CN1098117A - Oil shale ash-polyolefin loading and preparation method thereof - Google Patents
Oil shale ash-polyolefin loading and preparation method thereof Download PDFInfo
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- CN1098117A CN1098117A CN 93108881 CN93108881A CN1098117A CN 1098117 A CN1098117 A CN 1098117A CN 93108881 CN93108881 CN 93108881 CN 93108881 A CN93108881 A CN 93108881A CN 1098117 A CN1098117 A CN 1098117A
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Abstract
The present invention is a kind of oil shale ash-polyolefin loading, and it is to be mixed in the high-speed mixer high speed by a certain percentage by kerosene shale ash, coupling agent, dispersion agent, cunning dose, resin, is cut into required particle again.Weighting agent of the present invention is owing to use suitable coupling agents, thereby improved shock strength, shearing resistance, the tensile strength of weighting agent, and preparation technology is simple, and weighting agent easily and plastics, rubber mix.
Description
The invention belongs to the composition of macromolecular compound, or rather, be a kind of be the filler for polylefines of main component with the kerosene shale ash.
In plastics and Rubber processing technical field, filling-modified is one of its important means, and therefore the research of filling-modified technology and filling-modified material more and more comes into one's own, and many meticulous powderies or granular filling master batch special product have occurred.They had both played the effect of filling and reducing cost, and had the effect that improves product properties again.At present, plastics, rubber-like weighting agent are many with lime carbonate or wollastonite, its filling mode: they are directly worn into the powder of certain fineness, be generally≤200 orders filled plastics, rubber item; Perhaps mixing through coupling agent modified processing, plastics processing mill powder lime carbonate or wollastonite, be a granulated into weighting agent (" plastics science and technology ", [6], 1990; " plastics ", [4], 1989).
Kerosene shale ash after the also useful oil shale distillation is made plastics, rubber filler (" plastics science and technology ", [3], 1990).It is that destructive distillation ashes drying is handled, and wears into≤200 purpose powder, directly as plastics, rubber filler again.
Above-mentioned weighting agent such as lime carbonate, kerosene shale ash powder packed rubber, plastics have brought the shortcoming of shock strength, toughness, degradation such as ageing-resistant.
The objective of the invention is to overcome the shortcoming of existing stopping composition, providing a kind of is the filling master batch and the technology of preparing thereof of main component with industrial waste-kerosene shale ash.
The objective of the invention is to realize by following proposal.
Weighting agent of the present invention is to be major ingredient with the kerosene shale ash, selects suitable coupling agents and dispersion agent, lubricant, resin, and they are mixed in the high-speed mixer high speed according to a certain percentage, be cut into again required particle filler for polylefines.
Characteristics of the present invention are that weighting agent is made up of kerosene shale ash, coupling agent, dispersion agent, resin, lubricant, it forms content (is 100 heavy % in kerosene shale ash): coupling agent 0.5～1.2 heavy %, dispersion agent 1～3 heavy %, resin 10～15 heavy %, lubricant 10～15 heavy %, all the other are kerosene shale ash.
Preparation method of the present invention:
1, resinous shale is pressed usual method pulverizing, dry, screening, it is become 〉=320 purpose kerosene shale ashs;
2, the kerosene shale ash after the screening adds in the high-speed mixer, and through the coupling agent coupling processing, 110～160 ℃ of coupling temperature are preferably 130～140 ℃;
3, the kerosene shale ash blend after dispersion agent and (2) the step coupling processing mixed 10～15 minutes in the mixing machine high speed;
4, heating open type plastic purificating set makes the temperature of its front and back roller reach 170 ℃, 165 ℃ respectively, and resin is put on the roller, treats that its fusing back adds solid paraffin blend 3～5 minutes, adds (3) again and goes on foot mixing 10～15 minutes of compound;
5, treat to send dicing machine after (4) step, the sheet stock temperature that obtains reached 30～40 ℃, be cut into required particle, be oil shale ash-polyolefin loading.
