CN102002188A - Method for preparing dynamic curing epoxy resin, inorganic filler and polyolefin composite - Google Patents
Method for preparing dynamic curing epoxy resin, inorganic filler and polyolefin composite Download PDFInfo
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- CN102002188A CN102002188A CN 201010547840 CN201010547840A CN102002188A CN 102002188 A CN102002188 A CN 102002188A CN 201010547840 CN201010547840 CN 201010547840 CN 201010547840 A CN201010547840 A CN 201010547840A CN 102002188 A CN102002188 A CN 102002188A
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Abstract
The invention relates to a method for preparing a dynamic curing epoxy resin, inorganic filler and polyolefin composite, comprising the following steps: adding inorganic filler, maleic anhydride grafted polyolefin, epoxy resin and a curing agent in sequence to the polyolefin in an internal mixer, an open mill or a screw extruder, and mixing the materials to obtain the dynamic curing epoxy resin, inorganic filler and polyolefin composite, wherein the used polyolefin is homopolymerized polyolefin and the mixing time is 5-20min. The dynamic curing epoxy resin, inorganic filler and polyolefin composite prepared by the method of the invention has stable performance and strong applicability, can meet requirements of engineering materials, can be used as a material for civil construction, automobile parts, household appliances and the like. The preparation method of the invention is convenient to operate and has simple processes and good industrialized prospects. Compared with the traditional inorganic fillers and glass fibre reinforcement polyolefin, the tensile strength and impulse strengthen of the materials prepared by the method of the invention are slightly improved under the condition that the rigidity and modulus are not reduced.
Description
Technical field
The present invention relates to a kind of preparation method of polymer composites, the preparation method of particularly a kind of dynamical cure Resins, epoxy/mineral filler/composite polyolefine material.
Background technology
Dynamic vulcanization technology is mainly used in rubber/plastic blend system, and it is applied to thermosetting resin/thermoplastic resin system, rare bibliographical information.Resins, epoxy is a kind of important thermosetting resin, have excellent cementability, wear resistance, electrical insulation capability, chemical stability, resistant of high or low temperature, high modulus and rigidity and advantages such as shrinking percentage is low, easy machine-shaping, at tackiness agent, electronic instrument, light industry, building, machinery, space flight and aviation, coating, bonding and electric insulating material, be used widely in fields such as advanced composite material matrix.Polyolefine such as polyethylene, polypropylene are two kinds of thermoplastic resins of present consumption maximum, have good mechanical performance and processing characteristics, but its rigidity and modulus are not high, are difficult to satisfy the requirement of engineering materials.In order to improve polyolefinic rigidity and modulus, add mineral filler, glass fibre etc. usually therein.
Though add the rigidity that the mineral filler filler can improve material to a certain extent in the polyolefine, mineral filler polarity is stronger, and is relatively poor with nonpolar polyolefine interface compatibility, often make matrix become more crisp, reduced the impact property of matrix material, and mobile variation, be unfavorable for processing.In order to address this problem,,, improve the various performances of matrix material to increase the cohesive force between polyolefine and filler by means of coupling agent inorganic filler surface is carried out modification habitually in the past.Though coupling agent has stronger interaction with inorganic filler surface, its functional group and nonpolar polyolefine difficulty have stronger interaction.Adopt modified polyolefin of common occurrence as interface modifier, its application is increasingly extensive, as acrylic acid-grafted polyolefine and maleic anhydride graft polyolefine the performance of polyolefine/inorganic filler composite material is had to a certain degree modification.
Summary of the invention
Problem to be solved by this invention is the preparation method who proposes a kind of dynamical cure Resins, epoxy/mineral filler/composite polyolefine material at above-mentioned prior art, and production technique is simple, good processability, advantage such as suitability is strong.
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: the preparation method of dynamical cure Resins, epoxy/mineral filler/composite polyolefine material, it is characterized in that including following steps: at Banbury mixer, in mill or the screw extrusion press, under 160-220 ℃ blending temperature, in polyolefine, add mineral filler successively, the polyolefine of maleic anhydride graft, Resins, epoxy, solidifying agent carries out mixing, wherein used polyolefine is the homopolymerization polyolefine, the shared parts by weight of each raw material: polyolefine is 100 weight parts, the consumption of mineral filler is 5～70 weight parts, the polyolefinic consumption of maleic anhydride graft is 1～15 weight part, content of epoxy resin is 1～20 weight part, hardener dose is 0.1～5 weight part, the blend time is 5～20min, obtains dynamical cure Resins, epoxy/mineral filler/composite polyolefine material.
