海金发科技发展有限公司 | Low post-shrinkage polypropylene material and preparation method therefor |
| CN115094533A (en) * | 2022-08-26 | 2022-09-23 | 汕头市超越织造有限公司 | Nano-modified high-strength polypropylene fiber filament and preparation method and application thereof |
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Application publication date: 20191108 |