CN1339526A - Process for producing hollow micro bead filled resin base composite material - Google Patents
Process for producing hollow micro bead filled resin base composite material Download PDFInfo
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- CN1339526A CN1339526A CN 01141911 CN01141911A CN1339526A CN 1339526 A CN1339526 A CN 1339526A CN 01141911 CN01141911 CN 01141911 CN 01141911 A CN01141911 A CN 01141911A CN 1339526 A CN1339526 A CN 1339526A
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- cenosphere
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- micro bead
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Abstract
The production process of hollow micro bead and filled resin base composite material includes: sorting, iron elimination and carbon elimination of flyash to obtain hollow micro bead with spherical rate over 90 % and size of about 0.5-5 micron; aerosol process of surface modification of the hollow micro bead at temperature controlled in room temperature to 300 deg.c; drying treatment of superfine hollow micro bead, resin base material and assistant; high speed mixing through stirring; and finally deposition and pressing to form the composite material.
Description
Technical field
The present invention relates to a kind of manufacturing process of coal fly ash hollow micro bead filled resin base composite material, particularly, join resin-based materials (as: macromolecular materials such as polypropylene, polyvinyl chloride, high density polyethylene(HDPE), ABS, nylon) and make new matrix material by to the selected and surface modification treatment of coal fly ash hollow micro bead etc.
Background technology
Usually, the plastic filler major part is to adopt various nonmetalliferous ore powder materials, as light calcium carbonate, water-ground limestone, talcum, kaolin, wollastonite, the tremolite, mica etc., granularity does not wait between 1-40 μ m, these nonmetal breeze fillers are except reducing the plastics cost, and it also gives plastics some specific functions, as improve hardness, intensity, fire-retardant, reduce goods shrinking percentage etc., therefore, nonmetal breeze is widely used as plastic filler.The development and the market requirement along with this class matrix material, nonmetal breeze is because the some shortcomings part of itself, the hardness (Mohs' hardness 1-3) of, material irregular as particle shape and intensity are low etc., cause intensity and shock resistance can reach higher requirement.Recently, nano nonmetal breeze material arises at the historic moment, and as nano-calcium carbonate and nano imvite material, adds in the plastics and has obtained result preferably, has reached toughness reinforcing, enhanced purpose.But it is to be noted, from the current experiments result, the add-on of nano nonmetal mineral powder filling materials and the production cost of goods may be factors of its development of restriction, because, the plastics that add nano nonmetal breeze material at present mostly are when the add-on of about 3-10%, its mechanical property reaches best state, and during greater than this add-on, mechanical properties decrease is very fast.If this nano nonmetal breeze material price is lower than plastics, its add-on is low to be a factor of its economic benefit of restriction, if be higher than the plastics price, just be difficult to be extensive use of, can only be used for some special needs, therefore, this also is an aspect of its economic benefit of restriction.Therefore, the economy of nano-composite material is an important factor of its development of restriction.
Summary of the invention
The objective of the invention is coal fly ash hollow micro bead is joined in the resin-based materials, make hollow micro bead filled resin base composite material, another object of the present invention provides a kind of manufacturing process of coal fly ash hollow micro bead filled resin base composite material.After this hollow tiny pearl adds in the resin base, can reach toughness reinforcing, enhanced purpose simultaneously, the amount of inserting can both reach mechanical property preferably at 20～30% o'clock, simultaneously can also improve hardness, rigidity, wear resistance, erosion resistance and heat-proof quality etc., reduce the goods shrinking percentage, anufacturability also can obviously improve.
The manufacturing process of coal fly ash hollow micro bead filled resin base composite material of the present invention comprises: selected, the surface modification treatment of cenosphere and preparation of matrix material etc.
The selected of described coal fly ash hollow micro bead is the coal fly ash hollow micro bead that classification obtains 0.5～5um from the dust of flyash, then by the high gradient magnetic separator deironing, by the semiconductor machine carbon elimination, obtains the very high cenosphere material of spherical rate at last again.
