CN102108150A - High-gloss high-rigidity polypropylene compound material and preparation method thereof - Google Patents
High-gloss high-rigidity polypropylene compound material and preparation method thereof Download PDFInfo
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- CN102108150A CN102108150A CN 200910200854 CN200910200854A CN102108150A CN 102108150 A CN102108150 A CN 102108150A CN 200910200854 CN200910200854 CN 200910200854 CN 200910200854 A CN200910200854 A CN 200910200854A CN 102108150 A CN102108150 A CN 102108150A
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Abstract
The invention discloses a high-gloss high-rigidity polypropylene compound material which comprises the following components by weight percent: 69-96% of polypropylene, 0-20% of inorganic filling material subjected to surface treatment with a coupling agent, 3-10% of high density polyethylene, 0.1-1% of antioxidant and 0-1% of other auxiliary agents. The invention has the following advantages: 1, the surface treatment is carried out on the inorganic filling material, and a proper amount of the high density polyethylene is used in a compound material system, so that the prepared polypropylene compound material has high gloss; 2, the prepared polypropylene compound material has high rigidity while the high gloss of the material is ensured; and 3, the method for improving the high gloss of the polypropylene compound material is simple in process and low in production cost.
Description
Technical field
The present invention relates to a kind of high gloss, high rigid polypropylene matrix material and preparation method thereof, belong to polymer modification and processing technique field.
Background technology
Polypropylene (PP) has good processing properties and physics, mechanics, chemical property because of it, and light weight, inexpensive is a kind of widely used general-purpose plastics simultaneously.Thereby be widely used in fields such as automotive industry, household electrical appliance, electronic instrument.
Utilizing the Inorganic Fillers Filled polypropylene to obtain the modified polypropylene material of low-cost and high-performance, is one of effective, the most most economical approach that obtains in the high performance polymer matrix material.People adopt mineral-filled method to improve rigidity, thermotolerance and the dimensional stability of polypropylene material usually.But when using mineral filled polypropylene, the surface gloss of polypropylene material also can significantly reduce along with the increase of mineral-filled amount.Therefore will be cost to sacrifice polypropylene material surface luster with the inorganic materials filled modified polypropylene.And application such as household appliances shell have higher requirements to the surface gloss of material.At this problem, people attempt adopting the whole bag of tricks to solve.Application number 00117199 discloses a kind of household electrical appliances with the ageing-resistant polypropylene material of high gloss, and this method promotes crystalling propylene by nucleator, yet along with the progress of polypropylene synthesis technique, high-crystallinity polypropylene is better than the use nucleator on crystal property; The Chinese patent of application number 200610027888.3 has also been announced the shock-resistant filled modified polypropylene of a kind of high gloss and method for making and application, it mainly is the toughness that improves material by polyolefin elastomer, but also makes the glossiness of material and rigidity all be subjected to certain influence like this.Also there is high gloss PP to adopt in addition and in homopolymerization PP, adds the glossiness that barium sulfate improves modified polypropene.Japanese Patent JP58171423 adopts ethylene-propylene rubber(EPR) and filler barium sulfate, and the material modified surface gloss that makes is 82 (60 ° of angular measurements).
Summary of the invention
The objective of the invention is in order to provide a kind of high gloss, high inflexible modified polypropylene material to form and preparation method thereof.By the glossiness of surface treatment mineral filler and interpolation high density polyethylene(HDPE) raising polypropylene composite material, material has favorable rigidity and dimensional stability simultaneously.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of high gloss, high rigid polypropylene matrix material, by weight percentage, its composition and proportioning:
Polypropylene 69～96
The mineral filler 0～20 that coupling agent is surface-treated
High density polyethylene(HDPE) 3～10
Oxidation inhibitor 0.1～1
Other auxiliary agents 0～1.