Preparation method of the present invention can also go out the machine extruding pelletization by direct economy, concrete steps are as follows: the kerosene shale ash of screening is added in the high-speed mixer, at 110～160 ℃, best 130～140 ℃ of following coupling processing, add dispersion agent, resin, lubricant respectively by proportioning again, mixed 10～15 minutes; Add hot extruder; reach 100～120 ℃ in I district; 140～160 ℃ in II district; 170～180 ℃ in III district; 140～150 ℃ in IV district; above-mentioned compound is joined lentamente directly granulation in the forcing machine of rotating speed 50～80r/min, perhaps compound is cut into required particle through dicing machine again after the forcing machine extrusion.
Described kerosene shale ash is through overflow ash after the Boiling Combustion or the destructive distillation slag after the gas retort destructive distillation.It is an industrial waste, it is the random thing of piling up of a kind of surface irregularity porous, particle size distribution range with broad, the non-single mineral composition of forming by multiple metal oxide, as select suitable coupling agents, can make the weighting agent of kerosene shale ash that better tensile strength and shock resistance are arranged.
Described coupling agent is rare earth 820G-C
1Or phthalate, preferably rare earth 820G-C
1, it is developed jointly by Beijing Chemical Engineering College and Anshan macromolecular material factory.Adopt this coupling agent can improve the impact strength and the shearing resistance of kerosene shale ash weighting agent; Because rare earth can change inorganics surface energy at the interface, makes its viscosity degradation, improves the rheological property of polymkeric substance under the weighting agent high filler loading capacity, improve the degree of scatter of kerosene shale ash particle in resin.
Described resin can be selected high-pressure polyethylene (LDPE) or low pressure polyethylene, preferably LDPE for use.The LDPE that the present invention uses is method home-made FDO274, and low pressure polyethylene is the 5000S that plastic molding and processing plant of Daqing Ethylene headquarters produces.Its effect mainly is that the kerosene shale ash particle is played coating, bonding effect.
Described dispersion agent is the stearic acid of using always, and its effect is to make the kerosene shale ash of coupling processing be dispersed into particulate, makes it no longer cohesion in the course of processing.
Described lubricant is a solid paraffin, preferably selects 48～58 ℃ solid paraffin for use, requires cleaning, inclusion-free, moisture content, and it mainly acts on is to improve processing characteristics.
It is the mixing machine of GH50 type that described high-speed mixer can be selected the trade mark for use, and its rotating speed is 725～1440r/min; It is SJ20A plastic forcing machine that described forcing machine can be selected the trade mark for use, and its length-to-diameter ratio is 25: 1, rotating speed 20～160r/min; It is the SK400B open type plastic purificating set that described mill can be selected the trade mark for use, roller velocity ratio 1: 1.2727, roller working temperature＜170 ℃.
Major advantage of the present invention:
1, the main component of weighting agent of the present invention is a kerosene shale ash, because it is an industrial residue, so raw material sources are easy, and turn harm into good, and reduce environmental pollution.
2,, thereby improve impact strength, shearing resistance and the tensile strength of kerosene shale ash weighting agent owing to find suitable coupling agents.For example compare with filling out filling parent material of calcium carbonate, when loading level all was 10%, weighting agent tensile strength of the present invention improved 41.5%; The resistance to impact shock 1.527KJ/m of virgin pp (PP) for another example
2, when loading level all was 10%, the PP impact strength decreased of calcium carbonate filled masterbatch was to 0.27KJ/m
2, and the PP impact strength decreased of filling weighting agent of the present invention is to 1.3KJ/m
2
3, the high filler loading capacity of weighting agent of the present invention can reach 50～60m%, and the kerosene shale ash loading level that non-modified is handled then is 20～30m%.
4, weighting agent good flowing properties of the present invention, melt index MI=11.2g/10min in the time of 100 ℃, and calcium carbonate-filled dose of melt index MI=4.4g/10min in the time of 210 ℃.
5, weighting agent humidity resistance of the present invention is good, and water content reduces to 0.91% by 1.48% after depositing 3 years naturally.
6, preparation technology of the present invention is simple, easily with plastics, rubber mix, and the kerosene shale ash powder shortening mixing time of handling than non-modified 10%, and also free from environmental pollution.
Further specify characteristics of the present invention below by example.