Described cenosphere surface modification treatment is at the very thin modified layer of cenosphere surface-coated one deck (as silane etc.).This processing technology for surface modification is the modifier solution (as silane etc.) that needs is coated to the cenosphere surface, mix with it by the high speed rotating air-flow, by superonic flow nozzzle this air-flow mixture is equipped with in the fluidized-bed of cenosphere suspensoid with very high speed spirt again, can deposit the very thin organic membrane of one deck on solid cenosphere surface, the temperature of this fluidized-bed can be regulated and control in normal temperature and 300 ℃ of scopes.By the aerosol surface modification treatment, can be in the thin modified layer of cenosphere surface applied one deck.This treatment process is simple, and modification is complete, and coating is thin and firm.
Wherein properties-correcting agent is not special restriction, can be those that use always in the prior art, for example is selected from silane, stearic acid, titanic acid ester, the aluminic acid ester etc. one or more.
The main technique of the manufacturing of described coal fly ash hollow micro bead filled resin base composite material is: earlier cenosphere and macromolecular material are carried out drying treatment (can use baking oven and hot blast etc.), then these two kinds of materials and some promoter materials with high-speed mixers through after a while combination treatment, wherein the loading level of cenosphere generally is 5～50%, preferably 10～40%, more preferably 20～30% (based on the gross weights of matrix material) are extruded by screw mixing forcing machine or roller plastics processing mill etc. again, inject, lamination or alternate manner are shaped and promptly make the matrix material of being invented.
Wherein said resin-based materials is not special restriction, includes but not limited to polypropylene, polyvinyl chloride, polyethylene, polymeric amide, polyester, urethane, polyacrylic ester, polymethacrylate, ABS, ASA and silicon rubber etc.Promoter material is those that use always in this area, for example is selected from antioxidant, tinting material, static inhibitor, fire retardant, other weighting agent (as silicon-dioxide, lime carbonate etc.) etc. one or more.
The characteristics of matrix material of the present invention are: Young's modulus height, hardness height, Vicat softening point height, rheological are good, little, the surperficial good hand touch of goods shrinking percentage, wear-resisting, acid and alkali-resistance, heat insulation and sound insulation good, low cost of manufacture etc., are a kind of type materials that can widespread use.
Description of drawings
Fig. 1 is the Cenosphere Filled Polypropylene Composite flow chart making.
Fig. 2 is a cenosphere filling polyvinyl chloride matrix material hardboard flow chart making.
Fig. 3 is a cenosphere filling polyvinyl chloride composite material pipe flow chart making.
Describe the present invention by the following examples, it should be noted, these embodiment are illustrative, do not constitute any limitation of the invention.
The specific embodiment
Embodiment 1:
A kind of manufacturing process of coal fly ash hollow micro bead filling polypropylene composite material as shown in Figure 1. It comprises: the classification of flyash dust, and can classification from the flyash dust by gas flow sizing machine Go out the cenosphere material of particle diameter 0.5～5um; The high gradient magnetic separator deironing, this magnetic separator is Current version, by magnetic separation, the oxides-containing iron of cenosphere is reduced to from 3%～15% Below 1%; Semiconductor machine de-carbon, carbon granules impurity are a kind of semi-conducting materials, by semiconductor machine Friction pulley changes the electrical of carbon granules, utilizes and electrically remove carbon granule impurity from flyash; Hollow The surface modification treatment of microballon, it is that triethyl group triethoxysilane modification liquid is passed through High Rotation Speed Air-flow mixes with it, by superonic flow nozzzle this air-flow mixture is filled with very high speed spirt again Have in the fluid bed of cenosphere suspended substance, it is very thin to deposit one deck on solid cenosphere surface Organic film, the temperature of this fluid bed can regulate and control in normal temperature and 300 ℃ of scopes, this making Modified layer is thin and firm, and modification is complete; Drying and processing is by baking oven or hot blast, to the sky of modification Heart microballon and polypropylene powder carry out drying to be processed; The two mixes in 2: 8 ratio, above-mentioned two Plant material by the high-speed mixer mixed processing; Screw mixing extruder melt blending extruding pelletization, And acquisition pellet; The plastic injection equipment injection moulding obtains Cenosphere Filled Polypropylene Composite Goods.
Embodiment 2
Technological process as shown in Figure 1, step is with embodiment 1, just the modification cenosphere is in poly-third The mixing ratio of alkene powder is 3: 7.
