CN101580625A - Technology and process of cyclic utilization and cyclic remolding of waste thermosetting plastic (epoxide resin) - Google Patents
Technology and process of cyclic utilization and cyclic remolding of waste thermosetting plastic (epoxide resin) Download PDFInfo
- Publication number
- CN101580625A CN101580625A CNA2008100372723A CN200810037272A CN101580625A CN 101580625 A CN101580625 A CN 101580625A CN A2008100372723 A CNA2008100372723 A CN A2008100372723A CN 200810037272 A CN200810037272 A CN 200810037272A CN 101580625 A CN101580625 A CN 101580625A
- Authority
- CN
- China
- Prior art keywords
- waste
- polyvinyl chloride
- epoxide resin
- epoxy resin
- waste epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a technology and a process of cyclic utilization and cyclic remolding of waste thermosetting plastic (epoxide resin), which realizes an assumption of recycling waste thermosetting plastic (such as waste epoxide resin) on a general thermoplastic processing device for the first time. The process comprises the following steps: crashing waste epoxide resin with a cleaned surface into 100-120 meshes; fully drying the crashed waste epoxide resin (adopting a general vacuum oven for 5-15 minutes at the temperature of 120 DEG C) and then evenly mixing the waste epoxide resin with polyvinyl chloride (or cleaned and crashed waste polyvinyl chloride) according to the following weight proportion part: 100 of waste epoxide resin and 30-400 of polyvinyl chloride (or waste polyvinyl chloride); adding an appropriate amount (0.5-3 percent of formulation total amount generally) of processing additives (such as stabilizing agent, lubricant, and the like); and being processed and formed by an extruder or a hydraulic machine. The product manufactured according to the process has the advantages of high pressure-resistance strength, high tensile strength, strong bending-resistance capacity and strong creep-resistance capacity; the unit strength index of the product is not as good as the corresponding thermosetting plastic-cross-linked epoxide resin, but exceeds the corresponding thermoplastic (such as polyvinyl chloride) and can be recycled; and the process has no solid or liquid waste pollution.
Description
Technical field
The invention of the recycle of a kind of discarded thermoset(ting)plastic (Resins, epoxy) and circulate again molding technology and technology.
Background technology
Plastics are formed by polymer, are divided into thermoplastics and thermosetting resin two big classes.So-called thermosetting resin (also claiming thermoset(ting)plastic) as its name suggests, has the heat hardening shaping characteristics of (also claiming thermosetting to be shaped).In contrast, thermoplastics then has thermoplastic (also claiming thermoplastic) characteristics.Plastics after the thermoplastic must be through overcooling ability solidifying formation.
Thermosetting resin is different with thermoplastics and even metal.Basic reason that can thermoset forming is that thermosetting resin in the process of its machine-shaping chemical reaction has taken place, and has formed firm 3-dimension reticulated microstructure.This 3-dimension reticulated microstructure make its goods hardness height, good rigidly, dimensional stability and strong, the incompressible intensity of creep resisting ability and shear strength height, have insoluble infusible characteristics, thereby be widely used in electronic industry, electrical industry, mechanical industry, automotive industry etc.Common have Resins, epoxy, resol and a urethane etc.
1
Extreme hardness after also in a single day heating is shaped just because of thermoset(ting)plastic can't be dissolved or thermoplastic once more, and the circulation of thermoset(ting)plastic is moulded with recycle again and just become a global problem.
2Take an overall view of the production of countries in the world thermoset(ting)plastic (comprising Resins, epoxy) and in the application in fields such as electronics, electrical equipment, instrument, office appliance, launch vehicle, existing technology in various countries and technology all are feature with once-forming and disposable the use.In academia, thermoset(ting)plastic can't be moulded also precocity final conclusion again.
3
According to estimates, the thermoset(ting)plastic of scrapping global every year has 1,000,000 ton more than.
4The thermoset(ting)plastic that the overwhelming majority scraps has all advanced landfill yard.This not only threatens to environment, especially to the huge waste (thermoset(ting)plastic stems from oil as petroleum chemicals) of resource.
