CN102276912B - Polypropylene composition for low foaming and preparation process thereof - Google Patents
Polypropylene composition for low foaming and preparation process thereof Download PDFInfo
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- CN102276912B CN102276912B CN 201110191232 CN201110191232A CN102276912B CN 102276912 B CN102276912 B CN 102276912B CN 201110191232 CN201110191232 CN 201110191232 CN 201110191232 A CN201110191232 A CN 201110191232A CN 102276912 B CN102276912 B CN 102276912B
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Abstract
The invention discloses a polypropylene composition for low foaming and a preparation process thereof. According to the invention, polypropylene is used as a matrix material for the composition, an anti-oxidant system comprises a hindered phenol anti-oxidant and a phosphite anti-oxidant, powdered steatite or calcium carbonate is used as a nucleating agent, and monoglyceride is used as an activator. The polypropylene composition for low foaming prepared in the invention has molecular weight distribution in the range of 3.0 to 12.0, a melt flow rate in the range of 0.1 to 5.0 g/10 min and melt tensile strength in the range of 10 cN to 20 cN, and has the characteristics of a simple and stable preparation process, good processing properties and the like; extruded low range foamed plate and sheet products of the composition have a density of 300 to 700 kg/m<3>; the process of foaming is stable; the obtained products have the characteristics of a closed pore structure, fine and uniform foamed pores, etc.
Description
Technical field
The present invention relates to a kind of low foaming polypropylene composition and preparation method thereof, said composition is applicable to the manufacturing of low range polypropylene extrusion foaming sheet material, sheet material, and foaming product intensity and impact property are remarkable, can be used for the industries such as food product pack, automobile, building.
Background technology
General purpose polypropylene material expandability is relatively poor, and viscosity and the temperature range of its suitable foaming are narrower.Therefore, be to improve expandable energy and the processing stability of polypropylene material, should select to have the polypropylene material of higher melt tensile stress and wider molecular weight distribution, and add other stablizers, to adapt to polypropylene expanded requirement.Polypropylene foam material is determined the difference of its performance by the difference of its expansion ratio, be applicable to different Application Areass.
Provide a kind of polypropylene foaming premix and preparation method thereof in Chinese patent CN1765976, related to polypropylene foam material.It is that 3.5～6.5wt%, molecular weight distribution are that 3.0～9.0 atactic copolymerized polypropene and melt flow rate (MFR) are that 1～4g/10min, melt tensile stress are that the polypropylene of 30cN～60cN is matrix resin that ethylene content is adopted in this invention, and organic chemistry whipping agent melt blending obtains foaming premix.The foam material that this Preblend obtains after foaming by routine, its expansion ratio can reach 7～12 times, and its foam density is 75～129Kg/m
3But the not mentioned 300～700kg/m of this patent
3Low foaming product and foaming material performance feature, 300～700kg/m
3Low foaming product has the mechanical properties such as better rigidity and shock strength than the high-foaming goods, be specially adapted to the fields such as automobile, motorcycle, packing, building.
Document " " development of Polypropylene High Density Foamed Sheet " " (plastics industry, 2004.03), disclose and adopted common forcing machine, take blending the plain polypropylene (PP) of the high melt strength, propylene of massfraction as 10%～15% be raw material, add chemical foaming agent, nucleator to produce Polypropylene High Density Foamed Sheet; And studied the impact on the foam sheet performance of composition of raw materials, whipping agent kind and processing mode.When the high melt strength, propylene massfraction is 10%～15%, and the foam sheet over-all properties that the PP that has added 10% ethylene/octene (POE) produces is better, when the whipping agent addition is 2%～3%, it is 650～750kg/m that common single screw extrusion machine can be used for production density
3Polypropylene High Density Foamed Sheet.Mention the ethylene/octene that needs interpolation 10% in the document, increase material cost, and affect the rigidity of material, and the foam sheet density range is at 650～750kg/m
3, energy-conservation not obvious with weight loss effect to goods.
