CN102924781A - Calcium carbonate high-filling polyethylene foam material and preparation method thereof - Google Patents
Calcium carbonate high-filling polyethylene foam material and preparation method thereof Download PDFInfo
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- CN102924781A CN102924781A CN2012104316042A CN201210431604A CN102924781A CN 102924781 A CN102924781 A CN 102924781A CN 2012104316042 A CN2012104316042 A CN 2012104316042A CN 201210431604 A CN201210431604 A CN 201210431604A CN 102924781 A CN102924781 A CN 102924781A
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Abstract
Disclosed is a calcium carbonate high-filling polyethylene foam material. The material comprises, by weight, 15-45 of polyethylene, 55-85 of calcium carbonate, 0.2-0.5 of coupling agent, 0.5-2 of cross linking agent and 1-5 of foaming agent. The polyethylene, the calcium carbonate, the coupling agent, the cross linking agent and the foaming agent are mixed evenly, heated, pressurized and subjected to foam extrusion, and the material is formed. The preparation method comprises step of firstly, drying calcium carbonate of more than 300 meshes of fineness; secondly, stirring dried calcium carbonate and the coupling agent in a high mixing machine, and heating and activating the mixture; thirdly, mixing the centered foaming agent evenly in accordance with the set formula of the foaming agent; fourthly, cooling the activated calcium carbonate naturally, adding a mixture of the polyethylene, the cross linking agent and the foaming agent to the high mixing machine in accordance with the set formula and mixing the mixture evenly; and fifthly, conducting the foam extrusion for the mixture of the step four by using an extruder and preparing the polyethylene foam material. The density and the strength of the polyethylene foam material can be effectively improved, the production cost is low, the preparation process is simple, and the material is economical and practical.
Description
Technical field
The present invention relates to a kind of polyethylene foam material and preparation method thereof, particularly a kind of with high filled polyethylene foam materials of the inorganic powder filled calcium carbonate of high-content and preparation method thereof.
Background technology
Polyethylene foam material has good toughness, chemical stability, insulation and heat-proof quality, and relative low price, becomes kind maximum in the current foam materials.Current polyethylene is generally take polyvinyl resin as base material, and take azo foaming agent or carbonic acid gas as whipping agent, dicumyl peroxide is linking agent.And add as required part blowing promotor and fire retardant etc. and be prepared from, in recent years in order to improve polyethylene melt intensity, there are scientific and technical personnel to study the polyethylene foam material of nanon calcium carbonatefilled, (the foam performance research of nanon calcium carbonatefilled Polyethylene/polypropylene, Li Gang, model is outstanding, New Chemical Materials, 2007,35(2): 49-51).Also there is the people in the polyethylene foam material system, to add a small amount of calcium carbonate for the rigidity that improves foam materials.But the calcium carbonate proportion of adding is generally all lower, and the amount of calcium carbonate in system generally is no more than 30%.And because the adding of calcium carbonate has caused the processing temperature of resin system, blowing temperature to significantly improve, the resin melt strength decreased, existing foaming system can't be used, therefore there is the people study the blowing temperature that interpolation ethylene-vinyl acetate copolymer (EVA) reduces system, also the someone has developed the new technology (reducing the method for processing temperature of calcium carbonate granule filling high density polyethylene composite material, 200810242659.2) that how to reduce processing temperature after calcium carbonate-filled.But the total content of the calcium carbonate in these systems generally all is no more than 30% of system.
In actual applications, density is low no doubt to be an advantage of porous plastics, but a lot of occasion needs the slightly high heat insulating polyethylene foam material of density, so the polyethylene foam material that high carbon acid calcium is filled has its certain market in actual applications.And the calcium carbonate-filled polyethylene intensity of high-content is good, and modulus is high, and own unique performance advantage is arranged.But because the polyethylene system processing temperature that high carbon acid calcium is filled can significantly improve, existing foaming cross-linking system is not suitable with the foaming processing of the polythene material of high carbon acid calcium contents.