Embodiment 3
Step just replaces polypropylene with polyethylene with embodiment 1, makes cenosphere and fills poly-The ethene composite.
Embodiment 4:
A kind of manufacturing process of cenosphere filling polyvinyl chloride composite hardboard as shown in Figure 2. It comprises: the classification of flyash dust, and can classification from the flyash dust by gas flow sizing machine Go out the cenosphere material of particle diameter 0.5～5um; The high gradient magnetic separator deironing, this magnetic separator is Current version, by magnetic separation, the oxides-containing iron of cenosphere is reduced to from 3%～15% Below 1%; Semiconductor machine de-carbon, carbon granules impurity are a kind of semi-conducting materials, by semiconductor machine Friction pulley changes the electrical of carbon granules, utilizes and electrically remove carbon granule impurity from flyash; Hollow The surface modification treatment of microballon, it is mixed by High Rotation Speed air-flow and its titanate esters modification liquid Close, by superonic flow nozzzle this air-flow mixture is equipped with cenosphere with very high speed spirt again In the fluid bed of suspended substance, can deposit the very thin organic film of one deck on solid cenosphere surface, The temperature of this fluid bed can be regulated and control in normal temperature and 300 ℃ of scopes, this modified layer of making thin and The jail, modification is complete; Drying and processing is by baking oven or hot blast, to the cenosphere of modification and poly-The vinyl chloride powder carries out drying to be processed; Mix and stirring, above-mentioned bi-material (3: 7 weight Than) and auxiliary agent by high-speed mixer mixing and stir process; Banbury is in mixing chamber, floating Hammer and rotate in opposite directions in force to plasticate, make material plastify at short notice homogeneous bulky; Plasticator above-mentioned block material, through the shear action of two different rotating speeds running rollers, makes and plasticates more Evenly; Calender is pressed into the semi-finished product sheet to above-mentioned homogeneous material by calender; Laminating machine, Tablet is put into laminating machine after coinciding, under certain temperature and pressure, material is in hot steel plate Flow into a uniformly integral body, material cools off gradually, and it is poly-to obtain the cenosphere filling through sawing Vinyl chloride composite hardboard.
Embodiment 5:
A kind of manufacturing process of cenosphere filling polyvinyl chloride composite material pipe as shown in Figure 3. It comprises: the classification of flyash dust, and can classification from the flyash dust by gas flow sizing machine Go out the cenosphere material of particle diameter 0.5～5um; The high gradient magnetic separator deironing, this magnetic separator is Current version, by magnetic separation, the oxides-containing iron of cenosphere is reduced to from 3%～15% Below 1%; Semiconductor machine de-carbon, carbon granules impurity are a kind of semi-conducting materials, by semiconductor machine Friction pulley changes the electrical of carbon granules, utilizes and electrically remove carbon granule impurity from flyash; Hollow The surface modification treatment of microballon, it is mixed by High Rotation Speed air-flow and its titanate esters modification liquid Close, by superonic flow nozzzle this air-flow mixture is equipped with cenosphere with very high speed spirt again In the fluid bed of suspended substance, can deposit the very thin organic film of one deck on solid cenosphere surface, The temperature of this fluid bed can be regulated and control in normal temperature and 300 ℃ of scopes, this modified layer of making thin and The jail, modification is complete; Drying and processing is by baking oven or hot blast, to the cenosphere of modification and poly-The vinyl chloride powder carries out drying to be processed; Mix, above-mentioned bi-material (2: 8 weight ratios) and Auxiliary agent is by the high-speed mixer mixed processing; Directly extrude composite material tube with double screw extruder Son when extruding, needs the control temperature between 50 ℃～300 ℃.