Summary of the invention
The purpose of this invention is to provide a kind of polypropene composition that is applicable to the low range foaming, when said composition was used for extrusion foaming sheet material, sheet material, the extrudate density scope was at 300～700kg/m
3, the abscess pore diameter range is fine and closely woven evenly at 100um～500um, aperture, and foaming product intensity and impact property are remarkable, can be applicable to the fields such as automobile, packing, building, realize the effect of the energy-conservation and environmental protection of loss of weight.
Polypropene composition disclosed by the invention is that molecular weight distribution is 3.0～12.0, be preferably 6.0～10, more preferably 7.0～9.0, melt mass flow rate (melting index) scope is at 0.1～5.0g/10min, be preferably 0.3～3.0g/10min, 0.5～2.0g/10min more preferably, melt tensile stress scope is at 10cN～20cN, be preferably 12cN～16cN, 13cN～15cN more preferably, comprise the foaming improvement systems such as a certain proportion of nucleator and promoting agent, and the simple preparation method of this kind composition and technique are provided.
prepare polypropylene board at the interpolation chemical foaming agent, the sheet material extrusion and foaming process, the molecular weight distribution width of polypropylene material, melt flow rate (MFR), the melt tensile stress is the principal element of extruding processing characteristics and foaming effect impact, the polypropylene that the present invention adopts is the homopolymer of propylene, the multipolymer of propylene and ethene, polypropylene and poly mixture, the mixture of polypropylene and polyethylene and ethylene-propylene copolymer, polyacrylic chemical modification product, suitable molecular weight Tile Width and melt flow rate (MFR) guarantee Drawing abillity, suitable melt expansion force guarantees growth and the typing of foaming process bubble.Add antioxidant systems, can make goods have long term thermal oxidative stability and forming process stability; Add the nucleator system, liquid-solid, the liquid-vapor interface that the gentle body of nucleator and melt forms can be used as the catalyzer of bubble nucleating, reduce the activation energy of bubble nucleating, bring out heterogeneous nucleation, produce a large amount of nuclei of bubbles, cell density, abscess-size and cell size distribution tool are had a significant impact; Add the promoting agent system, can make whipping agent be easy to be evenly distributed in polymer melt, play all bubble and steady effect of steeping, play simultaneously anti-contraction.
The present invention is take molecular weight distribution as 3.0～12.0, the melt flow rate (MFR) scope is at 0.1～5.0g/10min, melt tensile stress scope is body material at the polypropylene of 10cN～20cN, antioxidant systems is comprised of Hinered phenols antioxidant and phosphite ester kind antioxidant, talcum powder or calcium carbonate etc. are as nucleator, and mono-glycerides etc. are as promoting agent.Adopt azo-compound, nitroso compound, triazo-compound, carbonate, supercarbonate and/or nitrite etc. as whipping agent when being used for extruding the low range foaming.
Mainly comprise in foaming polypropylene composition of the present invention: 100 parts of molecular weight distribution are 3.0～12.0, melt mass flow rate (melting index) scope is at 0.1～5.0g/10min, and melt tensile stress scope is at polypropylene (A), 0.2～2.0 part of oxidation inhibitor (B), 1～5 portion of nucleator (C) and 5～10 portions of promoting agents (D) of 10cN～20cN.
A is selected from mixture and/or the polyacrylic chemical modification product of multipolymer, polypropylene and poly mixture, polypropylene and polyethylene and the ethylene-propylene copolymer of homopolymer, propylene and the ethene of propylene.
The B antioxidant systems is comprised of Hinered phenols antioxidant and phosphite antioxidant, and the ratio of Hinered phenols antioxidant and phosphite antioxidant is 1:0.5～5.Hindered phenol antioxygen is selected from four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, (2,4,6 trioxy--1,3,5-triazine-1,3-5(2H, 4H, 6H)-three bases) trivinyl [three-(3,5-di-tert-butyl-hydroxy phenyl)] CALCIUM ACRYLATE.Phosphite antioxidant is selected from three (2,4-di-t-butyl) phenyl-phosphite, tetramethylolmethane diphosphite two (2.4-di-tert-butyl phenyl) ester.