In the polypropylene composite material system that the present invention was suitable for:
Described polypropylene be degree of crystallinity more than 70%, degree of isotacticity is greater than 99% homo-polypropylene, its melt flow rate (MFR) is 2～60g/10min (test condition: 230 ℃ * 2.16kg).
In the surface-treated mineral filler of described coupling agent, coupling agent is 0.05～2 weight percent.Preferred 1% coupling agent treatment mineral filler.
In the surface-treated mineral filler of described coupling agent, mineral filler is lime carbonate, barium sulfate or their composition, and its particle size range is 1～10 micron.
Described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant can select for use hindered phenol or thioesters kind antioxidant as 3114,1010, DSTP wherein one or more; Auxiliary anti-oxidant can select for use the phosphorite kind antioxidant as 618,168 etc.
High density polyethylene(HDPE) density of the present invention is 0.941～0.960g/cm
3, melting index is 2～15g/10min, molecular weight is between 40000～300000.
Other auxiliary agents of the present invention are pigment toners.
The preparation method of above-mentioned high gloss, high rigid polypropylene matrix material is as follows:
(1) takes by weighing raw material by weight ratio;
(2) the premix 10min in high-speed mixer with mineral filler and a certain amount of coupling agent makes the surface-treated mineral filler.
(3) polypropylene, surface treated mineral filler, high density polyethylene(HDPE), oxidation inhibitor and other additives were done in super mixer mixed 5～15 minutes;
(4) raw materials mixed is placed dual-screw-stem machine, through melt extruding, granulation, its technology is: 190～200 ℃ in a district, 200～210 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18Mpa.
The present invention has carried out surface treatment and has added certain high density polyethylene(HDPE) mineral filler in the basic components of polypropylene composite material, prepares high gloss, high inflexible polypropylene composite material.
Advantage of the present invention is:
1, the present invention carries out surface treatment to mineral filler, and uses an amount of high density polyethylene(HDPE) in composite system, makes polypropylene compound material prepared have high gloss.
2, polypropylene compound material prepared of the present invention is when guaranteeing the material high gloss, and material has high rigidity.
3, the method preparation technology of the raising polypropylene composite material glossiness of the present invention's proposition is simple, production cost is low.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and Comparative Examples composite-material formula, polypropylene is the homo-polypropylene of Shanghai petrochemical iy produced, and commodity are called M1200HS.Described barium sulfate is that jump particle diameter that the river produces is 5 microns a barium sulfate.Described high density polyethylene(HDPE) is the HDPE 5070 of Panjin ethylene production.Described coupling agent is the titanate coupling agent NDZ-101 that NanJing Shuguang Chemical Group Co., Ltd. produces.Described primary antioxidant is the DSTP that Britain ICE company produces, and trade names are Negonox DSTP, and chemical name is the thio-2 acid octadecyl ester, and Ciba company produce 3114, trade names are Irganox 3114, and chemical name is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid.Auxiliary anti-oxidant is 168 of Ciba company product, and trade names are Irgafos 168, and chemical name is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Comprise black toner in addition.
The premix 10min in high-speed mixer with an amount of mineral filler and coupling agent, make the surface-treated mineral filler, acrylic resin, surface treated mineral filler, high density polyethylene(HDPE), oxidation inhibitor and other additives were done in super mixer mixed 3～5 minutes, again in twin screw extruder through melt extruding, granulation, its technology is: 190～200 ℃ in a district, 200～210 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The whole extrusion residence time is 1～2 minute, and pressure is 12～18Mpa.
Performance evaluation mode and implementation standard:
With the particulate material for preparing as stated above, drying is 2～3 hours in 90～100 ℃ convection oven, and then the particulate material that drying is good carries out the injection molding sample preparation on injection moulding machine.
Glossiness test: try with 60 ° of angular measurements of vancometer by standard GB8807.