Embodiment 6
A kind of manufacturing process of coal fly ash hollow micro bead filled nylon-6 6 composites such as Fig. 1 institute Show. It comprises: the classification of flyash dust, and can be from the flyash dust by gas flow sizing machine Classification goes out the cenosphere material of particle diameter 0.5～5um; The high gradient magnetic separator deironing, this magnetic separation Machine is current version, by magnetic separation, the oxides-containing iron of cenosphere is fallen from 3%～15% Low to below 1%; Semiconductor machine de-carbon, carbon granules impurity are a kind of semi-conducting materials, by partly leading The friction pulley of body machine changes the electrical of carbon granules, utilizes and electrically remove carbon granule impurity from flyash; The surface modification treatment of cenosphere, it is by High Rotation Speed air-flow and its stearic acid modified liquid Mix, be equipped with this air-flow mixture hollow little with very high speed spirt by superonic flow nozzzle again In the fluid bed of pearl suspended substance, can deposit very thin organic of one deck on solid cenosphere surface Film, the temperature of this fluid bed can be regulated and control in normal temperature and 300 ℃ of scopes; Drying and processing is by baking Case or hot blast carry out drying to the cenosphere of modification and nylon-66 and process; The two was by 2: 8 Ratio mix, above-mentioned bi-material is passed through the high-speed mixer mixed processing; Extrude or spinning, Namely obtain the goods of cenosphere filled nylon-6 6 composites.
Claims (9)
1, a kind of manufacturing process of coal fly ash hollow micro bead filled resin base composite material comprises: flyash dust raw material is handled the back through classification, deironing, carbon elimination and is obtained the cenosphere of spherical rate more than 90%, and the granularity of cenosphere is 0.5～5um; Carry out surface modification treatment by aerosol processing again, at the very thin organic solution film of cenosphere surface deposition one deck; Then cenosphere (loading level 5～50%), resin-based materials and auxiliary agent by drying treatment, high-speed mixing or stirring again extruded, injection moulding, lamination or alternate manner be shaped.
2, technology according to claim 1, the classification of cenosphere adopt air classification to carry out.
3, technology according to claim 1, the aerosol processing surface modification treatment is that organically-modified solution is mixed with it by the high speed rotating air-flow, by superonic flow nozzzle this air-flow mixture is equipped with in the fluidized-bed of cenosphere suspensoid with very high speed spirt again, can deposit the very thin organic membrane of one deck on solid cenosphere surface, the temperature of this fluidized-bed can be regulated and control in normal temperature and 300 ℃ of scopes.
4, technology according to claim 3, wherein organically-modified solution is selected from one or more in silane, titanic acid ester, stearic acid, the aluminic acid ester.
5, technology according to claim 1, wherein resin-based materials is a macromolecule polymeric material.
6, according to the technology of claim 5, wherein macromolecule polymeric material is selected from one or more in polypropylene, polyvinyl chloride, polyethylene, polymeric amide, polyester, urethane, polyacrylic ester, polymethacrylate, ABS, ASA and the silicon rubber.
7, according to the technology of claim 1, wherein said auxiliary agent is selected from one or more in tinting material, antioxidant, static inhibitor, fire retardant, other weighting agent.
8, the cenosphere that obtains by the technology of claim 1 polymer matrix composites of filling.
9, the purposes of the polymer matrix composites of the cenosphere of claim 8 filling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB011419113A CN1193066C (en) | 2001-09-21 | 2001-09-21 | Process for producing hollow micro bead filled resin base composite material |
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| CNB011419113A CN1193066C (en) | 2001-09-21 | 2001-09-21 | Process for producing hollow micro bead filled resin base composite material |
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| CN1339526A true CN1339526A (en) | 2002-03-13 |
| CN1193066C CN1193066C (en) | 2005-03-16 |