The present invention is directed to calcium carbonate content and surpass 50% high carbon acid calcium filled polyethylene system, invented the new peak filled polyethylene foam process that adopts the heat absorption heat release whipping agent heat absorption-exothermic equilibrium type high temperature foaming system that adapts to high filled polyethylene foaming and high-temperature cross-linking agent etc. and calcium carbonate-filled polyethylene foam-material.
Summary of the invention
The technical problem to be solved in the present invention is, high polyethylene foam material of filling of a kind of calcium carbonate and preparation method thereof is provided, solve the problem that the high filled polyethylene material processing of calcium carbonate fusing point height and foaming cross-linking system can not prepare high filled polyethylene, make the content of calcium carbonate in this polyethylene can be up to more than 50% of whole material, and can keep the performance characteristics of high carbon acid calcium contents material, has high-modulus, high-intensity characteristics.
The technical scheme that adopts is:
The high filled polyethylene foam materials of a kind of calcium carbonate, by following component mix and heat, pressurize, foaming to extrude forms, meter being respectively by weight:
Polyethylene 15-45
Calcium carbonate 55-85
Coupling agent 0.2-0.5
Linking agent 0.5-2
Whipping agent 1-5
Above-mentioned polyethylene is high density polyethylene(HDPE) or Low Density Polyethylene or its two kinds of compounds.
Above-mentioned calcium carbonate requires its fineness more than 300 orders, can be water-ground limestone, also can be the calcium carbonate of light calcium carbonate and both arbitrary proportions thereof.
Above-mentioned coupling agent mainly is that titanium is that coupling agent, aluminium are coupling agent, aluminium titanium composite coupler.
Above-mentioned linking agent is high-temperature cross-linking agent, and crosslinking reaction occurs in 150 ℃ ~ 180 scopes, such as 2,5-dimethyl-2, and 5-di-tert-butyl peroxide hexin, together with-diperoxy tertiary butyl-3,3,5-trimethyl-cyclohexane, 1,3-di-tert-butyl peroxidation isopropyl benzene.
Above-mentioned whipping agent is the thermal equilibrium mixed foaming agent that is mixed by heat release type whipping agent and endothermic blowing agent, the Enthalpies of Formation of require mixing rear foaming agent in-150J/g to 150J/g scope by weight components through mixing:
Cellmic C 121 (AC) 10
Sodium carbonate salt 1-8
Polyhydroxy acid sodium salt 0-6
The preparation method of the high filled polyethylene foam materials of a kind of calcium carbonate comprises the steps:
Step 1: fineness is dried to water content≤0.1% greater than 300 purpose calcium carbonate under 80-200 ℃ of temperature in drying plant;
Step 2: the coupling agent of the dried calcium carbonate of step 1 and preset proportion is stirred in high mixer, and heat-activated is mixed 10-20min and is not less than 115 ℃ to compound temperature;
Step 3: set prescription according to whipping agent and will concentrate whipping agent to mix;
Step 4: after the calcium carbonate that has activated in the step 2 naturally cooled to 60 ℃ by setting prescription with polyethylene, polyethylene is added in the high mixer mix by setting prescription after mixing the calcium carbonate cooling that maybe will activate in the adding such as linking agent, the blowing agent blends high mixer and naturally cooling to 60 ℃, and use the forcing machine granulation.Calcium carbonate polyethylene composite grain and linking agent, blowing agent blends etc. are being mixed in mixing device;
Step 5: the mixture in the step 4 is even with the Banbury mixer banburying at 90-150 ℃, then use with in the melt moulded from foam machine with 180-230 ℃, foamed under the 5-40MPa condition 3 ~ 20 minutes, cooling and demolding, and be warming up to 180-230 ℃ of second time of foaming at this and can make polyethylene foam material or under 180-230 ℃, utilize extruder for shaping to prepare polyethylene foam-material in the mixture in the step 4.
