CN1207135C - Method for making microporous foamed engineering plastic by mould pressing - Google Patents
Method for making microporous foamed engineering plastic by mould pressing Download PDFInfo
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- CN1207135C CN1207135C CN 03118818 CN03118818A CN1207135C CN 1207135 C CN1207135 C CN 1207135C CN 03118818 CN03118818 CN 03118818 CN 03118818 A CN03118818 A CN 03118818A CN 1207135 C CN1207135 C CN 1207135C
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Abstract
The present invention discloses a method for a preparing micro-hole foamed engineering plastic with a die pressing method. Carrier resins and foamer are mixed at the temperature of 100 to 120DEGC to prepare foamer base materials; the foamer base materials and the engineering plastic are put into a die cavity in common, the die is arranged on a heat pressing machine at the temperature of 130 to 230DEGC, pressure less than 20MPas is exerted, and the foamer base materials and the engineering plastic are foamed by constant pressure; and the pressure is relieved, and a foamed test sample is taken out from the die and is cooled. Compared with the existing micre-hole foaming technique, the method is suitable for engineering plastics which are not suitable for being processed with a specific micro-hole foaming, extruding and injecting method. An ordinary heat pressing machine is used for processing, and therefore, the preparation cost of the micro-hole foamed engineering plastic is low. Through improving processing temperature, accelerating gas diffusion in a polymer, and reducing processing time, processing efficiency is improved. The method has the advantages of simple process flow, easy operation, mild processing condition and strong adaptability, can be used for the micro-hole foaming and processing of a polymer at high glass transition temperature, and is suitable for popularization and use.
Description
Technical field
The invention belongs to the microporous foam technology, be specifically related to process the microporous foam technology of the low engineering plastics of melt viscosity.
Background technology
Microcellular foam material is meant cell diameter between 5～100 μ m, and density of material reduces by 5～95% thermal plasticity high polymer, and its basic conception is in the eighties in 20th century, by professor's Suh proposition of Massachusetts Institute Technology.His basic imagination is that the inorganic particulate according to small particle diameter can strengthen, the fact of toughened plastics, can proposition use that the bubble less than the critical crack size of polymeric material strengthens, the toughening polymer material, reaches the weight of the density that both reduces material, lightening material and improve the purpose of material property.Show that through 20 years of researches the micropore foamed polymer material has good physical and mechanical properties, long as notched Izod impact strength height, good toughness, intensity height, fatigue life, good insulation preformance, advantage such as dielectric constant is low.
At present, the processing forward industrialization direction of microcellular foam material is flourish, and is wherein successful to the development and the exploitation of microcellular foam material with the Suh group of Massachusetts Institute Technology especially.The eighties, they prepared micropore polystyrene (PS) material with the still platen press, and the nineties is semicontinuous production PS microcellular foam on extruder, adopted again subsequently and extruded the production capillary copolymer material continuously; 1994, this technology transfer to the Trexel company of the U.S., is begun to change breadboard achievement in research over to industrial-scale production, and the trade mark registration that will produce microcellular foam material is Mucell.Trexel company and famous material processing plant company such as the Krass Maffei of the whole world tens families, Uniloy-Milacron, Engel, Husky, Arburg, Alusisse Composite etc. develops equipment such as to be used for the extruding of microcellular foam material processing, injection and blowing cooperatively, and is used for multiple MICROCELLULAR FOAM POLYMER MATERIALS such as suitability for industrialized production polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polysulfones (PSU), thermoplastic elastomer (TPE).And China is at the early-stage at the microporous foam manufacture field, prepare the microporous foam composite and applied for patent with the still platen press as the He Jiasong of Institute of Chemistry, Academia Sinica in recent years, South China Science ﹠ Engineering University is also developing the continuous extrusion equipment of microporous foam processing.