Press such scheme, described polyolefine is the multipolymer of polypropylene, polyethylene or ethylene-octene.
Press such scheme, the polyolefine of described maleic anhydride graft is the polypropylene (PP-MA) of maleic anhydride graft, the polyethylene (PE-MA) of maleic anhydride graft or the ethylene-octene copolymer (POE-MA) of maleic anhydride graft.
Press such scheme, described Resins, epoxy is bisphenol-A diglycidyl ether type epoxy resin, and its molecular weight is 500～2000, the Bisphenol F diglycidyl ether-type epoxy resin, its molecular weight is 500～2000 or line style phenolic aldehyde polyglycidyl ether type Resins, epoxy, and its molecular weight is 500～2000.
Press such scheme, described solidifying agent is dicyanamide, imidazolium compounds or dihydrazide compound.
Press such scheme, described imidazolium compounds is glyoxal ethyline or 2-ethyl 4-methylimidazole (EMI-2,4).
Press such scheme, described dihydrazide compound is an adipic dihydrazide, m-phthalic acid two hydrazides or certain herbaceous plants with big flowers hydrazine.
Press such scheme, described mineral filler is talcum powder, lime carbonate, silicon powder or potter's clay, and its diameter of particle is 50～300 orders.
The present invention is applied to dynamic vulcanization technology in Resins, epoxy/mineral filler/polyolefine, proposes a kind of increase polyolefine/inorganic filler composite material interface interaction and promotes mineral filler homodisperse novel method in polyolefin substrate.It is simple that this method has production technique, good processability, advantage such as suitability is strong.Polyolefine with maleic anhydride graft of active group can react with hydroxyl in the Resins, epoxy and epoxide group, Resins, epoxy and polyolefinic consistency have been promoted, after adding solidifying agent, because under the effect of high shear force, Resins, epoxy " solidifies on the spot " and is dispersed into micron particles, be evenly distributed in the polyolefine, greatly improved polyolefinic rigidity and modulus.
Dynamical cure Resins, epoxy/mineral filler/composite polyolefine material that the present invention makes, stable performance, suitability is strong, can satisfy the requirement of engineering materials, can be used as materials such as civil construction, auto parts machinery, household electrical appliance.Preparation method provided by the present invention is easy to operate, and technology is simple, and excellent industrial application foreground is arranged.Compare with glass fiber reinforced polyester alkene with conventional inorganic fillers, the material that the present invention makes, under the condition that rigidity and modulus do not reduce, tensile strength and shock strength have raising slightly.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
The preparation method of embodiment 1-7 dynamical cure Resins, epoxy/mineral filler/composite polyolefine material
By the prescription in the table-1, under 190 ℃ temperature, in Banbury mixer or mill, at first add polypropylene, add lime carbonate (200 order) or talcum powder, PP-MA, Resins, epoxy (bisphenol-A diglycidyl ether type epoxy resin then successively, the trade mark: DGEBA, molecular weight are 500～2000), 2-ethyl 4-methylimidazole (EMI-2,4), the blend time is 10 minutes, discharging.The matrix material that makes is in blocks with the vulcanizing press mold pressing.Tailor batten by standard size, sample is pressed ASTMD638 respectively, ASTM D790, performance index such as ASTM D256 standard testing stretching, bending, impact.Test result is shown in table-1.
Table-1
Example 12345678
Prescription (parts by weight)
Polypropylene 100 100 100 100 100 100 100 100
Resins, epoxy 5 10 15 5 10 15
PP-MA 10 5 10 10 10 15 15
EMI-2，4 0.2?0.4 0.6 0.2 0.4 0.6
Lime carbonate (200 order) 10 10 15 20
Talcum powder 10 15 20
Physical and mechanical properties
Shock strength, J/m 30 30 37 38 42 32 35 37
Tensile strength, MPa 30.5 30.8 34.6 37.3 36.2 34.8 36.7 37.6
Elongation at break, % 410 84 48 29 32 35 34 28
Modulus in flexure, MPa 1,310 1,735 1,898 2,070 2,203 1,877 2,087 2245
The preparation method of embodiment 8-14 dynamical cure Resins, epoxy/mineral filler/composite polyolefine material
By the prescription in the table-2, under 210 ℃ temperature, in Banbury mixer or mill, at first add high density polyethylene(HDPE), add potter's clay (100 order) or silicon powder (100 order), POE-MA, Resins, epoxy (bisphenol-A diglycidyl ether type epoxy resin then successively, the trade mark: DGEBA, molecular weight is 500～2000), the dicyanamide solidifying agent, the blend time is 8 minutes, discharging.Specimen preparation and testing standard are operated by example 1-7.Test result is shown in table-2.
