CN104072840A - Method for improving degree of crystallinity of thermoplastic resin micro-molded product - Google Patents
Method for improving degree of crystallinity of thermoplastic resin micro-molded product Download PDFInfo
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- CN104072840A CN104072840A CN201410299592.1A CN201410299592A CN104072840A CN 104072840 A CN104072840 A CN 104072840A CN 201410299592 A CN201410299592 A CN 201410299592A CN 104072840 A CN104072840 A CN 104072840A
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- Prior art keywords
- thermoplastic resin
- crystallinity
- micro
- dcp
- injection
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76498—Pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76531—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76585—Dimensions, e.g. thickness
- B29C2945/76591—Dimensions, e.g. thickness volume
Abstract
The invention relates to method for improving degree of crystallinity of a thermoplastic resin micro-molded product, and belongs to the field of high polymer materials. The method for improving degree of crystallinity of the thermoplastic resin micro-molded product provided by the invention comprises the following steps of adding DCP (dicumyl peroxide) while preparing the thermoplastic resin micro-molded product, wherein addition of the DCP is 0.05-0.2wt% of that of the thermoplastic resin. In a normal injection-molding process, the DCP is usually used as an initiator for degrading polyolefin resin such as PP (polypropylene), and the like; in the method disclosed by the invention, the DCP (dicumyl peroxide) is founded to be added in the thermoplastic resin in a micro injection-molding process, so that degree of crystallinity of the resin can be improved.
Description
Technical field
The present invention relates to a kind of method that improves thermoplastic resin micro shaping goods degree of crystallinity, belong to polymeric material field.
Background technology
Follow modern industrial technology development, microminiaturized and precise treatment has become the main flow of present production development.Simple based on moulding process, adaptability for materials is strong, economical and efficient, can continuous automatic production etc. series of advantages, micro shaping has become the important processing technology of processing precise micro parts.Provide the definition of micro shaping according to goods feature Kukla C: micro shaping refers to that the quality of moulded products is milligram level, geometrical dimension is that micron-sized forming method is (referring to Kukla C, Loibl H, Detter H, et al.Mikrospritzgiessen:Ziele einer Projektpartnerschaft[J] .Kunststoffe, 1998,88 (9): 1331-1336).
Miniature plastic because of its scantlings of the structure and volume small, in injection molding process the flow behavior of polymer melt in miniature die cavity from have in traditional macro injection moulding different significantly, existing injection molding technology and correlation theory have not been suitable for micro shaping process, apply regular injection molding technological condition and can not produce high-quality miniature plastic.
The performances such as its viscosity of micro shaping material requirements is low, good fluidity, fast setting, good mechanical stability, polymkeric substance is a kind of common micro shaping material.Due to micro shaping runner and cavity dimension very small, therefore require the plastics that selective flow is good; The material major part of micro shaping application is at present still common engineering plastics and special engineering plastics, and in document both domestic and external, mainly mentioning applicable micro shaping material is polyoxymethylene, polycarbonate, polymethylmethacrylate, polypropylene etc.
For the research of micro shaping processing parameter, be just the main stage in quantitative analysis now, often by commercial software, micro shaping process simulation is analyzed, and carried out check analysis analog result in conjunction with test.For example: Lou C W has studied the filling of micro-lens array (referring to Lou C W, Chiang Y C, Cheng H C, et al.A novel and rapid fabrication for microlens arrays using microinjection molding[J] .Polymer Engineering & Science, 2011,51 (2): 391-402.), found that the formability of PMMA is better than PC.Dai Yachun (Dai Yachun, Wang Yun, Zhou Jianzhong etc. micro-gear injection moulding orthogonal optimization and numerical simulation [J]. material engineering, 2010, (7): 46-48) based on the impact of PP, PC, the stowing operation of tri-kinds of materials of ABS on micro-gear that adopted numerical simulation analysis of the method for orthogonal, result shows the mould-filling time that injection temperature raises, injection pressure increases, die temperature rising all can be shortened micro shaping, in three kinds of materials, ABS is best to micro-gear filling suitability, next is PP, is finally PC.
But due to the difference of test conditions and test method, do not obtain unified conclusion about the research of micro shaping processing parameter at present.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that improves thermoplastic resin micro shaping goods degree of crystallinity.
Technical scheme of the present invention:
The invention provides a kind of method that improves thermoplastic resin micro shaping goods degree of crystallinity, in the time preparing thermoplastic resin micro shaping goods, add dicumyl peroxide (DCP), wherein, 0.05～0.2wt% that the add-on of DCP is thermoplastic resin.