Summary of the invention
The present invention has realized the imagination of the waste and old thermoset(ting)plastic of regeneration (for example waste epoxy resin) on general thermoplastic processing units first.Technological process of the present invention is:
(1) appearance of waste epoxy resin is cleaned,
(2) then it is crushed to 100～150 orders,
(3) fully oven dry (the universal vacuum baking oven, got final product in 5～15 minutes by 120 ℃),
(4) mix by following part by weight with polyvinyl chloride (or the waste polyvinyl chloride after clean the pulverizing)
Evenly: 100 parts of waste epoxy resins: 20～400 parts of polyvinyl chloride (or waste polyvinyl chloride),
(5) add the processing aid (as stablizer, lubricant etc.) of an amount of (be generally prescription total amount 0.5～6%),
(6) shape by forcing machine or hydropress.
What produce by technological process of the present invention is the matrix material of a kind of Resins, epoxy and polyvinyl chloride.The stoichiometric chemistry of this matrix material is characterized as: epoxy resin content is that 20-80% (weight percent), polyvinyl chloride content are 79-16% (weight percent).Other contains on a small quantity processing aid such as stablizer, the lubricant etc. (weight percentage is the 0.5-6% of prescription total amount usually) of (weight percent＜10%).The epoxy particles that the material structure of this matrix material is characterized as island is coated among the external phase of polyvinyl chloride.Combine securely through surface chemical reaction between the polyvinyl chloride of epoxy particles and external phase.
Therefore, the product of making by technological process of the present invention has ultimate compression strength height, tensile strength height, the warp resistance ability is strong, creep resisting ability is strong characteristics.Though its unit tenacity index is not as good as the Resins, epoxy behind the corresponding thermoset(ting)plastic-crosslinked, on corresponding thermoplastic plastic (for example polyvinyl chloride).
The present invention be directed to that recycle waste thermosetting Resins, epoxy proposes.Also cyclic regeneration use once more of product by technological process making of the present invention.
Prescription is to the reconstituted product Effect on Performance
(7) mechanical property of the percentage composition reconstituted product of waste epoxy resin (for example ultimate compression strength, tensile strength, warp resistance intensity etc.) is strengthened gradually along with the increase of waste epoxy resin content in prescription.The kind of other component and the influence of consumption in granularity after the specific performance data are pulverized by waste epoxy resin also and the prescription.Generally speaking, hardness and ultimate compression strength at first strengthen when the percentage composition of waste epoxy resin surpasses 15% in prescription after.When the percentage composition of waste epoxy resin surpasses after 60%, hardness, ultimate compression strength and warp resistance intensity all begin obvious raising.Granularity with waste epoxy resin is that 120 orders are example, and when the percentage composition of waste epoxy resin arrived 80～85%, ultimate compression strength and warp resistance intensity all increased to maximum value.Continue to increase the percentage composition of waste epoxy resin, then each relevant mechanical property all begins obvious decline.
(8) granularity of waste epoxy resin generally speaking, the granularity after waste epoxy resin is pulverized is thin more, the mechanical property of reconstituted product is superior more.But because the pulverizing of waste epoxy resin requires the expenditure of energy, the granularity of requirement is thin more, needs the energy that consumes just many more in the crushing process.Comparatively desirable granularity is 100～150 orders in the practice.
(9) selection of stabilizers and use zinc-stablizer, calcium zinc-stablizer and barium calcium-stablizer (for example: Zinic stearas, barium stearate and calcium stearate) all can use.Consumption should be decided in conjunction with treat the heating intensity that reprocessed plastic(s) are stood in the heating former.With the twin screw extruder is example, if the spiral shell piece is designed to strong shear-type, but material stays the time not long at a shearing section Stagnation, and stabilizing agent dosage can be controlled in 0.5～2%, needn't be too high.If twin screw is tapered arrangement, the gap is less between screw rod, and stabilizing agent dosage can rise to 0.5～3%, but should not be high again.Excessive use stablizer can cause the regenerative response of waste epoxy resin incomplete, descends, becomes fragile thereby cause being moulded the shape mechanical performance of products again.If use the hydropress heating to be shaped, and temperature is controlled between 200～230 ℃, and pressure-controlling is at about 50 normal atmosphere, and the time was controlled at about about 10 minutes, and then stabilizing agent dosage can be controlled between 1～2%.