Useful technique effect of the present invention is:
The present invention can foam high carbon acid calcium contents polyethylene, the polyethylene foam material of preparation calcium carbonate content, density and intensity that can the Effective Raise polyethylene foam material can utilize simultaneously the polythene material of calcium carbonate partially filled, satisfy the demand of different occasions.Polyethylene production cost of the present invention is low, and preparation technology is simple, and economic and practical is strong.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one
At first, choose 7 kilograms of 500 purpose water-ground limestone fineness, lower dry 2 hours at 115 ℃; Mixing at high mixer, and add 0.2 kilogram of zinc titanate ester coupling agent, is 115 ℃ by high-speed stirring to temperature; Add again 5 kilograms of high density polyethylene(HDPE)s, low speed mixing 5 minutes.Add mixture in the Banbury mixer and add 300 and restrain 2,5-dimethyl-2,5-di-tert-butyl peroxide hexin, 150 gram polyhydroxy acid sodium salts, 200 gram Cellmic C 121s, 120 ℃ of banburyings 10 minutes, compound joined the moulded from foam machine, at 195 ℃, reaction is 13 minutes under the 25MPa condition, pressure release cooling, the demoulding, then foam is placed into 200 ℃ of baking oven relaying supervention bubbles 30 minutes, can obtains the target polyethylene foam-material.
Embodiment two
Choose 10 kilograms of 2500 order light calcium carbonate fineness, lower dry 3 hours at 100 ℃; Mix at high mixer, and add 0.3 kilogram of aluminium titanium composite coupler, temperature is 150 ℃, mixes 10min; Add again 10 kilograms of Low Density Polyethylenes, 500 grams, 1,3-di-tert-butyl peroxidation isopropyl benzene, 400 gram sodium bicarbonate salts, 300 gram Cellmic C 121s, low speed mixing 5 minutes.Mixture added in the twin screw extruder extrudes under 205 ℃ of conditions, then with foam by 200 ℃ of hot-air channels 3 minutes, can obtain the target polyethylene foam-material.
Claims (7)
1. high filled polyethylene foam materials of calcium carbonate, it is characterized in that by following component mix and heat, pressurize, foaming to extrude forms, meter being respectively by weight:
Polyethylene 15-45
Calcium carbonate 55-85
Coupling agent 0.2-0.5
Linking agent 0.5-2
Whipping agent 1-5.
2. the high filled polyethylene foam materials of a kind of calcium carbonate according to claim 1 is characterized in that described polyethylene is high density polyethylene(HDPE) or Low Density Polyethylene or its two kinds of compounds.
3. the high filled polyethylene foam materials of a kind of calcium carbonate according to claim 1 is characterized in that described its fineness of calcium carbonate requirement more than 300 orders, can be water-ground limestone, also can be the calcium carbonate of light calcium carbonate and both arbitrary proportions thereof.
4. the high filled polyethylene foam materials of a kind of calcium carbonate according to claim 1 is characterized in that described coupling agent is that titanium is that coupling agent, aluminium are coupling agent, aluminium titanium composite coupler.
5. the high filled polyethylene foam materials of a kind of calcium carbonate according to claim 1, it is characterized in that described linking agent is high-temperature cross-linking agent, crosslinking reaction occurs in 150 ℃ ~ 180 scopes, such as 2,5-dimethyl-2,5-di-tert-butyl peroxide hexin, together with-diperoxy tertiary butyl-3,3,5-trimethyl-cyclohexane, 1,3-di-tert-butyl peroxidation isopropyl benzene.
6. the high filled polyethylene foam materials of a kind of calcium carbonate according to claim 1, it is characterized in that described whipping agent is the thermal equilibrium mixed foaming agent that is mixed by heat release type whipping agent and endothermic blowing agent, the Enthalpies of Formation of require mixing rear foaming agent in-150J/g to 150J/g scope, by weight components through mixing:
Cellmic C 121 (AC) 10
Sodium carbonate salt 1-8
Polyhydroxy acid sodium salt 0-6.