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| CNB011419113A Expired - Fee Related CN1193066C (en) | 2001-09-21 | 2001-09-21 | Process for producing hollow micro bead filled resin base composite material |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100378153C (en) * | 2006-04-11 | 2008-04-02 | 山西新阳新材料有限公司 | Process for preparing nano CaCO3 modified tremolite powder filling master |
| CN100384941C (en) * | 2005-04-16 | 2008-04-30 | 中国科学院合肥物质科学研究院 | Resin/hollow glass bead composite material and its prepn process |
| CN101962474A (en) * | 2010-09-02 | 2011-02-02 | 海聚高分子材料科技（广州）有限公司 | Environment-friendly high-flame retardance rigid polyurethane foam and preparation method and application thereof |
| CN102993553A (en) * | 2011-09-14 | 2013-03-27 | 比亚迪股份有限公司 | Smell master batch and its preparation method |
| CN103214714A (en) * | 2013-03-26 | 2013-07-24 | 安徽五洲特种电缆集团有限公司 | Silicone-rubber-insulated control cable outer protective sleeve material, and preparation method thereof |
| CN104086883A (en) * | 2014-07-03 | 2014-10-08 | 合肥杰事杰新材料股份有限公司 | Mobile phone noise reduction cover material and preparation method thereof |
| CN106496790A (en) * | 2016-10-27 | 2017-03-15 | 福州大学 | A kind of fly ash hollow ball/PP composites and preparation method thereof |
| CN108084498A (en) * | 2017-12-29 | 2018-05-29 | 成都新柯力化工科技有限公司 | A kind of thermoplastic cellular konilite and preparation method for plastics |
| CN112916200A (en) * | 2019-12-05 | 2021-06-08 | 山西奇色环保科技有限公司 | Method for preparing plastic filler by taking gasified slag as raw material |
| CN113652089A (en) * | 2021-01-12 | 2021-11-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gradient hollow microsphere enhanced high-speed impact resistant composite material and preparation method and application thereof |
| CN115322560A (en) * | 2022-08-24 | 2022-11-11 | 湖北合聚新材料有限公司 | Wear-resistant nylon material and preparation method and application thereof |
| CN116061483A (en) * | 2023-02-09 | 2023-05-05 | 深圳市赛尔美电子科技有限公司 | Manufacturing method of heat insulation shell and heat insulation shell |
-
2001
- 2001-09-21 CN CNB011419113A patent/CN1193066C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384941C (en) * | 2005-04-16 | 2008-04-30 | 中国科学院合肥物质科学研究院 | Resin/hollow glass bead composite material and its prepn process |
| CN100378153C (en) * | 2006-04-11 | 2008-04-02 | 山西新阳新材料有限公司 | Process for preparing nano CaCO3 modified tremolite powder filling master |
| CN101962474A (en) * | 2010-09-02 | 2011-02-02 | 海聚高分子材料科技（广州）有限公司 | Environment-friendly high-flame retardance rigid polyurethane foam and preparation method and application thereof |
| CN102993553A (en) * | 2011-09-14 | 2013-03-27 | 比亚迪股份有限公司 | Smell master batch and its preparation method |
| CN103214714B (en) * | 2013-03-26 | 2016-02-10 | 安徽五洲特种电缆集团有限公司 | A kind of silicon rubber insulating control cable oversheath material and preparation method thereof |
| CN103214714A (en) * | 2013-03-26 | 2013-07-24 | 安徽五洲特种电缆集团有限公司 | Silicone-rubber-insulated control cable outer protective sleeve material, and preparation method thereof |
| CN104086883A (en) * | 2014-07-03 | 2014-10-08 | 合肥杰事杰新材料股份有限公司 | Mobile phone noise reduction cover material and preparation method thereof |
| CN106496790A (en) * | 2016-10-27 | 2017-03-15 | 福州大学 | A kind of fly ash hollow ball/PP composites and preparation method thereof |
| CN108084498A (en) * | 2017-12-29 | 2018-05-29 | 成都新柯力化工科技有限公司 | A kind of thermoplastic cellular konilite and preparation method for plastics |
| CN112916200A (en) * | 2019-12-05 | 2021-06-08 | 山西奇色环保科技有限公司 | Method for preparing plastic filler by taking gasified slag as raw material |
| CN112916200B (en) * | 2019-12-05 | 2022-06-17 | 山西奇色环保科技股份有限公司 | Method for preparing plastic filler by taking gasified slag as raw material |
| CN113652089A (en) * | 2021-01-12 | 2021-11-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gradient hollow microsphere enhanced high-speed impact resistant composite material and preparation method and application thereof |
| CN113652089B (en) * | 2021-01-12 | 2022-08-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gradient hollow microsphere enhanced high-speed impact resistant composite material and preparation method and application thereof |
| CN115322560A (en) * | 2022-08-24 | 2022-11-11 | 湖北合聚新材料有限公司 | Wear-resistant nylon material and preparation method and application thereof |
| CN116061483A (en) * | 2023-02-09 | 2023-05-05 | 深圳市赛尔美电子科技有限公司 | Manufacturing method of heat insulation shell and heat insulation shell |
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| CN1193066C (en) | 2005-03-16 |
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