CN102888050A - Reversible crosslinked polypropylene material and preparation method thereof - Google Patents
Reversible crosslinked polypropylene material and preparation method thereof Download PDFInfo
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- CN102888050A CN102888050A CN201210347032XA CN201210347032A CN102888050A CN 102888050 A CN102888050 A CN 102888050A CN 201210347032X A CN201210347032X A CN 201210347032XA CN 201210347032 A CN201210347032 A CN 201210347032A CN 102888050 A CN102888050 A CN 102888050A
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Abstract
The invention discloses a reversible crosslinked polypropylene material which is prepared from the following components by weight: 100 parts of polypropylene material, 0.1-1 part of peroxide, 0.1-1 part of sulphur, 0.01-1 part of accelerant, 0.01-1 part of potassium peroxodisulfate and 0.01-1 part of plant oil. According to the preparation method, the defects of complicated modified production process of polypropylene, high energy consumption and non-repeatability utilization of the prior art are overcome; and the polypropylene material disclosed by the invention has high melt strength and good machinability, and the toughness is greatly enhanced.
Description
Technical field
The present invention relates to polypropylene material of a kind of reversible crosslink and preparation method thereof, belong to technical field of polymer materials.
Technical background
Polypropylene is a kind of crystallinity mixture of compound with regular structure, low price, is easy to machine-shaping and high comprehensive performance, so purposes is very extensive.Polypropylene is except having above many merits, the some shortcomings part is also arranged, such as poor toughness (particularly notched Izod impact strength is low), hot strength and insufficient rigidity, easily produce buckling deformation etc., these deficiencies have limited it in the more particularly application in the engineering materials field of wide field.Polypropylene is carried out the high performance study on the modification, make it that some important performance index reaches or the requirement of approaches engineering plastics, thereby with polypropylene application extension some Application Areas to traditional engineering plastics, have important using value.
Meanwhile, along with the continuous increase of China's polypropylene product consumption and production amount, the annual waste and old polypropylene that produces is also more and more.At present, mainly be to burn and landfill to the treatment process of waste and old polypropylene.All there is larger shortcoming in two kinds of methods, and wherein, burning method is processed incinerator is had relatively high expectations, and the reactant of generation enters in the mud of burning ash, dust and wastewater treatment, consists of the pollution to water body and atmospheric environment.Landfill method is processed then because polypropylene is difficult to be degraded becomes permanent rubbish.Therefore, recycle waste and old polypropylene and become increasingly serious environment and social concern.
By the method for physics, chemical modification, add in the polypropylene all kinds of material modified be to obtain the low-cost and high-performance polypropylene and recycle polyacrylic effective way.The mineral fillers such as that the method for physically modified is included in is calcium carbonate filled in the macromolecule matrix, glass fibre prepare polymer composite, have obtained very ten-strike at aspects such as improving the intensity of macromolecular material, rigidity, heat-drawn wire and dimensional stability.But, at material in use and since matrix material be separated and polyacrylic chain rupture and degraded still can cause the decline of material property.
