CN107599296B - Micropore injection moulding foaming preparation polylactic acid-natural rubber porous material method and material - Google Patents
Micropore injection moulding foaming preparation polylactic acid-natural rubber porous material method and material Download PDFInfo
- Publication number
- CN107599296B CN107599296B CN201710891259.3A CN201710891259A CN107599296B CN 107599296 B CN107599296 B CN 107599296B CN 201710891259 A CN201710891259 A CN 201710891259A CN 107599296 B CN107599296 B CN 107599296B
- Authority
- CN
- China
- Prior art keywords
- natural rubber
- polylactic acid
- porous material
- glycidyl methacrylate
- preparation
- 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.)
- Active
Links
Landscapes
- Biological Depolymerization Polymers (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention belongs to micropore injection moulding foaming technique field, a kind of micropore injection moulding foaming preparation polylactic acid-natural rubber porous material method and material are disclosed, graft is prepared by emulsion polymerization；Dry polylactic acid pellet is mixed in proportion with glycidyl methacrylate-natural rubber graft, using double screw extruder melt blending, extruding pelletization；The injection molding machine equipped with gas compression unit is used to carry out micropore injection moulding foaming blend pellet, with supercritical CO2Fluid is foaming agent, obtains polylactic acid/natural rubber porous material.The present invention carries out toughening modifying to polylactic acid using natural rubber, and the polarity of natural rubber is improved by the method to natural rubber graft glycidyl methacrylate, increases its compatibility with polylactic acid.Foam process of the present invention is simple, and gained foamed material abscess-size size and distribution are all more uniform, while foamed material has preferable toughness.
Description
Technical field
The invention belongs to micropore injection moulding foaming technique field more particularly to a kind of micropore injection moulding foaming preparation polylactic acid-days
Right rubber porous material method and material.
Background technique
The development of micropore injection moulding foaming technique starts from 1970 and 1980.Three steps of micropore injection moulding foaming process point: nucleation,
Abscess becomes larger and cell stabilization.Firstly, supercritical fluid (usually nitrogen or carbon dioxide) is dissolved in polymerization as foaming agent
Polymer-gas uniform solution is formed in object melt, i.e., polymer melt is by gas over-saturation.Then, gas pressure is unexpected
Saturated pressure is reduced to hereinafter, thermodynamic instability is caused to cause the nucleation of abscess.The growth of abscess by gas diffusion rate
With the strength control of polymer-gas melt.The cell density of micropore injection moulding foamed plastic is general >=109cells/cm3, hole
Diameter < 10 μm.Preparing material using micropore injection moulding foaming technique, there are many advantages, can such as reduce the usage amount of raw material, material
Good stability of the dimension, the material process-cycle is short, and energy consumption is small etc., and also contribute to the mechanical property of material.Plastic substrate
The micropore of middle formation can prevent the extension of crackle, to improve the toughness of material, impact strength and fatigue life.It introduces overcritical
Fluid can form the mixing melt of polymer-gas, so that the viscosity of polymer melt is reduced, so that polymer can be relatively more
It is molded under low temperature and pressure, is conducive to be molded those to humidity and the more sensitive boiomacromolecule of temperature, such as poly- cream
Acid.Polylactic acid (PLA) is known as " green plastic ", is the environment-friendly polymers that China widelys popularize application in recent years.
However, the molecule branch quantity of PLA is few, property is crisp, and melt viscosity and melt strength are low, so that walls film-strength when PLA foams
Deficiency, difficult forming, and obtained foaming PLA more brittleness.Chinese patent CN102321269, CN101880404,
CN102936401, CN104910596 etc. relate to utilize supercritical CO2Fluid swollen sample, last fast pressure relief, preparation are poly-
The method of lactic acid blend foaming sample.At present in the domestic patented technology about the preparation of PLA foamed material, do not occurred facing with super
Boundary CO2Fluid is foaming agent, and the application of toughened polylactic foamed material is prepared by micropore injection moulding foaming.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of micropore injection moulding foaming preparation polylactic acid-natural rubber is more
Porous materials method and material.
The invention is realized in this way the present invention prepares methyl by emulsion polymerization aiming at the problem that polylactic acid poor toughness
Glycidyl acrylate-natural rubber graft, the plasticized modifier as polylactic acid.Polylactic acid and methacrylic acid are contracted
Water glyceride-natural rubber graft carries out micropore injection moulding foaming after using double screw extruder melt blending, with supercritical CO2
Fluid is foaming agent, obtains polylactic acid/natural rubber porous material.
The present invention the following steps are included:
Step 1 prepares glycidyl methacrylate-natural rubber graft by emulsion polymerization, in vacuum drying
40 DEG C of dryings shred spare to constant weight in case；By polylactic acid pellet in a vacuum drying oven 80 DEG C of dry 4h with spare.