(10) a small amount of outward appearance of using paraffin wax type or clorafin type lubricant can help to reduce forcing machine energy consumption and improvement extruded product of selection of lubricants and use.But lubricant should not be how with (generally should not more than 3%).Excessive making with lubricator can cause screw rod shearing efficient to reduce, thereby causes the regenerative response of waste epoxy resin incomplete, and then causes being moulded the decline of shape mechanical performance of products again.The excessive back pressure of melt in mouth mould exit that with lubricator also can cause in the forcing machine that make is not enough and then influence the dense property of extruded product quality and the regularity of profile.
(11) other considers according to the mouth mould design details of forcing machine differently, perhaps needs to dispose a Melt Pump to improve the back pressure in exit before the mouth mould of parallel double-screw extruder, makes that the extruded product profile is more regular, quality is more dense, performance is more superior.(detailed ginseng accompanying drawing 1)
Explanation about some details of use of the present invention
(12) selection of forcing machine and screw rod
(12.1) get final product after the general all-purpose double-screw forcing machine of the selection of forcing machine is made an amendment slightly (parallel double-screw extruder or tapered twin screw extruder all can, see for details following).
(12.2) whether screw slenderness ratio is the concrete selection of cord wood and spiral shell piece and arrangement and different according to screw rod.Generally speaking, screw slenderness ratio can be controlled in 24～36.If forcing machine configuration Melt Pump, then screw slenderness ratio can be smaller.Otherwise should be more than 32.
(12.3) kind of other component and consumption in granularity after the spiral shell piece is selected to pulverize according to waste epoxy resin and the prescription and different are to introduce an amount of purpose that is cut into before the compression section of forcing machine.With waste epoxy resin be crushed to～100 orders are example, the angle of shear generally can be controlled between 45～90 °.
(13) selection of extruding dies
(13.1) the general main restriction that is subjected to the shape and size of extruded product of the design of runner runner, not too big adjustable leeway.But when the grinding particle size of waste epoxy resin when the dimensional thickness of thick (for example 50～80 orders) or product is big, runner unimpeded just very important.Yet unimpeded usually the meaning of runner increases runner, widen.In most of the cases this will cause that runner exit place melt back pressure descends, the quality of extruded product is dense inadequately, the neat appearance degree descends.If before the compression section of screw rod, do not introduce shear screw block again, then runner increase, widen also can cause treating melt extrusion be heated inequality and deficiency (for example with bath surface that metal flow passage directly contacts be heated more, the melt body deficiency of being heated mutually).Melt is heated uneven and deficiency can cause the regenerative response of waste epoxy resin incomplete, and then causes being moulded the decline of shape mechanical performance of products again.Remedial measure is to add a controlled heating zone again increasing melt heated time and intensity and to improve the melt back pressure between mouth mould and cooling shaping section, thereby further strengthens the mechanical property of extruded product.
(13.2) the control heating adds the mechanical property that a controlled heating zone can further be strengthened extruded product between mouth mould and cooling shaping section.Further the quantitative scope of strengthening according to this before process operation parameter, the waste epoxy resin of each workshop section after pulverizing granularity and prescription in the influence of the kind of other component and consumption and different.Add a controlled heating zone between extruding dies and follow-up cooling shaping section, this technology is that existing expressing technique of characteristics and extrusion equipment are unexistent, is new feature of the present invention (detailed ginseng accompanying drawing 2).In Development Practice of the present invention, this controlled heating zone is the rectangular pipe design of 7.0 centimetres of coupling 3.0 centimetres of pipes of diameter and 10.0 cm x.Along extruding the controlled heat block that direction is 1～2 assemble type (detailed ginseng accompanying drawing 3).Further production practice need not be confined to above-mentioned size and design details.