In general, the technical process of microporous foam processing can be divided into following three phases: the formation of (1) gas-polymer homogeneous system; (2) reduce pressure or rising temperature, system becomes the supersaturation attitude, the gas homogeneous nucleation; (3) complex growth and cooling and shaping.For the still platen press, owing to adopt and diffuse into the homogeneous system that forms gas-polymer in the polymer with gases at high pressure at normal temperatures, pressure is up to 25MPa, because of temperature low, the diffusion velocity of gas is very slow, the time that forms homogeneous system is long, generally more than 20 hours, and is not suitable for industrialized production; For extrude continuously, processing method such as injection or blowing, it is not suitable for being used for processing the low macromolecular material of melt viscosity; And its technical process needs to plastify, each stage coordination such as formation, gas nucleation, air bubble growth control and setting of the injection of gas, homogeneous system, need complicated process equipment and strict process condition, microcellular foam material manufacturing cost height, complicated operation.Only have at present by equipment such as extruding of having that molding machine manufacturer that the Patent right Trexel of microporous polymer company authorizes can the production capillary processing, injections.The enforcement of this patent needs complicated process equipment and strict process condition, microcellular foam material manufacturing cost height, complicated operation.
Summary of the invention
The object of the present invention is to provide a kind of technology simple, utilize the preparation method of the die pressing microporous foam engineering plastics that common hot press processes, to overcome the defective of above-mentioned patent and technology.
Technical scheme of the present invention is: it is vector resin and blowing agent to be carried out mixing at 100～120 ℃, makes the blowing agent base material; Blowing agent base material and engineering plastics are put into mold cavity jointly, and mould placed on 120～230 ℃ the hot press, applies the pressure of 8～20MPa, through foaming in 2～20 minutes; Release is taken out in the sample from mould that will foam, cooling.
Identical or have a temperature difference between the temperature of the temperature of upper plate and lower plate in the described hot press.
Carrying out also adding crosslinking agent when mixing.
Going up plate temperature in the hot press is 180～230 ℃, and following plate temperature is 120～200 ℃.
The weight part ratio of blowing agent, vector resin, crosslinking agent is: 4～30: 100: 0.1～10.
The present invention compares with existing microporous foam technology, has following advantage: the present invention is applicable to and should not adopts special microporous foam to extrude the engineering plastics of processing with injection.The equipment that its uses be the mould of common hot press and no special seal as the capital equipment of processing, cost of equipment is cheap, the microcellular foam material preparation cost is low.It controls the decomposition rate of blowing agent by the mode of control temperature, the pressure constant state that maintenance system is long, encapsulant that need not be special and encapsulating method.Crucial is it by improving processing temperature, quicken the diffusion of gas in polymer, reduce process time, improved the efficient of processing.Technological process of the present invention is simple, easy operating, processing conditions gentleness, adaptability are strong, can be used for the microporous foam processing of the higher polymer of vitrification point, should promote the use of.
The specific embodiment
Blowing agent is selected Celogen Az, diisopropyl azodiformate, N for use, N-dinitroso five methine tetramines, 3,3-disulfonyl diphenyl sulphone (DPS), 4, a kind of in the 4-OBSH.
Vector resin is selected polyethylene, polypropylene for use, EP rubbers, butadiene-styrene rubber, acrylonitrile-butadiene-styrene (ABS), a kind of in the natural rubber.
Engineering plastics select polybutylene terephthalate (PBT), Merlon, polyether-ether-ketone, a kind of in the polyimides.Above-mentioned engineering plastics are sheet.
Embodiment 1
With 4 parts of Celogen Azs (AC), 100 parts of polyethylene (PE) and 0.1 part of cumyl peroxide (DCP) in 100～120 ℃ the time in two roller mills mixing evenly, preparation blowing agent base material.
With blowing agent base material and PETG (PET) sample put into die cavity jointly, mould places on the hot press, plate temperature is at 185 ± 5 ℃ on the hot press, and following plate temperature is preheated to the vector resin fusion at 125 ± 5 ℃, apply 8～20MPa, constant voltage 3～20Min foaming.
Release, cooling PET sample promptly makes microporous PE T expanded material.
Embodiment 2
With 12 parts of Celogen Azs (AC), 100 parts of polyethylene (PE) and 1 part of cumyl peroxide (DCP) in 100～120 ℃ the time in two roller mills mixing evenly, preparation blowing agent base material.