Can find out from table-1 and table-2, Resins, epoxy generation curing reaction in the blend process, and under high shear, dynamical cure Resins, epoxy can promote the interface interaction of polyolefine and mineral filler in the matrix material, cause performance to be improved to some extent, particularly shock strength and modulus in flexure increase are comparatively remarkable.
Table-2
Example 89 10 11 12 13 14
Prescription (parts by weight)
High density polyethylene(HDPE) 100 100 100 100 100 100 100
Resins, epoxy 55 10 5 10 15
POF-MA 10 5 10 10 10 10
Dicyanamide 0.1 0.1 0.2 0.1 0.2 0.3
Potter's clay (100 order) 5 10 15
Silicon powder (100 order) 5 10
Physical and mechanical properties
Shock strength, J/m 28 29 35 38 36 39 37
Tensile strength, MPa 31.0 27.5 33.4 34.8 35.0 33.4 34.3
Elongation at break, % 124 220 78 38 43 41 32
Modulus in flexure, MPa 1,214 1,065 1,365 1,423 1,510 1,375 1396
The preparation method of embodiment 15-20 dynamical cure Resins, epoxy/mineral filler/composite polyolefine material
By the prescription in the table-3, under 190 ℃ temperature, in Banbury mixer or mill, at first add high density polyethylene(HDPE), add potter's clay (100 order) or silicon powder (100 order), POE-MA, Resins, epoxy (Bisphenol F diglycidyl ether-type epoxy resin or line style phenolic aldehyde polyglycidyl ether type Resins, epoxy then successively, molecular weight is 500～2000), adipic dihydrazide, the blend time is 10 minutes, discharging.Specimen preparation and testing standard are operated by example 1-7.Test result is shown in table-3.
Table-3
Example 15 16 17 18 19 20
Prescription (parts by weight)
High density polyethylene(HDPE) 100 100 100 100 100 100
Bisphenol F diglycidylether 55 10
Line style phenolic aldehyde polyglycidyl ether type 5 10
POE-MA 10 5 10 10 10
Adipic dihydrazide 0.4 0.4 0.8 0.4 0.8
Potter's clay (100 order) 5 10 15
Silicon powder (100 order) 5
Physical and mechanical properties
Shock strength, J/m 27 28 36 39 40 39
Tensile strength, MPa 30.4 27.4 34.4 35.8 37.0 34.4
Elongation at break, % 114 203 69 42 46 43
Modulus in flexure, MPa 1,224 1,075 1,375 1,472 1,549 1395
Can find out from table-1～table-3, Resins, epoxy generation curing reaction in the blend process, and under high shear, dynamical cure Resins, epoxy can promote the interface interaction of polyolefine and mineral filler in the matrix material, cause performance to be improved to some extent, particularly shock strength and modulus in flexure increase are comparatively remarkable.
Claims (8)
1. the preparation method of dynamical cure Resins, epoxy/mineral filler/composite polyolefine material, it is characterized in that including following steps: at Banbury mixer, in mill or the screw extrusion press, under 160-220 ℃ blending temperature, in polyolefine, add mineral filler successively, the polyolefine of maleic anhydride graft, Resins, epoxy, solidifying agent carries out mixing, wherein used polyolefine is the homopolymerization polyolefine, the shared parts by weight of each raw material: polyolefine is 100 weight parts, the consumption of mineral filler is 5～70 weight parts, the polyolefinic consumption of maleic anhydride graft is 1～15 weight part, content of epoxy resin is 1～20 weight part, hardener dose is 0.1～5 weight part, the blend time is 5～20min, obtains dynamical cure Resins, epoxy/mineral filler/composite polyolefine material.
2. by the preparation method of the described dynamical cure Resins, epoxy/mineral filler of claim 1/composite polyolefine material, it is characterized in that described polyolefine is the multipolymer of polypropylene, polyethylene or ethylene-octene.
3. by the preparation method of claim 1 or 2 described dynamical cure Resins, epoxy/mineral filler/composite polyolefine materials, the polyolefine that it is characterized in that described maleic anhydride graft is the polypropylene of maleic anhydride graft, the polyethylene of maleic anhydride graft or the ethylene-octene copolymer of maleic anhydride graft.
4. press the preparation method of claim 1 or 2 described dynamical cure Resins, epoxy/mineral filler/composite polyolefine materials, it is characterized in that described Resins, epoxy is bisphenol-A diglycidyl ether type epoxy resin, its molecular weight is 500～2000, the Bisphenol F diglycidyl ether-type epoxy resin, its molecular weight is 500～2000 or line style phenolic aldehyde polyglycidyl ether type Resins, epoxy, and its molecular weight is 500～2000.