(14) regeneration of the selection waste epoxy resin of hydropress and mould and heating are moulded also again and can be realized by hydropress and corresponding mould.The hydropress of universal (being furnished with 0～300 ℃ of heating, temperature control device and 0～100 atmospheric pressure exerting device) gets final product.The permission thickness of maximum cavity is subjected to the grinding particle size on waste epoxy resin in the mould.Especially when the consumption of waste epoxy resin is higher (for example＞50%), grain is thick more, and the allowed thickness of maximum cavity is just thin more in the mould.Ignoring this point can influence waste epoxy resin and polyvinyl chloride uniform distribution in mold cavity, and then causes being moulded the decline of shape mechanical performance of products again.
The performance test of reconstituted product
By regeneration that the present invention produced again the performance of molding product can detect by following relevant international testing method.
Tensile strength ASTM D638-98
Tensile creep modulus ASTM D2990-95
Warp resistance intensity A STM 790
Texturing temperature ASTM D648-98c
Thermal linear expansion coefficient ASTM E831-93
Water-absorbent ASTM 570-98
The secondary recirculation of reconstituted product
Regeneration shown in the present molding process again is reusable.Arrive at the terminal point in its work-ing life when reconstituted product after, become discarded (waiting to regenerate) product once more.At this moment only need with its be crushed to once more designated size (for example still being crushed to 100～150 orders) then by prescription slightly through adjusting with after polyvinyl chloride and a small amount of processing aid mix mutually, once more thermal regeneration, be moulded shape again and get final product.
Broken againUse commercial ball mill to get final product.
Mould againProcessing condition are identical with aforementioned page 2 " summary of the invention " (3)～(6) section.
The environmental protection index of technological process of the present invention and product
Noxious waste pollutionTechnological process of the present invention does not produce noxious waste pollution.The limit pin waste material recyclable regenerative of the minute quantity that produces in the heating forming process uses.
Liquid waste pollutionTechnological process of the present invention does not produce liquid.Directly the waste epoxy resin from electronic industry generally need not to clean.Even if some surface dirt dirt needs to clean, generation also be and laundry, the similar waste water capable of circulation of carwash.
The gas waste pollutionThe liquid processing aid (as stablizer, lubricant etc.) of minute quantity is in the back vaporization of being heated, and polyvinyl chloride is subjected to can discharge gas decomposition product in the hot procedure in addition.These gases and degradation production have detailed research and final conclusion to the influence of environment in the industrial practice of modern polrvinyl chloride product.No longer repeat inferior.Polyvinyl chloride industry is second-biggest-in-the-world plastics industry, produces 2～3,000 ten thousand tons per year.
5The Environmental Protection Practice of polrvinyl chloride product industry at present is a small amount of gas emptying that produces in the heating forming process.More careful way be before the gas emptying with absorption column of gas will be wherein acidic component sponge.
Noise pollutionTechnological process of the present invention does not have particular noise and pollutes.The noise pollution of minute quantity is from the mechanicalness noise of pulverizing and heat former.Because the employed equipment of technological process of the present invention is general-purpose equipment, the degree of its noise pollution and control method can directly obtain from relevant devices manufactory.
Description of drawings
The schematic flow sheet of accompanying drawing 1 Melt Pump of configuration before the mouth mould of parallel double-screw extruder
Accompanying drawing 2 adds the schematic flow sheet of a controlled heating zone between extruding dies and follow-up cooling shaping section
The controlled heat block design diagram of accompanying drawing 3 this patents assemble type invention and that in Development Practice, use
Specific embodiments
1. embodiment 1: get 1.0 kilograms on 29.4 kilograms of the dry useless Resins, epoxy (grey) of 120 orders, 68.6 kilograms of polyvinyl chloride (white), 1.0 kilograms in paraffin and zinc-calcium stable agent, extrude (195 ℃ of die temperatures) by tapered twin screw extruder, can get Resins, epoxy and polyvinyl chloride weight ratio and be 3: 7 black composite plastic product.