And be in recent years novel researchdevelopment direction as cross-linking modified in the chemical modification.The polymkeric substance of the line style in the plastics or slight branching is converted into the process of three-dimensional netted three dimensional structure, is called the crosslinked of plastics.Polyacrylicly crosslinkedly its morphological stability, creep resistant be can improve, intensity and thermotolerance and melt strength improved, reduction shaping cycle etc.Be divided into radiation crosslinking and chemically crosslinked from method is crosslinked, its key distinction is to cause that the formation mechanism in activity of cross-linking reaction source is different.Radiation crosslinking is to carry out under the effect of light or energetic ray, needs to use expensive equipment, and restricted again to the thickness of irradiation thing, therefore is difficult to realize in actual production with the radiation method crosslinked polypropylene.The polyacrylic chemically crosslinked of initial research adds a small amount of superoxide mostly in polypropylene, to causing polyacrylic chemically crosslinked.Owing to containing a large amount of tertiary carbon atoms on the polypropylene molecular chain, the crosslinked and degraded of macromolecular radical occurs simultaneously in cross-linking process, and often preponderates in low free radical density loss solution, is difficult to obtain satisfied cross-linking effect.Therefore, chemical crosslink technique must could carry out under the effect that crosslinking coagent is arranged effectively.Compare with plain polypropylene such as the crosslinked with silicane polypropylene, its thermotolerance has improved 30～50 ℃, tensile strength, rigidity significantly increase, shock strength has improved 1.5 times～5.0 times, creep resistant, oil-proofness, wear resistance and shrinking percentage are also improved greatly, it can be the same with organosilane crosslinked polyethylene, is widely used in the every field of industrial production and daily life, but have complex process, the power consumption shortcoming such as large.Make linking agent with triazo-compound, also can make polypropylene crosslinked.Be used for the crosslinked triazo-compound of polypropylene and mainly contain poly-sulfonyl azide and nitrine formate.But triazo-compound is unstable, explosive, brings difficulty to practical application, has therefore developed again and has carried out crosslinked with monomers such as divinylbenzenes to polypropylene.The cross-link bond of the generations such as divinylbenzene only is made of the stable hydrocarbon key, therefore have excellent thermotolerance, tensile strength, tear strength, elasticity and compressibility, at present the divinylbenzene crosslink technology successfully is applied to make sheet continuous P P foam, but also has the shortcomings such as complex process, power consumption are large.
The performance that above method by chemically crosslinked is improved polypropylene material has obtained certain achievement, but central complex manufacturing, the shortcoming that energy consumption is larger of also existing, and all do not relate to crosslinked reversibility, the recycling meeting of existing polypropylene material causes material property greatly to descend, if occur crosslinked be reversible, will greatly be conducive to the recycling of polypropylene material.
Technology contents
The invention provides polypropylene material of a kind of reversible crosslink and preparation method thereof, overcome that prior art polypropylene modification complex process, energy consumption are larger, the shortcoming of not reproducible utilization, and polypropylene material of the present invention has higher melt strength and better workability, and toughness significantly strengthens.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of polypropylene material of reversible crosslink is prepared from by following component: 100 parts of polypropylene materials, and superoxide 0.1-1 part, sulphur 0.1-1 part, promotor 0.01-1 part, Potassium Persulphate 0.01-1 part, vegetables oil 0.01-1 part, described mark is mass fraction.
The contriver finds, the adding of promotor has realized that the formation of large free radical and crosslinking reaction occur simultaneously, the life-span of large free radical is relevant with selected superoxide, the adding of Potassium Persulphate also helps to prolong the life-span of large free radical, and the adding of vegetables oil helps pulverous linking agent to be dispersed in the polypropylene granules better.
In order to prolong the life-span of large free radical, the decomposition temperature of described superoxide is higher than 100 ℃.
In order further to promote formation and the crosslinking reaction of large free radical to occur simultaneously, preferred, the activation temperature of described promotor is higher than 140 ℃.Further preferred, described promotor is the mixture of one or more any proportionings in tetramethyl-thiuram disulfide (TMTD), monothio tetra methylthiuram (TMTM) or the dibenzothiazyl disulfide (MBTS).
Contriver's discovery, the active rate that can improve sulphur is used in the mixing of above-mentioned multiple promotor.
In order to enhance product performance, described polypropylene material is that thermoplastics and polypropylene mass ratio are (0-3): 1 mixture.
In order further to enhance product performance, described polypropylene is the mixture of one or both any proportionings of isotactic homo-polypropylene or Co-polypropylene, and the monomer of described Co-polypropylene is propylene and ethene.
For performance and the scope of application of extended products, described thermoplastics is polyethylene.
In order to guarantee the active rate of sulphur, the mass ratio of described promotor and sulphur is (1: 4)～(1: 1).
