CN1176146C - Process for preparing dynamic cured epoxy resin/polypropylene blend - Google Patents
Process for preparing dynamic cured epoxy resin/polypropylene blend Download PDFInfo
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- CN1176146C CN1176146C CNB021550077A CN02155007A CN1176146C CN 1176146 C CN1176146 C CN 1176146C CN B021550077 A CNB021550077 A CN B021550077A CN 02155007 A CN02155007 A CN 02155007A CN 1176146 C CN1176146 C CN 1176146C
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Abstract
The present invention provides a process for preparing a dynamic cured epoxy resin/polypropylene blend. In a Banbury mixer, a blender mill or a screw extruder, at a certain blending temperature, polypropylene grafted by maleic anhydride, epoxy resin and a curing agent are orderly added in polypropylene resin for mixing; the epoxy resin is cured in situ and is dispersed into micron order particles under the function of high shear force, and the micron order particles are evenly distributed in the polypropylene so as to enhance the rigidity and the modulus of the polypropylene; the prepared blend can satisfy the requirements of engineering materials. The process has the advantages of simple production technology, good machining performance, strong applicability, etc.; the prepared dynamic cured epoxy resin/polypropylene blend can be used for civil constructions, automobile fittings, household appliances and other materials.
Description
Technical field: the present invention relates to a kind of preparation method of blend polymer, particularly a kind of preparation method of dynamical cure Resins, epoxy/polypropylene blend.
Background technology: 1962, U.S. A.M.Gessler at first proposes to prepare rubber plastic blend type thermoplastic elastomer (US Patent 3 with dynamic vulcanization process, 037,954), after after the K.Fisher systematic study of U.S. Uniroyal company, the said firm developed dynamic part sulfuration EPT rubber/thermoplastic elastomer (USPatent 3,758,643) in 1972.The beginning of the eighties, A.Y.Coran proposed the dynamic full vulcanization technology on the basis of summing up forefathers, by the development research of U.S. Monsanto company, make the dynamic full vulcanization EPT rubber/thermoplastic elastomer, and formally realized suitability for industrialized production with trade(brand)name Santoprene in nineteen eighty-two.The dynamic full vulcanization technology is that rubber and plastics carry out melt blending in mixing machinery, adds vulcanizing agent and other Synergist S-421 95s then, in blend rubber by after crosslinked fully, with dispersed phase distribution in plastics.Machine-shaping is convenient because this thermoplastic elastomer has, and waste material can reuse, the production efficiency height, and the characteristics such as low and high comprehensive performance that consume energy cause the great interest of people.
Dynamic vulcanization technology is mainly used in rubber/plastic blend system, and it is applied to thermosetting resin/thermoplastic resin system, yet there are no 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.Polypropylene is a kind of polyolefin resin of present consumption maximum, has the good mechanical performance, but its rigidity and modulus are not high, is difficult to satisfy the requirement of engineering materials.In order to improve polyacrylic rigidity and modulus, add mineral filler and glass fibre usually therein.
Summary of the invention: the objective of the invention is to dynamic vulcanization technology is applied in Resins, epoxy/polypropylene, propose a kind of novel method of Reinforced Polypropylene.It is simple that this method has production technique, good processability, advantage such as suitability is strong.Polypropylene with maleic anhydride graft of active group can react with hydroxyl in the Resins, epoxy and epoxide group, Resins, epoxy and polyacrylic 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 polypropylene, greatly improved polyacrylic rigidity and modulus.
The preparation method of dynamical cure Resins, epoxy/polypropylene blend of the present invention, be in Banbury mixer, mill or screw extrusion press, under 190-200 ℃ blending temperature, the polypropylene, Resins, epoxy, the solidifying agent that add maleic anhydride graft in acrylic resin successively carry out mixing.Wherein used polypropylene is a homo-polypropylene, its consumption is 50～85 weight parts, the consumption of the polypropylene of maleic anhydride graft (PP-MA) is 10～15 weight parts, content of epoxy resin is 5～50 weight parts, hardener dose is 0.1～10 weight part, the blend time is 7～15min, obtains dynamical cure Resins, epoxy/polypropylene blend.
The Resins, epoxy that uses among the present invention is bisphenol-A diglycidyl ether type (molecular weight＞500), Bisphenol F diglycidyl ether-type (molecular weight＞500) and line style phenolic aldehyde polyglycidyl ether type Resins, epoxy (molecular weight＞400).
The solidifying agent that the present invention uses is dicyanamide, imidazolium compounds (glyoxal ethyline, 2-ethyl-4-methylimidazole (EMI-2,4) etc.) and dihydrazide compound (adipic dihydrazide, m-phthalic acid two hydrazides, certain herbaceous plants with big flowers hydrazine etc.).
Dynamical cure Resins, epoxy/polypropylene blend 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-reinforced polypropylene 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: following embodiment is to further specify of the present invention, rather than restriction the present invention.
The preparation method of embodiment 1-7 dynamical cure Resins, epoxy/polypropylene blend
By the prescription in the table-1, under 190 ℃ temperature, in Banbury mixer or mill, at first add polypropylene, add PP-MA, Resins, epoxy (bisphenol-A diglycidyl ether type then successively, the trade mark: DGEBA), 2-ethyl-4-methylimidazole (EMI-2,4), Resins, epoxy generation curing reaction in the blend process, and under high shear, disperse to be particulate state and be distributed in the polypropylene.The blend that makes is in blocks with the vulcanizing press mold pressing.Tailor batten by standard size, sample is pressed ASTM D638 respectively, ASTM D790, performance index such as ASTM D256 standard testing stretching, bending, impact.