Example 1
Take by weighing kerosene shale ash (the fluidizing furnace overflow ash) 20kg after the screening, add in the mixing machine, be heated to 110 ℃, dry 10 minutes, divides adding rare earth 820G-C three times
10.2kg each stirred three minutes, added stearic acid 0.4kg, paraffin 0.8kg again, high-speed stirring discharging in 5 minutes is stand-by.The heating open type plastic purificating set makes preliminary roller reach 170 ℃, 165 ℃ on back roller; roll spacing 1mm adds LDPE 2kg therebetween, adds paraffin 1.2kg again; treat to add when the plucking phenomenon appears in its fusing the material for preparing; mixing 10 minutes, make tablet roll spacing during for 0.5mm by three times, when strengthening roll spacing to 3mm; again by three times; be 3mm sheet at present in roll spacing at last, treat to send when the sheet temperature is cool slightly the dicing machine pelletizing, oil shale ash-polyolefin loading Y
1
Example 2
Take by weighing kerosene shale ash (destructive distillation ashes) 10kg after the screening, put into the mixing machine inner drying 10 minutes that is heated to 150 ℃, divide to add coupling agent rare earth 820G-C for three times
10.05kg, stirred 3 minutes at every turn, add hard ester acid 0.1kg then, paraffin 0.6kg, high-speed stirring after 5 minutes discharging stand-by.The heating open type plastic purificating set makes 170 ℃ of preliminary rollers, 165 ℃ on back roller; 1mm is transferred in roll spacing, adds LDPE 1.2kg and paraffin 0.9kg, treats to add when the plucking phenomenon appears in fusion the material for preparing; at this moment roll spacing is increased to 6mm, and mixing 10 minutes, therebetween; tablet is passed through three times when roll spacing 3mm; when roll spacing 0.5mm, by three times, then at distance 3mm sheet at present; send the dicing machine pelletizing when sheet temperature is cool slightly, oil shale ash-polyolefin loading Y
2
Example 3
Take by weighing kerosene shale ash (the fluidizing furnace overflow ash) 30kg after the screening, put into the mixing machine that is heated to 140 ℃, dry 15 minutes, divides adding rare earth 820G-C three times
10.36kg, stirred 3 minutes at every turn, add stearic acid 0.8kg then, paraffin 2kg, LDPE 3.6kg, high-speed stirring discharging in 10 minutes is stand-by.Add hot extruder, make to reach: 100 ℃ in I district, 140 ℃ in II district, 170 ℃ in III district, 140 ℃ in IV district, the material that mixes is slowly added in the forcing machine, forcing machine rotating speed 50～80r/min extrudes diameter 3mm bar, send the dicing machine pelletizing slightly after the cold, weighting agent Y
3
Example 4
Take by weighing kerosene shale ash (destructive distillation ashes) 20kg after the screening, input is heated in 170 ℃ the mixing machine, dry 15 minutes, adding the trade mark is the mixture 0.4kg of No. 15 white oils of OL-T671 titanic acid ester and the production of white oil factory of Maoming petrochemical corporation (complex), its ratio of mixture is 1: 1, high-speed stirring 3 minutes adds stearic acid 0.6kg, paraffin 25kg, LDPE 3.0kg, high-speed stirring after 10 minutes discharging stand-by.Add hot extruder; make to reach 120 ℃ in I district, 160 ℃ in II district, 180 ℃ in III district, 150 ℃ in IV district, the material that mixes is added in the forcing machine lentamente, under rotating speed 50～80r/min, extrude the bar of diameter 3mm; send dicing machine to be cut into 3 * 3 * 3mm particle slightly after the cold, weighting agent Y
4
Example 5
This example is weighting agent Y
1The performance that the kerosene shale ash powder (hereinafter to be referred as powder) of (hereinafter to be referred as pellet) and unmodified processing is filled behind the PP compares, and it the results are shown in Table 1.
Find out by table 1, the powder of filling 30%, breaking tenacity drops to 8.2MPa, other several indexs can't measure data, and the degradation of filling 30% pellet is little, up to filling 50%, 70% o'clock, breaking tenacity still reaches 13.2MPa, 10.7MPa respectively, and shock strength all is better than the shock strength (1.52KJ/m of pure PP
2).
Example 6
This example is weighting agent Y of the present invention
2Compare with calcium carbonate-filled dose of performance of filling PP, the results are shown in Table 2.