The preparation method of the polypropylene material of above-mentioned reversible crosslink comprises the steps:
A, with 100 parts of polypropylene materials, superoxide 0.1-1 part, sulphur 0.1-1 part, promotor 0.01-1 part, Potassium Persulphate 0.01-1 part, mixing;
B, with steps A gained material and vegetables oil 0.01-1 part mixing;
C, with step B gained material melt extrudes, granulation obtains reversible crosslink polypropylene material;
Wherein, described mark is mass fraction.
In order to guarantee the performance of product, melt temperature is 150-210 ℃ among the above-mentioned steps C.
For the convenient quality that guarantees simultaneously product of producing, step C, with step B gained material through single screw extrusion machine melt extrudes, granulation obtains reversible crosslink polypropylene material, described single screw extrusion machine L/D=20, screw diameter is 25mm, screw speed is 60 rev/mins, and the blend time is 3 minutes, and district's temperature is 155 ℃, two district's temperature are 180 ℃, and three district's temperature are 200 ℃.
The contriver finds: in whole extrusion reaction process, superoxide causes polypropylene and produces large free radical, and the large free radical of formation couples together by sulphur becomes longer chain, and then forms a stable cross-linked network structure.Meanwhile, the effect of large free radical and the fracture that shear history can cause the part polymer segment, in the later stage of extrusion, crosslinking reaction and splitting of chain reaction finally reach balance, thereby form a stable crosslinking reaction degree.Therefore in this course, polyacrylic crosslinking reaction process is reversible, and the crosslinked polypropylene ene product of gained also can be again or repeatedly extruded processing.
The present invention has overcome that prior art polypropylene modification complex process, energy consumption are larger, the shortcoming of not reproducible utilization, performance was without obvious decline after the polypropylene material of gained of the present invention recycled and reused repeatedly, and polypropylene material of the present invention has higher melt strength and better workability, and toughness significantly strengthens.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Among following each embodiment, isotatic polypropylene (iPP) commodity are called SABIC Vestolen, and model is PP P9000-67404, and producer is husky uncle basis, available from dragon innovation (world) trade Co., Ltd; Dicumyl peroxide reaches chemical company limited available from Shanghai Fang Rui; Sulphur is available from Wuxi Huasheng Rubber Technical Co., Ltd., the trade mark: insoluble sulfur 6033; Accelerant disulfide tetra methylthiuram (TMTD), monothio tetra methylthiuram (TMTM), dibenzothiazyl disulfide (MBTS) are available from Huangyan, Zhejiang East Zhejiang province rubber ingredients company limited; Potassium Persulphate causes Chemical Industry Science Co., Ltd far away available from the Wujiang; Vegetables oil is available from the east of a river, Ningbo City Food Co., Ltd of Yongxin, kind: sweet oil; Low Density Polyethylene (LDPE) is available from the LDPE10803 of card front yard, Shanghai chemical industry company limited, and umber is mass fraction among each embodiment.
The test of socle girder notched Izod impact strength records shock strength and tests by the ISO180 standard.
Below each routine preparation method as follows:
A, with 100 parts of polypropylene materials, superoxide 0.1-1 part, sulphur 0.1-1 part, promotor 0.01-1 part, Potassium Persulphate 0.01-1 part, mixing;
B, with steps A gained material and vegetables oil 0.01-1 part mixing;
C, with step B gained material through single screw extrusion machine melt extrudes, granulation obtains reversible crosslink polypropylene material, described single screw extrusion machine L/D=20, screw diameter is 25mm, screw speed is 60 rev/mins, the blend time is 3 minutes, one district's temperature is 155 ℃, and two district's temperature are 180 ℃, and three district's temperature are 200 ℃; For the mass distribution that makes material is even, performance is more stable, extrudes twice of circulation.Described umber is mass fraction.
Used material, umber and performance see Table 1, embodiment 3,4 in each example, 5 intensity of recycling repeatedly see Table circulation in 2, two years, and the preparation method is with reference to the present invention during recycling.