2. embodiment 2: get 1.0 kilograms on 49.0 kilograms of the dry useless Resins, epoxy (grey) of 120 orders, 49.0 kilograms of polyvinyl chloride (white), 1.0 kilograms in paraffin and zinc-calcium stable agent, extrude (195 ℃ of die temperatures) by tapered twin screw extruder, can get Resins, epoxy and polyvinyl chloride weight ratio and be 5: 5 black composite plastic product.
3. embodiment 3: get 1.0 kilograms on 68.6 kilograms of the dry useless Resins, epoxy (grey) of 120 orders, 29.4 kilograms of polyvinyl chloride (white), 1.0 kilograms in paraffin and zinc-calcium stable agent, stir, be shaped in (50 normal atmosphere, 220 ℃, 10 minutes) by the hydropress heating and pressurizing, can get Resins, epoxy and polyvinyl chloride weight ratio and be 7: 3 black composite plastic product.
Many other embodiments can be arranged in addition.
Reference
1.I.I.Rubin?edt.，“Handbook?of?Plastic?Materials?and?Technology”，John?Wiley?&Sons，Inc.，New?York(1990).
2.C.A.Harper?edt.，“Modern?Plastic?Handbook”，McGraw-Hill，New?York(1999).
3.U.S.Environmental?Protection?Agency，“Characterization?of?Municipal?SolidWaste?in?the?United?States”，EPA?530-R-98-007(1998).
4.Merchant?Research?&?Consulting?Ltd.，“Epoxy?Resin?Market?Research”，Singapore(2006).
5.T.Rehm，R.Werner?“Polyvinylchloride?Kunststoffe”，86：1474-1476(1996).
Claims (4)
- (1) mechanically will be crushed to the waste epoxy resin and the polyvinyl chloride (or the waste polyvinyl chloride after cleaning pulverizing) of specifying the order number at suitable thermoplastic mixes by proper proportion, add an amount of processing aid again, the regenerative response that common heating just can be by bringing out waste epoxy resin so that make have high compressive strength, tensile strength, anti-around Qu Nengli, creep resisting ability and new composite plastic that recyclable regenerative uses.
- (2) suitable thermoplastic machinery refers to suitable (or slightly modified) forcing machine or hydropress.Suitable blending ratio refers to following part by weight between waste epoxy resin and the polyvinyl chloride: 100 parts of waste epoxy resins: 30～400 parts of polyvinyl chloride (or waste polyvinyl chloride).An amount of processing aid refer to weight be the prescription total amount 0～10% as stablizer, lubricant etc.Wherein when the blending ratio between waste epoxy resin and the polyvinyl chloride be 100 parts of waste epoxy resins: 50 parts of polyvinyl chloride, and the tool favorable mechanical performance of the regeneration composite plastic that makes during for 0.5～3% left and right sides of prescription total amount of processing aid consumption.
- (3) process of utilizing waste epoxy resin and polyvinyl chloride between extruder screw (or spiral shell piece), to be sheared, and consequent heat brings out the regenerative response of waste epoxy resin, so make have high compressive strength, tensile strength, anti-around Qu Nengli, creep resisting ability and new composite plastic that recyclable regenerative uses.