With blowing agent base material and PETG (PET) sample put into die cavity jointly, mould places on the hot press, plate temperature is at 200 ± 5 ℃ on the hot press, and following plate temperature is preheated to the vector resin fusion at 155 ± 5 ℃, apply 8～20MPa, constant voltage 3～20Min foaming.
Release, cooling PET sample promptly makes microporous PE T expanded material.
Embodiment 3
With 30 parts of Celogen Azs (AC), 100 parts of polyethylene (PE) and 10 parts of cumyl peroxides (DCP) in 100～120 ℃ the time in two roller mills mixing evenly, preparation blowing agent base material.
With blowing agent base material and PETG (PET) sample put into die cavity jointly, mould places on the hot press, plate temperature is at 225 ± 5 ℃ on the hot press, and following plate temperature is preheated to the vector resin fusion at 165 ± 5 ℃, apply 8～20MPa, constant voltage 3～20Min foaming.
Release, cooling PET sample promptly makes microporous PE T expanded material.
Embodiment 4
With the cumyl peroxide (DCP) of 12 parts of Celogen Azs (AC), 100 parts of polyethylene (PE) and 1 in 100～120 ℃ the time in two roller mills mixing evenly, preparation blowing agent base material.
With blowing agent base material and PETG (PET) sample put into die cavity jointly, mould places on the hot press, plate temperature is at 195 ± 5 ℃ on the hot press, and following plate temperature is preheated to the vector resin fusion at 195 ± 5 ℃, apply 8～20MPa, constant voltage 2Min foaming.
Release, cooling PET sample promptly makes microporous PE T expanded material.
Embodiment 5
With the cumyl peroxide (DCP) of 12 parts of Celogen Azs (AC), 100 parts of polyethylene (PE) and 1 part in 100～120 ℃ the time in two roller mills mixing evenly, preparation blowing agent base material.
With blowing agent base material and PETG (PET) sample put into die cavity jointly, mould places on the hot press, plate temperature is at 195 ± 5 ℃ on the hot press, and following plate temperature is preheated to the vector resin fusion at 195 ± 5 ℃, apply 8～20MPa, constant voltage 20Min foaming.
Release, cooling PET sample promptly makes microporous PE T expanded material.
5 embodiment that make the results are shown in Table 1
Table 1:
Cell diameter relative density density reduces the intensity elongation at break
(μm) (％) (MPa) (％)
PET
★ 1 164 96
Embodiment one
171 0.79 21 172 128
Embodiment two
260 0.58 42 183 136
Embodiment three
343 0.43 57 177 145
Embodiment four
452 0.75 25 185 138
Embodiment five
597 0.56 44 155 95
★ is a control sample; 1,2,3 is temperature differential method; 4,5 is isothermal method.
Claims (10)
1, a kind of preparation method of die pressing microporous foam engineering plastics is characterized in that: it is vector resin and blowing agent to be carried out mixing at 100～120 ℃, makes the blowing agent base material; Blowing agent base material and engineering plastics are put into mold cavity jointly, and mould placed on 120～230 ℃ the hot press, applies the pressure of 8～20MPa, through foaming in 2～20 minutes; Release is taken out in the sample from mould that will foam, cooling.
2, the preparation method of die pressing microporous foam engineering plastics according to claim 1 is characterized in that: identical or have a temperature difference between the temperature of the temperature of upper plate and lower plate in the described hot press.
3, the preparation method of die pressing microporous foam engineering plastics according to claim 1 is characterized in that: going up plate temperature in the described hot press is 180～230 ℃, and following plate temperature is 120～200 ℃.
4, the preparation method of die pressing microporous foam engineering plastics according to claim 1, it is characterized in that: described blowing agent is selected Celogen Az, diisopropyl azodiformate, N for use, N-dinitroso five methine tetramines, 3,3-disulfonyl diphenyl sulphone (DPS), 4, a kind of in the 4-OBSH.。
5, the preparation method of die pressing microporous foam engineering plastics according to claim 1, it is characterized in that: described vector resin is selected polyethylene, polypropylene for use, EP rubbers, butadiene-styrene rubber, acrylonitrile-butadiene-styrene (ABS), a kind of in the natural rubber.