7. the preparation method of the high filled polyethylene foam materials of calcium carbonate, its feature comprises the steps:
Step 1: fineness is dried to water content≤0.1% greater than 300 purpose calcium carbonate under 80-200 ℃ of temperature in drying plant;
Step 2: the coupling agent of the dried calcium carbonate of step 1 and preset proportion is stirred in high mixer, and heat-activated is mixed 10-20min and is not less than 115 ℃ to compound temperature;
Step 3: set prescription according to whipping agent and will concentrate whipping agent to mix;
Step 4: after the calcium carbonate that has activated in the step 2 naturally cooled to 60 ℃ by setting prescription with polyethylene, polyethylene is added in the high mixer mix by setting prescription after mixing the calcium carbonate cooling that maybe will activate in the adding such as linking agent, the blowing agent blends high mixer and naturally cooling to 60 ℃, and use the forcing machine granulation, calcium carbonate polyethylene composite grain and linking agent, blowing agent blends etc. are being mixed in mixing device;
Step 5: the mixture in the step 4 is even with the Banbury mixer banburying at 90-150 ℃, then use with in the melt moulded from foam machine with 180-230 ℃, foamed under the 5-40MPa condition 3 ~ 20 minutes, cooling and demolding, and be warming up to 180-230 ℃ of second time of foaming at this and can make polyethylene foam material or under 180-230 ℃, utilize extruder for shaping to prepare polyethylene foam-material in the mixture in the step 4.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061864A (en) * | 2015-08-03 | 2015-11-18 | 苏州新区佳合塑胶有限公司 | LDPE high-foaming calcium-plastic sheet material |
| CN105462042A (en) * | 2016-01-11 | 2016-04-06 | 宁波高新区辉门科技有限公司 | Microcellular foam light plastic and preparation method thereof |
| CN109401006A (en) * | 2018-09-30 | 2019-03-01 | 三斯达（江苏）环保科技有限公司 | A kind of enhanced composite foam material and preparation method thereof |
| CN109761633A (en) * | 2019-03-09 | 2019-05-17 | 大连地拓环境科技有限公司 | A kind of unburned boron mud PVC haydite and preparation method thereof |
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| CN102391557A (en) * | 2011-07-07 | 2012-03-28 | 宋旭 | High-filling controllable oxidative degradation packaging material and preparation method thereof |
| CN102443214A (en) * | 2011-09-23 | 2012-05-09 | 福建师范大学 | Preparation method for high foaming ratio polyethylene foaming material |
| CN102604223A (en) * | 2012-03-16 | 2012-07-25 | 武汉富蒂亚新型材料有限公司 | Polypropylene resin foam concentrate and preparation method thereof |
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- 2012-11-02 CN CN2012104316042A patent/CN102924781A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101649559A (en) * | 2009-08-31 | 2010-02-17 | 四川大学 | Energy-saving and emission-reduction method for production line of PVC artificial leather |
| CN102391557A (en) * | 2011-07-07 | 2012-03-28 | 宋旭 | High-filling controllable oxidative degradation packaging material and preparation method thereof |
| CN102268164A (en) * | 2011-08-04 | 2011-12-07 | 厦门大学 | Micro-foaming polystyrene all-plastic wood-like material and production method thereof |
| CN102443214A (en) * | 2011-09-23 | 2012-05-09 | 福建师范大学 | Preparation method for high foaming ratio polyethylene foaming material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061864A (en) * | 2015-08-03 | 2015-11-18 | 苏州新区佳合塑胶有限公司 | LDPE high-foaming calcium-plastic sheet material |
| CN105462042A (en) * | 2016-01-11 | 2016-04-06 | 宁波高新区辉门科技有限公司 | Microcellular foam light plastic and preparation method thereof |
| CN109401006A (en) * | 2018-09-30 | 2019-03-01 | 三斯达（江苏）环保科技有限公司 | A kind of enhanced composite foam material and preparation method thereof |
| CN109761633A (en) * | 2019-03-09 | 2019-05-17 | 大连地拓环境科技有限公司 | A kind of unburned boron mud PVC haydite and preparation method thereof |
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Application publication date: 20130213 |