Table 2
As shown in Table 2, when loading level was 10%, the shock strength of calcium carbonate filled PP dropped to 0.27KJ/m
2, and fill Y
2PP then drop to 1.3KJ/m
2; When loading level is 15%, fill Y
2PP improve 300% than the digestion time of calcium carbonate filled PP, improve 33% than pure PP.
Example 7
This example is the application test result of weighting agent of the present invention.
With Y
2Weighting agent adds in the powerful polypropylene (FRPP), makes accumulator jar.Accumulator jar is used for the colliery, and requires acid and alkali-resistance, and price is more expensive.Past, some producers tried out multiple weighting agent, did not all reach national standard (JB3076).With Y of the present invention
2Behind the add-on injection accumulator jar with 5～10m%, every performance of goods all is better than national standard, and reduces cost.Acid-proof alkaline sees Table 3.
Table 3
Example 8
This example is the Another application test-results of weighting agent of the present invention.
With Y of the present invention
2And Y
4Weighting agent is filled rubber-plastic foamed sole.The pyrogenous kerosene shale ash weighting agent of past producer lime carbonate commonly used and non-modified, loading level 10～15%, and also resin demand can not reduce in the prescription.Use weighting agent Y of the present invention
2And Y
4, during loading level 60%, product properties meets standard GB 10508 fully, and loading level is 20～30% o'clock, also can reduce by 5% resin demand, has reduced cost.
Claims (8)
1, a kind of oil shale ash-polyolefin loading, it is characterized in that it is made up of kerosene shale ash, coupling agent, dispersion agent, lubricant, resin, it forms content (is 100 heavy % in kerosene shale ash): coupling agent 0.5～1.2 heavy %, dispersion agent 1～3 heavy %, resin 10～15 heavy %, lubricant 10～15 heavy %, all the other are kerosene shale ash.
2, according to the described weighting agent of claim 1, its preparation method is characterised in that preparation according to the following steps: (1) by usual method pulverizing, dry, screening, becomes 〉=320 purpose kerosene shale ashs it in resinous shale; (2) kerosene shale ash after the screening adds in the high-speed mixer, through the coupling agent coupling processing, and 110～160 ℃ of temperature, best 130～140 ℃; (3) the kerosene shale ash blend after dispersion agent and (2) the step coupling processing, high-speed mixing 10～15 minutes; (4) heating open type plastic purificating set makes the temperature of its front and back roller be respectively 170 ℃, 165 ℃, and resin is put on the roller, treats that its fusing adds solid paraffin blend 3～5 minutes, adds (3) step compound more mixing 10～15 minutes; Treat (5) that the sheet stock that obtains of (4) step reaches and send dicing machine to be cut into required particle after 30～40 ℃.
3; according to the described weighting agent of claim 1; its preparation method is characterised in that the kerosene shale ash with screening adds in the high-speed mixer; at 110～160 ℃; best 130～140 ℃ of following coupling processing; add dispersion agent more by a certain percentage; resin; lubricant; mixed 10～15 minutes; add hot extruder; reach 100～120 ℃ in I district; 140～160 ℃ in II district, 170～180 ℃ in III district, 140～150 ℃ in IV district; above-mentioned compound is joined directly granulation in the forcing machine of rotating speed 50～80r/min, perhaps compound is cut into required particle through dicing machine again after the forcing machine extrusion.
4,, it is characterized in that described resinous shale is through ash of the overflow after the Boiling Combustion or the destructive distillation slag after the gas retort destructive distillation according to claim 2 or 3 described preparation methods.
5,, it is characterized in that described coupling agent is rare earth 820G-C according to claim 1,2 or 3 described weighting agent or its preparation methods
1Or phthalate, preferably rare earth 820G-C
1
6,, it is characterized in that described resin is high-pressure polyethylene or low pressure polyethylene, preferably high-pressure polyethylene according to claim 1,2 or 3 described weighting agent or its preparation methods.
7,, it is characterized in that described dispersion agent is a stearic acid according to claim 1,2 or 3 described weighting agent or its preparation methods.