Used material, umber and performance table in each example of table 1
Each embodiment of table 2 reuses the performance table
Claims (11)
1. the polypropylene material of a reversible crosslink is characterized in that: be prepared from by following component: 100 parts of polypropylene materials, superoxide 0.1-1 part, sulphur 0.1-1 part, promotor 0.01-1 part, Potassium Persulphate 0.01-1 part, vegetables oil 0.01-1 part, described mark are mass fraction.
2. the polypropylene material of reversible crosslink as claimed in claim 1, it is characterized in that: the decomposition temperature of described superoxide is higher than 100 ℃.
3. the polypropylene material of reversible crosslink as claimed in claim 1, it is characterized in that: the activation temperature of described promotor is higher than 140 ℃.
4. the polypropylene material of reversible crosslink as claimed in claim 3, it is characterized in that: described promotor is the mixture of one or more any proportionings in tetramethyl-thiuram disulfide, monothio tetra methylthiuram or the dibenzothiazyl disulfide.
5. such as the polypropylene material of the described reversible crosslink of claim 1 to 4 any one, it is characterized in that: described polypropylene material is that thermoplastics and polypropylene mass ratio are (0-3): 1 mixture.
6. the polypropylene material of reversible crosslink as claimed in claim 5, it is characterized in that: described polypropylene is the mixture of one or both any proportionings of isotactic homo-polypropylene or Co-polypropylene, the monomer of described Co-polypropylene is propylene and ethene.
7. the polypropylene material of reversible crosslink as claimed in claim 5, it is characterized in that: described thermoplastics is polyethylene.
8. such as the polypropylene material of the described reversible crosslink of claim 1 to 4 any one, it is characterized in that: the mass ratio of described promotor and sulphur is (1:4)～(1:1).
9. such as the preparation method of the polypropylene material of the described reversible crosslink of claim 1 to 8 any one, it is characterized in that: comprise the steps:
A, with 100 parts of polypropylene, superoxide 0.1-1 part, sulphur 0.1-1 part, promotor 0.01-1 part, Potassium Persulphate 0.01-1 part, mixing;
B, with steps A gained material and vegetables oil 0.01-1 part mixing;
C, with step B gained material melt extrudes, granulation obtains reversible crosslink polypropylene material.
10. method as claimed in claim 9, it is characterized in that: melt temperature is 150-210 ℃ among the step C.
11. such as claim 9 or 10 described methods, it is characterized in that: step C is through single screw extrusion machine melt extrudes, granulation obtains reversible crosslink polypropylene material with step B gained material, described single screw extrusion machine L/D=20, screw diameter is 25mm, screw speed is 60 rev/mins, and the blend time is 3 minutes, and district's temperature is 155 ℃, two district's temperature are 180 ℃, and three district's temperature are 200 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050261443A1 (en) * | 2001-04-22 | 2005-11-24 | Said Bouhelal | Article formed from cross-linking isotactic polymers in the presence of peroxide |
| US6987149B2 (en) * | 2001-04-22 | 2006-01-17 | Said Bouhelal | Isostatic polypropylene crosslinking in the presence of peroxide |
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- 2012-09-18 CN CN201210347032XA patent/CN102888050A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050261443A1 (en) * | 2001-04-22 | 2005-11-24 | Said Bouhelal | Article formed from cross-linking isotactic polymers in the presence of peroxide |
| US6987149B2 (en) * | 2001-04-22 | 2006-01-17 | Said Bouhelal | Isostatic polypropylene crosslinking in the presence of peroxide |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of Applied Polymer Science》 20061212 S. Bouhelal et al. "Structure modification of isotactic polypropylene through chemical crosslinking: Toughening mechanism 2968-2976 1-11 第103卷, 第5期 * |
| S. BOUHELAL ET AL.: ""Structure modification of isotactic polypropylene through chemical crosslinking: Toughening mechanism", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
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Application publication date: 20130123 |