The C nucleator can be selected from talcum powder, calcium carbonate, calcium stearate, Zinic stearas, aluminum oxide, calcium hydroxide, aluminium hydroxide and/or Sodium Benzoate.
The D promoting agent is single 18 (alkane) sour glycerine ester.
The present invention also provides the preparation method of above-mentioned composition:
Method 1: with above-mentioned composition melting mixing in two roller Banbury mixeies, extruding pelletization.Processing temperature: 160 ℃-230 ℃.
Method 2: join twin screw extruder melting mixing, extruding pelletization after above-mentioned composition is mixed in homogenizer.Extrusion temperature: 170 ℃-240 ℃, screw speed: 150-300rpm.
The present invention also provides the preparation method of foam sheet sample: utilize the Screw Extrusion sheet material machine, adopt AC whipping agent (Cellmic C 121), directly extrusion foaming obtains the foaming polypropylene sheet sample.
Beneficial effect of the present invention:
The present composition has the characteristics such as preparation technology's simple and stable, processing characteristics be good, composition extrude low range foaming product density at 300～700kg/m
3Controlled, have the tiny characteristics such as evenly of unicellular structure, abscess-size.Polypropylene low range foam sheet has the characteristics such as good comprehensive mechanical property, good heat resistance, the easy recovery of environmental protection, can substitute the low foaming product of polyethylene, polystyrene of present use.
Embodiment
Embodiment 1:
100 parts of Co-polypropylene;
0.1 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester;
0.1 part of three (2,4-di-t-butyl) phenyl-phosphite;
1.0 parts of talcum powder;
5.0 parts of single 18 (alkane) sour glycerine esters.
Embodiment 2:
100 parts of Co-polypropylene;
0.5 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester;
0.5 part of three (2,4-di-t-butyl) phenyl-phosphite;
2.0 parts of talcum powder;
8.0 parts of single 18 (alkane) sour glycerine esters.
Embodiment 3:
100 parts of homo-polypropylene;
1.0 parts of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters;
1.0 parts of three (2,4-di-t-butyl) phenyl-phosphites;
5.0 parts of talcum powder;
10.0 parts of single 18 (alkane) sour glycerine esters.
Embodiment 4:
100 parts of homo-polypropylene;
0.2 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester;
0.2 part of three (2,4-di-t-butyl) phenyl-phosphite;
2.0 parts of talcum powder;
7.0 parts of single 18 (alkane) sour glycerine esters.
Embodiment 5:
100 parts of Co-polypropylene;
0.2 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester;
0.2 part of three (2,4-di-t-butyl) phenyl-phosphite;
5.0 parts of talcum powder;
5.0 parts of single 18 (alkane) sour glycerine esters.
Embodiment 6:
100 parts of homo-polypropylene;
0.2 part of four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester;
0.2 part of three (2,4-di-t-butyl) phenyl-phosphite;
5.0 parts of talcum powder;
7.0 parts of single 18 (alkane) sour glycerine esters.
Table 1, embodiment performance
Indicate: in table 1, " ASTM D6474 " is U.S. material standard " high temperature gel permeation chromatography is measured the method for molecular polyolefin weight distribution and average molecular wt ".
The melt strength testing method: capillary rheometer, temperature: 200 ℃, velocity of plunger: 10mm/min, mouthful mould size: diameter 2mm, long 10mm, melt tensile stress when measuring melt traction tension fracture under constant acceleration.
The foaming product abscess-size is measured take electromicroscopic photograph as foundation.
Claims (11)
1. one kind is used for the low polypropene composition that foams, and it is characterized in that comprising following component and weight proportion:
A. body material is 100 parts
B. oxidation inhibitor is 0.2～2.0 part
C. nucleator is 1～5 part
D. promoting agent is 5～10 parts
Wherein oxidation inhibitor is comprised of Hinered phenols antioxidant and phosphite antioxidant, and the weight ratio of Hinered phenols antioxidant and phosphite antioxidant is 1:0.5～5;
Component A body material is selected from: the multipolymer of homopolymer polypropylene, propylene and ethene, polypropylene and poly mixture, polypropylene and polyethylene and with mixture or the polyacrylic chemical modification product of ethylene-propylene copolymer;
Component A molecular weight distribution is 3.0～12.0; The melt flow rate (MFR) scope is at 0.1～5.0g/10min; The Rupture Stress scope is at 10cN～20cN;
Promoting agent is single 18 (alkane) sour glycerine ester.