Preferably, the 0.15wt% that the add-on of DCP is thermoplastic resin.
Preferably, described thermoplastic resin is polyolefin resin; More preferably polypropylene.
In the method for described raising thermoplastic resin micro shaping goods degree of crystallinity, in the time adopting plunger tpe micro shaping equipment, injection speed≤70mm/s, injection pressure 3-15MPa, injection temperature 180-220 DEG C; Die temperature 30-80 DEG C.
The method of above-mentioned raising thermoplastic resin micro shaping goods degree of crystallinity, is specially: first thermoplastic resin and DCP are obtained to thermoplastic resin/DCP compound in 170～210 DEG C of melt blendings, then compound micro injection molding is obtained to micro shaping goods; Wherein, 0.05～0.2wt% that the add-on of DCP is thermoplastic resin.
The method of above-mentioned raising thermoplastic resin micro shaping goods degree of crystallinity, is preferably: first thermoplastic resin and DCP are obtained to thermoplastic resin/DCP compound in 170～210 DEG C of melt blendings, then compound micro injection molding is obtained to micro shaping goods; Wherein, thermoplastic resin is PP, and the add-on of DCP is 0.05～0.2wt% of PP quality; Microinjection adopts plunger tpe micro shaping equipment, and micro injection molding processing condition are: injection speed :≤70mm/s, injection pressure 3-15MPa, injection temperature: 180-220 DEG C; Die temperature 30-80 DEG C.
Preferred, in the method for above-mentioned raising thermoplastic resin micro shaping goods degree of crystallinity, thermoplastic resin is PP, and the add-on of DCP is the 0.15wt% of PP quality; Microinjection processing condition are: injection speed 35.1mm/s, 200 DEG C of injection temperatures, 30 DEG C of die temperatures, injection pressure 4MPa.
Beneficial effect of the present invention:
DCP is generally used for and makees initiator, and it makes its degraded for polyolefin resines such as PP; DCP at high temperature resolves into group, attacks the tertiary carbon atom on high polymer main chain, forms macro-radical; Under conventional machining condition, rupture; Due to the equiprobability that the each tertiary carbon atom on polymer is attacked, the possibility that fracture occurs larger molecule is larger; Final molecular weight reduces, and molecular weight distribution narrows.And in the present invention, we find in micro injection molding technique, in thermoplastic resin, add DCP (dicumyl peroxide), can improve the degree of crystallinity of resin.
Brief description of the drawings
Fig. 1 is the schematic diagram of the micro-gear of embodiment of the present invention gained PP.
Embodiment
The invention provides a kind of method that improves thermoplastic resin micro shaping goods degree of crystallinity, in the time preparing thermoplastic resin micro shaping goods, add DCP, wherein, 0.05～0.2wt% that the add-on of DCP is thermoplastic resin.
Preferably, the 0.15wt% that the add-on of DCP is thermoplastic resin.
Preferably, described thermoplastic resin is polyolefin resin; More preferably polypropylene.
In the method for described raising thermoplastic resin micro shaping goods degree of crystallinity, micro shaping processing condition (injection speed, injection pressure, die temperature) adjust accordingly according to selected injection device; In the time adopting plunger tpe micro shaping equipment, injection speed≤70mm/s (the too small die cavity that can not be full of), injection pressure 3-15MPa (the too small die cavity that can not be full of), injection temperature 180-220 DEG C; Die temperature 30-80 DEG C; It is soft not easy-formation that die temperature is crossed high product.
The method of above-mentioned raising thermoplastic resin micro shaping goods degree of crystallinity, is specially: first thermoplastic resin and DCP are obtained to thermoplastic resin/DCP compound in 170～210 DEG C of melt blendings, then compound micro injection molding is obtained to micro shaping goods; Wherein, 0.05～0.2wt% that the add-on of DCP is thermoplastic resin.
The method of above-mentioned raising thermoplastic resin micro shaping goods degree of crystallinity, is preferably: first thermoplastic resin and DCP are obtained to thermoplastic resin/DCP compound in 170～210 DEG C of melt blendings, then compound micro injection molding is obtained to micro shaping goods; Wherein, thermoplastic resin is PP, and the add-on of DCP is 0.05～0.2wt% of PP quality; Microinjection adopts plunger tpe micro shaping equipment, and micro injection molding processing condition are: injection speed :≤70mm/s, injection pressure 3-15MPa, injection temperature: 180-220 DEG C; Die temperature 30-80 DEG C.