Test result is shown in table-1.
Table-1
Example 1234567
Prescription (parts by weight)
Polypropylene 85 80 70 60 40 95 100
Resins, epoxy (DGEBA) 5 10 20 30 50
PP-MA 10 10 10 10 10
EMI-2，4 0.2 0.4 0.8 1.2 2
CaCO
3 5
Physical and mechanical properties
Shock strength, J/m 33 36 33 42 34 24 30
Tensile strength, MPa 34.8 35 34.2 33.1 35.2 32.1 30.6
Elongation at break, % 10.6 6.9 4.3 3.6 3.0 142 450
Modulus in flexure, MPa 1,785 1,808 1,926 2,003 2,227 1,675 1245
The preparation method of embodiment 8-14 dynamical cure Resins, epoxy/polypropylene blend
By the prescription in the table-2, under 190 ℃ temperature, in Banbury mixer or mill, at first add polypropylene, add PP-MA, Resins, epoxy (bisphenol-A diglycidyl ether type then successively, the trade mark: DGEBA), the dicyanamide solidifying agent, Resins, epoxy dynamical cure in the blend process.Specimen preparation and testing standard are operated by example 1-7.Test result is shown in table-2.
Table-2
Example 89 10 11 12 13 14
Prescription (parts by weight)
Polypropylene 85 80 70 60 40 85 95
Resins, epoxy 5 10 20 30 50 10
PP-MA 10 10 10 10 10
Dicyanamide 0.1 0.4 0.8 1.2 2
Polynite 5
Glass fibre 5
Physical and mechanical properties
Shock strength, J/m 28 29 29 30 29 26 23
Tensile strength, MPa 34.0 33.5 34.9 33.8 35.2 33.4 31.4
Elongation at break, % 6.5 5.6 8.2 3.2 3.0 21 15
Modulus in flexure, MPa 1,714 1,767 1,865 2,040 2,210 1,675 1696
Claims (3)
1. dynamical cure Resins, epoxy/polypropylene blend preparation method, it is characterized in that, at Banbury mixer, in mill or the screw extrusion press, under 190-200 ℃ blending temperature, the polypropylene that in acrylic resin, adds maleic anhydride graft successively, Resins, epoxy, solidifying agent carries out mixing, wherein used polypropylene is a homo-polypropylene, its consumption is 50～85 weight parts, the polyacrylic consumption of maleic anhydride graft is 10～15 weight parts, content of epoxy resin is 5～50 weight parts, hardener dose is 0.1～10 weight part, and the blend time is 7～15min, obtains dynamical cure Resins, epoxy/polypropylene blend.
2. dynamical cure Resins, epoxy according to claim 1/polypropylene blend preparation method is characterized in that used Resins, epoxy is bisphenol-A diglycidyl ether type, molecular weight＞500; The Bisphenol F diglycidyl ether-type, molecular weight＞500 or line style phenolic aldehyde polyglycidyl ether type Resins, epoxy, molecular weight＞400.
3. dynamical cure Resins, epoxy according to claim 1/polypropylene blend preparation method is characterized in that used solidifying agent is a dicyanamide, glyoxal ethyline, 2-ethyl-4-methylimidazole, adipic dihydrazide, m-phthalic acid two hydrazides or certain herbaceous plants with big flowers hydrazine.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021550077A CN1176146C (en) | 2002-12-19 | 2002-12-19 | Process for preparing dynamic cured epoxy resin/polypropylene blend |
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| CNB021550077A CN1176146C (en) | 2002-12-19 | 2002-12-19 | Process for preparing dynamic cured epoxy resin/polypropylene blend |
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| CN1425709A CN1425709A (en) | 2003-06-25 |
| CN1176146C true CN1176146C (en) | 2004-11-17 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300239C (en) * | 2004-05-27 | 2007-02-14 | 上海交通大学 | Preparation of electrostatic resistant and conductive polypropylene blend |
| CN1320053C (en) * | 2005-12-29 | 2007-06-06 | 上海交通大学 | Process for preparing thermoplastic phenolic aldehyde resin/polypropylene coblend |
| CN102002188A (en) * | 2010-11-17 | 2011-04-06 | 武汉工程大学 | Method for preparing dynamic curing epoxy resin, inorganic filler and polyolefin composite |
| 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 |
| CN103724809B (en) * | 2013-12-31 | 2016-07-06 | 张锦碧 | A kind of additive of epoxy resin preparation method |
| CN103756144A (en) * | 2014-01-07 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Low-linear expansion scratch-resistant highlight polypropylene composite material |
| 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 |
| CN109135051A (en) * | 2018-07-12 | 2019-01-04 | 田秋珍 | A kind of preparation method of high-intensity wood plastic composite |
| CN109929170A (en) * | 2019-03-12 | 2019-06-25 | 扬州亚光电缆有限公司 | A kind of polyethylene foamed composite material, preparation method and the application in low-and high-frequency cable product |
| CN114410016B (en) * | 2021-12-17 | 2023-10-13 | 国家能源集团宁夏煤业有限责任公司 | Polypropylene composition, method for preparing toughened impact-resistant copolymer polypropylene resin, toughened impact-resistant copolymer polypropylene resin and application thereof |
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