2. polypropene composition according to claim 1, it is characterized in that: component A molecular weight distribution is 6.0～10, and the melt flow rate (MFR) scope is at 0.3～3.0g/10min, and the Rupture Stress scope is at 12cN～16cN.
3. polypropene composition according to claim 2, it is characterized in that: component A molecular weight distribution is 7.0～9.0, and the melt flow rate (MFR) scope is at 0.5～2.0g/10min, and the Rupture Stress scope is at 13cN～15cN.
4. according to claim 1-3 described polypropene compositions of any one, is characterized in that hindered phenol antioxygen is selected from four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
5. according to claim 1-3 described polypropene compositions of any one, is characterized in that phosphite antioxidant is selected from three (2,4-di-t-butyl) phenyl-phosphites or tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
6. polypropene composition according to claim 4, is characterized in that phosphite antioxidant is selected from three (2,4-di-t-butyl) phenyl-phosphites or tetramethylolmethane diphosphite two (2,4-di-tert-butyl phenyl) ester.
7. polypropene composition according to claim 5, is characterized in that nucleator is selected from: talcum powder, calcium carbonate, calcium stearate, Zinic stearas, aluminum oxide, calcium hydroxide, aluminium hydroxide or Sodium Benzoate.
8. the preparation method of the polypropene composition for low foaming as described in claim 1-7 any one, with described component melting mixing in two roller Banbury mixeies, extruding pelletization, processing temperature: 160 ℃-230 ℃.
9. the preparation method of the polypropene composition for low foaming as described in claim 1-7 any one, after being mixed, described component joins the twin screw extruder melting mixing in homogenizer, extruding pelletization, extrusion temperature: 170 ℃-240 ℃, screw speed: 150-300rpm.
10. an employing such as the described polypropene composition of claim 1-7 any one prepare the method for foaming polypropylene sheet, utilize the Screw Extrusion sheet material machine, adopt whipping agent, and directly extrusion foaming obtains the foaming polypropylene sheet sample.
11. a foaming polypropylene sheet that adopts the described method preparation of claim 10, density range is at 300～700kg/m
3, the abscess pore diameter range is fine and closely woven evenly in 100um～500um, aperture.
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| CN 201110191232 CN102276912B (en) | 2011-07-08 | 2011-07-08 | Polypropylene composition for low foaming and preparation process thereof |
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| CN103289412B (en) * | 2013-05-22 | 2017-06-16 | 易宝（福建）高分子材料股份公司 | Silicon rubber closed cell foamed material and preparation method thereof |
| CN103739906A (en) * | 2013-11-25 | 2014-04-23 | 吴江市董鑫塑料包装厂 | Barricade separation pile plastic |
| CN105175856B (en) * | 2015-08-28 | 2018-06-29 | 河南胜华电缆集团有限公司 | Regenerated polyolefin halogen-free flame-proof environmental protection foamed plastic and its production method |
| CN106751083A (en) * | 2016-12-06 | 2017-05-31 | 佛山市高明区生产力促进中心 | A kind of heat-insulated polystyrene |
| CN107286475B (en) * | 2017-08-03 | 2021-02-19 | 天津市大林新材料科技股份有限公司 | Polypropylene foam material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611539A (en) * | 2003-10-30 | 2005-05-04 | 中国石油化工股份有限公司 | Foamed poly propylene material and its preparing method |
| CN102115561A (en) * | 2009-12-30 | 2011-07-06 | 李晓丽 | Physical foaming polypropylene sheet material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611539A (en) * | 2003-10-30 | 2005-05-04 | 中国石油化工股份有限公司 | Foamed poly propylene material and its preparing method |
| CN102115561A (en) * | 2009-12-30 | 2011-07-06 | 李晓丽 | Physical foaming polypropylene sheet material |
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