6, the preparation method of die pressing microporous foam engineering plastics according to claim 1, it is characterized in that: described engineering plastics select polybutylene terephthalate (PBT), Merlon, polyether-ether-ketone, a kind of in the polyimides.
7, as the preparation method of die pressing microporous foam engineering plastics as described in the claim 6, it is characterized in that: described engineering plastics are sheets.
8, the preparation method of die pressing microporous foam engineering plastics according to claim 1 is characterized in that: carrying out also adding crosslinking agent when mixing.
9, as the preparation method of die pressing microporous foam engineering plastics as described in the claim 8, it is characterized in that: crosslinking agent adopts cumyl peroxide.
10, as the preparation method of die pressing microporous foam engineering plastics as described in the claim 8, it is characterized in that: the weight part ratio of blowing agent, vector resin, crosslinking agent is: 4～30: 100: 0.1～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118818 CN1207135C (en) | 2003-03-21 | 2003-03-21 | Method for making microporous foamed engineering plastic by mould pressing |
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| CN 03118818 CN1207135C (en) | 2003-03-21 | 2003-03-21 | Method for making microporous foamed engineering plastic by mould pressing |
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| CN1438104A CN1438104A (en) | 2003-08-27 |
| CN1207135C true CN1207135C (en) | 2005-06-22 |
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| CN 03118818 Expired - Fee Related CN1207135C (en) | 2003-03-21 | 2003-03-21 | Method for making microporous foamed engineering plastic by mould pressing |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100346956C (en) * | 2003-11-26 | 2007-11-07 | 刘坤钟 | Manufacturing method of foam with air holes |
| CN100398290C (en) * | 2005-08-05 | 2008-07-02 | 四川大学 | Method of preparing apertured micropore plastic product semifusion mould press shaping method |
| FR2899145B1 (en) * | 2006-03-29 | 2008-05-09 | Solvay | PROCESS FOR THE PRODUCTION OF AN ALVEOLAR STRUCTURE BASED ON PLASTIC MATERIAL |
| CN101856853B (en) * | 2010-06-18 | 2013-01-30 | 上海俊尔新材料有限公司 | Forming device and preparation method for plastic foam product |
| CN102367328B (en) * | 2011-08-31 | 2014-05-21 | 上海锦湖日丽塑料有限公司 | Microcellular foam PC/ABS alloy material for electroplating and preparation method thereof |
| CN105504754B (en) * | 2015-12-31 | 2017-10-31 | 祥兴(福建)箱包集团有限公司 | A kind of microporous foam makrolon casing and preparation method thereof |
| JP6809696B2 (en) * | 2016-09-09 | 2021-01-06 | 株式会社Ｔｂｍ | Sheet manufacturing method |
| CN107459799A (en) * | 2017-08-02 | 2017-12-12 | 北京汽车股份有限公司 | Composite foam material and preparation method thereof, part and automobile |
| CN107953647A (en) * | 2017-12-14 | 2018-04-24 | 祥兴(福建)箱包集团有限公司 | The method that chemical blowing prepares microporous polycarbonate composite sheet |
| CN107962718A (en) * | 2017-12-14 | 2018-04-27 | 祥兴(福建)箱包集团有限公司 | The method that chemical blowing prepares enhanced microporous polycarbonate composite sheet |
| CN108285578B (en) * | 2018-02-09 | 2020-08-18 | 郑州大学 | Preparation method of PP/ABS micro-foaming material |
| CN110876817B (en) * | 2019-08-22 | 2022-03-04 | 浙江师范大学 | Porous PEEK (polyetheretherketone) bionic bone repair material, PEEK bionic bone part with multilayer structure and preparation method thereof |
| CN110527129B (en) * | 2019-10-18 | 2021-06-04 | 吉林大学 | Polyether-ether-ketone porous foam material and preparation method thereof |
| CN111234301B (en) * | 2020-01-19 | 2021-07-30 | 吉林大学 | Polyether ketone ether ketone porous foam material and preparation method thereof |
| CN114750495A (en) * | 2022-03-25 | 2022-07-15 | 浙江普凯新材料有限公司 | Antibacterial and anti-aging PET (polyethylene terephthalate) sheet and preparation method thereof |
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