5. by the preparation method of claim 1 or 2 described dynamical cure Resins, epoxy/mineral filler/composite polyolefine materials, it is characterized in that described solidifying agent is dicyanamide, imidazolium compounds or dihydrazide compound.
6. by the preparation method of the described dynamical cure Resins, epoxy/mineral filler of claim 5/composite polyolefine material, it is characterized in that described imidazolium compounds is glyoxal ethyline or 2-ethyl-4-methylimidazole.
7. by the preparation method of the described dynamical cure Resins, epoxy/mineral filler of claim 5/composite polyolefine material, it is characterized in that described dihydrazide compound is an adipic dihydrazide, m-phthalic acid two hydrazides or certain herbaceous plants with big flowers hydrazine.
8. by the preparation method of claim 1 or 2 described dynamical cure Resins, epoxy/mineral filler/composite polyolefine materials, it is characterized in that described mineral filler is talcum powder, lime carbonate, silicon powder or potter's clay, its diameter of particle is 50～300 orders.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693596A (en) * | 2013-12-10 | 2015-06-10 | 合肥杰事杰新材料股份有限公司 | Scraping-resistant polypropylene resin and preparation method thereof |
| CN105860227A (en) * | 2016-06-06 | 2016-08-17 | 联塑科技发展(贵阳)有限公司 | EP prepolymer powder modified composite material and preparation method thereof |
| CN106243510A (en) * | 2016-08-29 | 2016-12-21 | 合肥会通新材料有限公司 | A kind of high abrasion modified polypropylene composite material and preparation method thereof |
| CN108794884A (en) * | 2018-05-25 | 2018-11-13 | 宁波星陆汽车部件有限公司 | Nano modification Anti-aging, high-strength degree wheel cover preparation process |
| CN114616279A (en) * | 2019-09-05 | 2022-06-10 | 新加坡科技研究局 | Mechanically reinforced polyolefin composites |
| CN114891249A (en) * | 2022-05-07 | 2022-08-12 | 重庆国际复合材料股份有限公司 | Preparation method of glass fiber reinforced epoxy resin composite material |
Citations (2)
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| CN1425709A (en) * | 2002-12-19 | 2003-06-25 | 上海交通大学 | Process for preparing dynamic cured epoxy resin/polypropylene blend |
| CN101092497A (en) * | 2007-07-26 | 2007-12-26 | 上海交通大学 | Method for preparing composite talcum powder filled material of polypropylene |
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2010
- 2010-11-17 CN CN 201010547840 patent/CN102002188A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1425709A (en) * | 2002-12-19 | 2003-06-25 | 上海交通大学 | Process for preparing dynamic cured epoxy resin/polypropylene blend |
| CN101092497A (en) * | 2007-07-26 | 2007-12-26 | 上海交通大学 | Method for preparing composite talcum powder filled material of polypropylene |
Non-Patent Citations (1)
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| 《中国塑料》 20040430 江学良，等 动态固化聚丙烯/马来酸酐接枝聚丙烯/滑石粉/环氧树脂复合材料研究 12-16 1-8 第18卷, 第4期 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693596A (en) * | 2013-12-10 | 2015-06-10 | 合肥杰事杰新材料股份有限公司 | Scraping-resistant polypropylene resin and preparation method thereof |
| CN104693596B (en) * | 2013-12-10 | 2018-01-09 | 合肥杰事杰新材料股份有限公司 | A kind of scratch-resistant acrylic resin and preparation method |
| CN105860227A (en) * | 2016-06-06 | 2016-08-17 | 联塑科技发展(贵阳)有限公司 | EP prepolymer powder modified composite material and preparation method thereof |
| CN106243510A (en) * | 2016-08-29 | 2016-12-21 | 合肥会通新材料有限公司 | A kind of high abrasion modified polypropylene composite material and preparation method thereof |
| CN108794884A (en) * | 2018-05-25 | 2018-11-13 | 宁波星陆汽车部件有限公司 | Nano modification Anti-aging, high-strength degree wheel cover preparation process |
| CN114616279A (en) * | 2019-09-05 | 2022-06-10 | 新加坡科技研究局 | Mechanically reinforced polyolefin composites |
| CN114891249A (en) * | 2022-05-07 | 2022-08-12 | 重庆国际复合材料股份有限公司 | Preparation method of glass fiber reinforced epoxy resin composite material |
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Application publication date: 20110406 |