Melt flow rate (MFR) (MFR) is measured: undertaken by the ISO1183 standard, probe temperature is 230 ℃, load 2.16kg;
The tensile property test: undertaken by ISO 527-2 standard, specimen size is 170 * 10 * 4mm, and draw speed is 50mm/min;
The bending property test: undertaken by ISO 178 standards, specimen size is 80 * 10 * 4mm, and rate of bending is 2mm/min, and span is 64mm, and modulus in flexure is undertaken by tangential direction;
The simple beam impact strength test: undertaken by ISO 179 standards, specimen size is 80 * 6 * 4mm, and notch depth is 1/3rd of a sample thickness;
Comprehensive mechanical performance is passed judgment on by the numerical value of notched Izod impact strength, tensile strength, flexural strength and the modulus in flexure of test gained.
Example formulations and every The performance test results be each table as follows:
Table 1 embodiment 1-5 and Comparative Examples 1-4 material prescription table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |
| M1200HS, weight % | 86.4 | 84.4 | 79.4 | 89.4 | 69.4 | 79.4 | 86.4 | 79.4 | 69.4 |
| Through 1% coupling agent surface-treated barium sulfate, weight % | 10 | 10 | 10 | - | 20 | - | - | - | - |
| Through 0.5% coupling agent surface-treated barium sulfate, weight % | - | - | - | - | - | 10 | - | - | - |
| Not surface treated barium sulfate, weight % | - | - | - | - | - | - | 10 | 10 | 20 |
| High density polyethylene(HDPE), weight % | 3 | 5 | 10 | 10 | 10 | 10 | 3 | 10 | 10 |
| 3114, weight % | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| 168, weight % | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| DSTP, weight % | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Black toner, weight % | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
The test result of each prescription is as follows:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |
| Melting index (g/10min) | 12.5 | 11.7 | 10.8 | 12.2 | 11.5 | 12.8 | 13.1 | 11.7 | 12.4 |
| Density (g/cm 3) | 0.982 | 0.984 | 0.985 | 0.908 | 1.062 | 0.986 | 0.980 | 0.986 | 1.063 |
| Notched Izod impact strength (kJ/m 2) | 4.6 | 5.1 | 5.7 | 5.5 | 4.3 | 5.4 | 4.2 | 4.7 | 4.0 |
| Tensile strength | 32.2 | 31.4 | 30.7 | 31.2 | 32.1 | 30.9 | 31.6 | 31.0 | 32.8 |
| (MPa) | |||||||||
| Modulus in flexure (MPa) | 1754 | 1710 | 1687 | 1722 | 1780 | 1714 | 1775 | 1744 | 1810 |
| 60 ° of glossiness | 64 | 66 | 69 | 72 | 64 | 65 | 51 | 60 | 59 |
From the contrast of the contrast of embodiment 1,2,3,4 and Comparative Examples 1,2,3 and embodiment 5 and Comparative Examples 4 as can be seen, through coupling agent surface treatment barium sulfate with after adding high density polyethylene(HDPE), the glossiness of PP matrix material all is significantly improved, and increase along with high density polyethylene(HDPE) consumption and coupling agent consumption, the glossiness of matrix material also improves gradually, and the basic physical and mechanical property of material also can keep well.
Claims (10)
1. a high gloss, high rigid polypropylene matrix material, it is characterized in that: by weight percentage, it is formed and proportioning is:
Polypropylene 69～96
The mineral filler 0～20 that coupling agent is surface-treated
High density polyethylene(HDPE) 3～10
Oxidation inhibitor 0.1～1
Other auxiliary agents 0～1.
2. a kind of high gloss according to claim 1, high rigid polypropylene matrix material is characterized in that: polypropylene be degree of crystallinity more than 70%, degree of isotacticity is greater than 99% homo-polypropylene, its melt flow rate (MFR) is 2～60g/10min.
3. a kind of high gloss according to claim 1, high rigid polypropylene matrix material is characterized in that: in the surface-treated mineral filler of described coupling agent, coupling agent is 0.05～2 weight percent.
4. a kind of high gloss according to claim 3, high rigid polypropylene matrix material is characterized in that: select 1% coupling agent treatment mineral filler for use.