Preferred, in the method for above-mentioned raising thermoplastic resin micro shaping goods degree of crystallinity, thermoplastic resin is PP, and the add-on of DCP is the 0.15wt% of PP quality; Microinjection processing condition are: injection speed 35.1mm/s, 200 DEG C of injection temperatures, 30 DEG C of die temperatures, injection pressure 4MPa.
Embodiment
Material: isotatic polypropylene, F401, PetroChina Lanzhou Petrochemical Company; Dicumyl peroxide (DCP), Tm=39～41 DEG C, Solution on Chemical Reagents in Shanghai company of Chinese Medicine group.
Major equipment and instrument: plunger tpe micro shaping machine, BABYPLAST6/10P, CRONOPLAST S.L; Differential scanning calorimeter, MDSC2920, TA instrument company of the U.S..
Sample preparation:
First polypropylene and DCP are obtained to PP/DCP compound by twin screw extruder melt blending extruding pelletization, wherein, the content of DCP is respectively 0.05%, 0.1%, 0.15%, 0.2% of PP quality; Temperature range is 170～210 DEG C; Compound is obtained to miniature gears by the injection molding of microinjection machine, and wherein, microinjection processing condition are: melt temperature: 200 DEG C, and injection speed 35.1 (mm/s), 30 DEG C of die temperatures, injection pressure 4MPa.As shown in Figure 1, its thickness is 450 microns to the micro-gear of gained of the present invention, long 1000 microns of tooth, and half 350 microns of the facewidth, gear centre to tooth top distance is 3.02mm.
DSC test
Respectively the toothed portion of goods is done to dsc analysis (in test of the present invention, the sample of every kind of content carries out the test of at least three samples, gained crystallinity value is mean value, DSC test is identical with prior art DSC test): the sample that accurately cuts respectively 5.5mg left and right from the tooth of micro-goods is put into DSC special copple, and press seal is placed in DSC instrument; Experimental arrangement unification is set as: be warming up to 200 DEG C since 50 DEG C with 10 DEG C/min, after insulation 5min, be cooled to 50 DEG C with 10 DEG C/min, be then warming up to 200 DEG C with the speed of 10 DEG C/min; With the brilliant relative content Φ of DSC method calculating style β
βas shown in the formula
Φ
β＝X
β/(X
β+Xα)×100％
X
βrefer to respectively the β crystalline substance of sample and the absolute crystallinity of α crystalline substance with X α;
The method of trying to achieve absolute crystallinity is: the heat content △ H that crystal intensification melting absorbs
ithe corresponding crystalline polymer melting that is 100% with degree of crystallinity absorbs hot heat content △ H
i 0ratio; If only contain α crystalline substance in test sample, can directly calculate, standard hot melt is 209J/g; If contain β crystalline substance and the brilliant two kinds of crystal of α, obtain respectively absolute crystallinity and tried to achieve by two formulas calculating below:
X
β＝△H
β/△Η
β 0×100％
X
α＝△H
α/△Η
α 0×100％
△ H
βwith △ H
αrespectively that β crystalline substance and the intensification melting separately of α crystalline substance absorb heat content; △ Η
β 0with △ Η
α 0be the standard heat enthalpy value of β crystalline substance and α crystalline substance, be respectively 168.5J/g and 177.0J/g; DSC test result is as shown in table 1.
The impact of table 1 different content DCP on the micro-gear degree of crystallinity of PP
| The content (%) of DCP | Sample overall crystallinity X c(％) |
| 0 | 45.09 |
| 0.05 | 45.81 |
| 0.1 | 46.32 |
| 0.15 | 47.46 |
| 0.2 | 46.09 |
| 0.25 | 44.02 |
As shown in Table 1, under this microinjection condition, add the DCP of certain content that the degree of crystallinity of micro-tooth is improved, visible DCP can adjust the size of molecular chain and distribute, and better crystallization of molecular chain after this adjustment is improved degree of crystallinity.In addition,, for micro-tooth, it is maximum that degree of crystallinity reaches in the time that DCP content is 0.15%.The variation of the variation of these degree of crystallinity and peak value correspondence position is all with dimension of polymer chain and distribute relevantly, and whether the size of this molecular chain and be embodied in the most significantly molecule segment corresponding to the variation of degree of crystallinity lax that distribute are conducive to high molecular crystallization to a certain extent.
Comparative example 1
The same embodiment of raw material and preparation method thereof, only changes the add-on of DCP, and DCP add-on is 0.25% of PP quality, adopts with the identical test of embodiment, and gained degree of crystallinity result is as shown in table 1.Visible, after DCP add-on exceedes 0.2%, the degree of crystallinity of PP/DCP compound gained microinjection goods reduces on the contrary.