8,, it is characterized in that described lubricant is a solid paraffin, preferably 48～58 ℃ solid paraffin according to claim 1,2 or 3 described weighting agent or its preparation methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93108881A CN1042545C (en) | 1993-07-29 | 1993-07-29 | Oil shale ash-polyolefin loading and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93108881A CN1042545C (en) | 1993-07-29 | 1993-07-29 | Oil shale ash-polyolefin loading and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1098117A true CN1098117A (en) | 1995-02-01 |
| CN1042545C CN1042545C (en) | 1999-03-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93108881A Expired - Fee Related CN1042545C (en) | 1993-07-29 | 1993-07-29 | Oil shale ash-polyolefin loading and preparing process thereof |
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| CN (1) | CN1042545C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434461C (en) * | 2007-03-16 | 2008-11-19 | 中国地质大学（武汉） | A kind of method that utilizes oil shale solid waste to prepare natural rubber filler |
| CN101353448B (en) * | 2008-09-13 | 2010-09-29 | 山东东高纳米科技有限公司 | Dustfree demolding agent for high polymer elastic particle |
| CN102504368A (en) * | 2011-11-10 | 2012-06-20 | 吉林大学 | Modified rubber prepared by oil shale waste slag and method for preparing modified rubber by oil shale waste slag |
| WO2012083972A1 (en) | 2010-12-23 | 2012-06-28 | Tallinn University Of Technology | Composite of polymeric material with mineral fillers |
| WO2017182043A1 (en) * | 2016-04-22 | 2017-10-26 | Mineralplast Oü | Polymeric composite material containing burnt oil shale fly ash and the method for the preparation thereof |
| CN110527151A (en) * | 2019-09-03 | 2019-12-03 | 沈阳化工大学 | For rubber product using shale ashes as the natural gum preparation method of filler |
| CN113150578A (en) * | 2021-04-23 | 2021-07-23 | 双星集团有限责任公司 | Novel modified pyrolysis carbon black and preparation method thereof |
| CN115322480A (en) * | 2022-08-16 | 2022-11-11 | 广东省鸿大碳基环保科技有限公司 | Plastic master batch containing oil shale ash and preparation method and application thereof |
| CN121064563A (en) * | 2025-11-06 | 2025-12-05 | 吉林建筑大学 | A method for improving the tensile strength and thermal stability of polypropylene filled with oil shale slag |
-
1993
- 1993-07-29 CN CN93108881A patent/CN1042545C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434461C (en) * | 2007-03-16 | 2008-11-19 | 中国地质大学（武汉） | A kind of method that utilizes oil shale solid waste to prepare natural rubber filler |
| CN101353448B (en) * | 2008-09-13 | 2010-09-29 | 山东东高纳米科技有限公司 | Dustfree demolding agent for high polymer elastic particle |
| WO2012083972A1 (en) | 2010-12-23 | 2012-06-28 | Tallinn University Of Technology | Composite of polymeric material with mineral fillers |
| CN102504368A (en) * | 2011-11-10 | 2012-06-20 | 吉林大学 | Modified rubber prepared by oil shale waste slag and method for preparing modified rubber by oil shale waste slag |
| WO2017182043A1 (en) * | 2016-04-22 | 2017-10-26 | Mineralplast Oü | Polymeric composite material containing burnt oil shale fly ash and the method for the preparation thereof |
| CN110527151A (en) * | 2019-09-03 | 2019-12-03 | 沈阳化工大学 | For rubber product using shale ashes as the natural gum preparation method of filler |
| CN113150578A (en) * | 2021-04-23 | 2021-07-23 | 双星集团有限责任公司 | Novel modified pyrolysis carbon black and preparation method thereof |
| CN113150578B (en) * | 2021-04-23 | 2022-04-15 | 双星集团有限责任公司 | Novel modified pyrolysis carbon black and preparation method thereof |
| CN115322480A (en) * | 2022-08-16 | 2022-11-11 | 广东省鸿大碳基环保科技有限公司 | Plastic master batch containing oil shale ash and preparation method and application thereof |
| CN121064563A (en) * | 2025-11-06 | 2025-12-05 | 吉林建筑大学 | A method for improving the tensile strength and thermal stability of polypropylene filled with oil shale slag |
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| Publication number | Publication date |
|---|---|
| CN1042545C (en) | 1999-03-17 |
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