5. a kind of high gloss according to claim 1, high rigid polypropylene matrix material, it is characterized in that: in the surface-treated mineral filler of described coupling agent, mineral filler is lime carbonate, barium sulfate or their composition, and its particle size range is 1～10 micron.
6. a kind of high gloss according to claim 1, high rigid polypropylene matrix material, it is characterized in that: described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant can be selected hindered phenol or thioesters kind antioxidant for use, and auxiliary anti-oxidant can be selected the phosphorite kind antioxidant for use.
7. a kind of high gloss according to claim 6, high rigid polypropylene matrix material is characterized in that: described primary antioxidant be 3114,1010 and DSTP wherein one or more; Auxiliary antioxidant is 618 and/or 168.
8. a kind of high gloss according to claim 1, high rigid polypropylene matrix material is characterized in that: high density polyethylene(HDPE) density of the present invention is 0.941～0.960g/cm
3, melting index is 2～15g/10min, molecular weight is between 40000～300000.
9. a kind of high gloss according to claim 1, high rigid polypropylene matrix material is characterized in that: other auxiliary agents are the pigment toner.
10. method for preparing the described matrix material of claim 1, its concrete steps are as follows:
(1) takes by weighing raw material by claim 1 weight proportion;
(2) the premix 10min in high-speed mixer with mineral filler and a certain amount of coupling agent makes the surface-treated mineral filler.
(3) polypropylene, surface treated mineral filler, high density polyethylene(HDPE), oxidation inhibitor and other additives were done in super mixer mixed 5～15 minutes;
(4) raw materials mixed is placed dual-screw-stem machine, through melt extruding, granulation, its technology is: 190～200 ℃ in a district, 200～210 ℃ in two districts, 210～220 ℃ in three districts, 205～215 ℃ in four districts; The residence time of whole extrusion is 1～2 minute, and pressure is 12～18Mpa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936372A (en) * | 2012-08-14 | 2013-02-20 | 深圳市科聚新材料有限公司 | Polypropylene composite material, preparation method and applications thereof |
| CN103073783A (en) * | 2011-10-25 | 2013-05-01 | 昆山博富新材料科技股份有限公司 | Polypropylene-high molecular weight high density polyethylene-filling material blend and preparation method thereof |
| CN107082960A (en) * | 2017-06-13 | 2017-08-22 | 陕西省石油化工研究设计院 | A kind of flame retardant type high-gloss polypropylene composite and preparation method thereof |
| CN109096669A (en) * | 2018-06-28 | 2018-12-28 | 太仓市晨洲塑业有限公司 | A kind of plastics for electric appliance mask |
-
2009
- 2009-12-25 CN CN 200910200854 patent/CN102108150A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073783A (en) * | 2011-10-25 | 2013-05-01 | 昆山博富新材料科技股份有限公司 | Polypropylene-high molecular weight high density polyethylene-filling material blend and preparation method thereof |
| CN103073783B (en) * | 2011-10-25 | 2016-04-06 | 昆山博富新材料科技股份有限公司 | Polypropylene-HMW (high molecular weight)-high density polyethylene-filler blends and preparation method thereof |
| CN102936372A (en) * | 2012-08-14 | 2013-02-20 | 深圳市科聚新材料有限公司 | Polypropylene composite material, preparation method and applications thereof |
| CN102936372B (en) * | 2012-08-14 | 2015-10-28 | 深圳市科聚新材料有限公司 | Polypropylene composite material, its preparation method and application |
| CN107082960A (en) * | 2017-06-13 | 2017-08-22 | 陕西省石油化工研究设计院 | A kind of flame retardant type high-gloss polypropylene composite and preparation method thereof |
| CN109096669A (en) * | 2018-06-28 | 2018-12-28 | 太仓市晨洲塑业有限公司 | A kind of plastics for electric appliance mask |
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Application publication date: 20110629 |