- (4) between extruding dies and cooling shaping section, add the mechanical property of a controlled heating zone with further reinforcement extruded product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100372723A CN101580625A (en) | 2008-05-12 | 2008-05-12 | Technology and process of cyclic utilization and cyclic remolding of waste thermosetting plastic (epoxide resin) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100372723A CN101580625A (en) | 2008-05-12 | 2008-05-12 | Technology and process of cyclic utilization and cyclic remolding of waste thermosetting plastic (epoxide resin) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101580625A true CN101580625A (en) | 2009-11-18 |
Family
ID=41362949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100372723A Pending CN101580625A (en) | 2008-05-12 | 2008-05-12 | Technology and process of cyclic utilization and cyclic remolding of waste thermosetting plastic (epoxide resin) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101580625A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891902A (en) * | 2010-07-23 | 2010-11-24 | 浙江理工大学 | Method for recycling waste epoxy resin |
| CN103408901A (en) * | 2013-08-07 | 2013-11-27 | 东华大学 | Method for irradiation induction modified waste epoxy resin |
| CN106618345A (en) * | 2016-11-24 | 2017-05-10 | 平湖市欧迪雅厨卫设备有限公司 | Epoxy resin liner waterless toilet |
-
2008
- 2008-05-12 CN CNA2008100372723A patent/CN101580625A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891902A (en) * | 2010-07-23 | 2010-11-24 | 浙江理工大学 | Method for recycling waste epoxy resin |
| CN103408901A (en) * | 2013-08-07 | 2013-11-27 | 东华大学 | Method for irradiation induction modified waste epoxy resin |
| CN103408901B (en) * | 2013-08-07 | 2016-05-04 | 东华大学 | A kind of method of radiation-induced modified waste epoxy resin |
| CN106618345A (en) * | 2016-11-24 | 2017-05-10 | 平湖市欧迪雅厨卫设备有限公司 | Epoxy resin liner waterless toilet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102061759B1 (en) | Manufacturing method of recycled plastic pellet for producing recycled plastic product | |
| Yan et al. | Particulate reinforced rotationally moulded polyethylene composites–mixing methods and mechanical properties | |
| CN105199379A (en) | Continuous long carbon fiber reinforced thermoplastic nanocomposite and preparation method and application thereof | |
| Homkhiew et al. | The optimal formulation of recycled polypropylene/rubberwood flour composites from experiments with mixture design | |
| Babagowda et al. | Study of Effects on Mechanical Properties of PLA Filament which is blended with Recycled PLA Materials | |
| CN101198451A (en) | Material to be injection molded, process thereof, and use therefore | |
| CN103753787B (en) | A kind of preparation method of the wood plastic composite for door and window | |
| CN105255096A (en) | Method for toughening waste ABS plastic of washing machines | |
| EP1318902B1 (en) | Method for producing a granulated intermediate product that is to be subjected to a subsequent processing in order to form plastic shaped bodies | |
| CN101580625A (en) | Technology and process of cyclic utilization and cyclic remolding of waste thermosetting plastic (epoxide resin) | |
| CN110105783A (en) | A kind of waterproof coffee slag plate and preparation method thereof | |
| CN104526904A (en) | Waste GMT material recycling granulation method for vehicle and special device thereof | |
| JP5850675B2 (en) | Nylon resin composition | |
| JP3215783U (en) | Recycled carbon fiber bundles | |
| CN106832753B (en) | A kind of phenoplasts waste material recovery method | |
| CN1306031A (en) | Extruding-out and injection method for producing composite products of used plastics and powdered coal ash | |
| CN106674742A (en) | PP (polypropylene) composite for thin-walled automobile bumper and preparation method of PP composite | |
| CN102618049A (en) | Anti-static bamboo fiber mould composite material | |
| CN106459493A (en) | Thermoplastic formed with renewable content | |
| CN102504409A (en) | Method for enhancing polypropylene using calcium sulfate whisker | |
| CN102198687A (en) | Method for enhancing wood-plastic composite material | |
| CN211105488U (en) | Double-screw extruder for adding powder through side feeding | |
| US6129877A (en) | Method and system for fabricating elastomeric articles | |
| CN106009635A (en) | Low-melting-point nylon wood/plastic product and preparation method thereof | |
| CN113667320A (en) | Preparation method of modified reclaimed material of waste polypropylene woven bag reclaimed material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice |
Addressee: Lu Shuyu Document name: the First Notification of an Office Action |
|
| DD01 | Delivery of document by public notice |
Addressee: Lu Shuyu Document name: Notification that Application Deemed to be Withdrawn |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20091118 |