Comparative example 2
The same embodiment of raw material and preparation method thereof, only changes the injection pressure in microinjection condition into 2MPa, and gained degree of crystallinity is 35.58%.Visible, when injection pressure changes into after 2MPa, the degree of crystallinity of PP/DCP compound gained microinjection goods reduces on the contrary.
Claims (7)
1. a method that improves thermoplastic resin micro shaping goods degree of crystallinity, is characterized in that, in the time preparing thermoplastic resin micro shaping goods, adds dicumyl peroxide, and wherein, the add-on of dicumyl peroxide is 0.05～0.2% of thermoplastic resin quality.
2. the method for raising thermoplastic resin micro shaping goods degree of crystallinity according to claim 1, is characterized in that, the add-on of dicumyl peroxide is the 0.15wt% of thermoplastic resin quality.
3. the method for raising thermoplastic resin micro shaping goods degree of crystallinity according to claim 1 and 2, is characterized in that, described thermoplastic resin is polyolefin resin.
4. the method for raising thermoplastic resin micro shaping goods degree of crystallinity according to claim 3, is characterized in that, described thermoplastic resin is polypropylene.
5. according to the method for the raising thermoplastic resin micro shaping goods degree of crystallinity described in claim 1～4 any one, it is characterized in that, comprise step: first thermoplastic resin and dicumyl peroxide melt blending are obtained to thermoplastic resin/dicumyl peroxide compound, then compound micro injection molding is obtained to micro shaping goods.
6. according to the method for the raising thermoplastic resin micro shaping goods degree of crystallinity described in claim 1～5 any one, it is characterized in that, micro injection molding adopts plunger tpe micro injection molding equipment, microinjection processing condition are: injection speed≤70mm/s, injection pressure 3-15MPa, injection temperature 180-220 DEG C, die temperature 30-80 DEG C.
7. the method for raising thermoplastic resin micro shaping goods degree of crystallinity according to claim 6, is characterized in that, thermoplastic resin is PP, and the add-on of DCP is 0.15% of PP quality; Microinjection processing condition are: injection speed 35.1mm/s, injection pressure 4MPa, 200 DEG C of injection temperatures, 30 DEG C of die temperatures.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4087486A (en) * | 1975-05-15 | 1978-05-02 | Standard Oil Company (Indiana) | Polypropylene composition containing EPR |
| JPS5993711A (en) * | 1982-11-22 | 1984-05-30 | Mitsui Petrochem Ind Ltd | Modification of polypropylene |
| CN102115558A (en) * | 2010-12-29 | 2011-07-06 | 四川大学 | High-conductivity polymer carbon nanotube composite material and micro-processing method thereof |
| CN103087422A (en) * | 2013-02-19 | 2013-05-08 | 复旦大学 | Random copolymerization polypropylene modified material |
| CN103788485A (en) * | 2014-01-13 | 2014-05-14 | 东华大学 | Method for improving heat stability of polypropylene plastic |
-
2014
- 2014-06-27 CN CN201410299592.1A patent/CN104072840B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4087486A (en) * | 1975-05-15 | 1978-05-02 | Standard Oil Company (Indiana) | Polypropylene composition containing EPR |
| JPS5993711A (en) * | 1982-11-22 | 1984-05-30 | Mitsui Petrochem Ind Ltd | Modification of polypropylene |
| CN102115558A (en) * | 2010-12-29 | 2011-07-06 | 四川大学 | High-conductivity polymer carbon nanotube composite material and micro-processing method thereof |
| CN103087422A (en) * | 2013-02-19 | 2013-05-08 | 复旦大学 | Random copolymerization polypropylene modified material |
| CN103788485A (en) * | 2014-01-13 | 2014-05-14 | 东华大学 | Method for improving heat stability of polypropylene plastic |
Non-Patent Citations (1)
| Title |
|---|
| 潘亚敏等: "微注塑与常规注塑等规聚丙烯的拉伸性能及微观结构对比研究", 《上海塑料》, no. 1, 20 August 2013 (2013-08-20), pages 9 - 12 * |
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Inventor after: Wang Shiwei Inventor after: Sun Bo Inventor after: Leng Yuting Inventor after: Jiang Jing Inventor after: Shao Chunguang Inventor after: Li Qian Inventor before: Wang Shiwei Inventor before: Sun Bo Inventor before: Leng Yuting Inventor before: Jiang Jing Inventor before: Shao Chunguang Inventor before: Li Qian Inventor before: Shen Changyu |
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