Step 2 presses dry polylactic acid pellet and glycidyl methacrylate-natural rubber graft respectively
Weight ratio 95/5,90/10,85/15,80/20 mixes, and carries out extruding pelletization using double screw extruder.Extrusion temperature be 160~
190 DEG C, screw speed is 60~100 turns/min.
Blend pellet is used the injection molding machine equipped with gas compression unit to carry out micropore injection moulding foaming by step 3, with
Supercritical CO2Fluid is foaming agent.170~200 DEG C of injection temperature, 10~50 DEG C of mould temperature, 30~50cm of injection speed3/ s is super to face
Boundary CO2Fluid accounts for the 0.5~2% of polymer quality, and injection molding obtains polylactic acid/natural rubber porous material.
Further, glycidyl methacrylate-natural rubber graft is according to patent application in the step 1
Method in 2015107936727 is prepared.Specifically, being first 100 parts of Heveatex of 60% by dry glue quality content
It is added in three-necked bottle, adds distilled water 100ml and be diluted, 10 parts of potassium hydroxide and 1 part ten are added in whipping process
Sodium dialkyl sulfate；10 parts of isopropanol are added after leading to nitrogen 30min at room temperature, continues that 50 parts are added dropwise again after stirring 30min
Glycidyl methacrylate；60 DEG C are warming up to after latex particle is sufficiently swollen, adds initiator isopropylbenzene peroxidating
2 parts of hydrogen, stirring 15min is added 2 parts of catalyst TEPA tetraethylene pentamine later；After reacting 8h, formation that reaction solution is volatilized under room temperature
Dry glue film is dried to constant weight in 40 DEG C of vacuum drying ovens after embathing 5 times with deionized water, it is sweet to obtain the Glycidyl methacrylate
Grease-natural rubber graft.
Further, the number-average molecular weight of the polylactic acid pellet is 12~180,000.
Advantages of the present invention and good effect are as follows: aiming at the problem that polylactic acid brittleness, the present invention is using natural rubber to poly-
Lactic acid carries out toughening modifying, and the pole of natural rubber is improved by the method to natural rubber graft glycidyl methacrylate
Property, increase its compatibility with polylactic acid, enables natural rubber effectively plasticizing polylactic acid.By polylactic acid and methacrylic acid
Micropore injection moulding foaming is carried out after ethylene oxidic ester-natural rubber graft melt blending, with supercritical CO2Fluid is foaming agent,
Obtain polylactic acid/natural rubber porous material.Foam process of the present invention is simple, gained foamed material abscess-size size and distribution
It is all more uniform, while foamed material has preferable toughness.
Detailed description of the invention
Fig. 1 is polylactic acid/natural rubber porous material stereoscan photograph that the embodiment of the present invention 2 provides.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
Respectively by weight by dry polylactic acid pellet and glycidyl methacrylate-natural rubber graft
95/5 mixing carries out extruding pelletization using double screw extruder.Extrusion temperature is 190 DEG C, and screw speed is 100 turns/min.
Blend pellet is subjected to micropore injection moulding foaming, with supercritical CO2Fluid is foaming agent.200 DEG C of injection temperature, mould
50 DEG C of temperature, injection speed 30cm3/ s, supercritical CO2Fluid accounts for the 1% of polymer quality, and injection molding obtains polylactic acid/natural rubber
Porous material.
Embodiment 2
Respectively by weight by dry polylactic acid pellet and glycidyl methacrylate-natural rubber graft
90/10 mixing carries out extruding pelletization using double screw extruder.Extrusion temperature is 180 DEG C, and screw speed is 90 turns/min.
Blend pellet is subjected to micropore injection moulding foaming, with supercritical CO2Fluid is foaming agent.190 DEG C of injection temperature, mould
40 DEG C of temperature, injection speed 30cm3/ s, supercritical CO2Fluid accounts for the 1% of polymer quality, and injection molding obtains polylactic acid/natural rubber
Porous material.
Embodiment 3
Respectively by weight by dry polylactic acid pellet and glycidyl methacrylate-natural rubber graft
85/15 mixing carries out extruding pelletization using double screw extruder.Extrusion temperature is 170 DEG C, and screw speed is 80 turns/min.
Blend pellet is subjected to micropore injection moulding foaming, with supercritical CO2Fluid is foaming agent.180 DEG C of injection temperature, mould
20 DEG C of temperature, injection speed 40cm3/ s, supercritical CO2Fluid accounts for the 0.5% of polymer quality, and injection molding obtains polylactic acid/natural rubber
Glue porous material.
Embodiment 4
Respectively by weight by dry polylactic acid pellet and glycidyl methacrylate-natural rubber graft
80/20 mixing carries out extruding pelletization using double screw extruder.Extrusion temperature is 160 DEG C, and screw speed is 60 turns/min.
Blend pellet is subjected to micropore injection moulding foaming, with supercritical CO2Fluid is foaming agent.170 DEG C of injection temperature, mould
10 DEG C of temperature, injection speed 50cm3/ s, supercritical CO2Fluid accounts for the 2% of polymer quality, and injection molding obtains polylactic acid/natural rubber
Porous material.
Comparative example: dry polylactic acid pellet is subjected to extruding pelletization using double screw extruder.Extrusion temperature is 190
DEG C, screw speed is 100 turns/min.
Polylactic acid pellet is subjected to micropore injection moulding foaming, with supercritical CO2Fluid is foaming agent.200 DEG C of injection temperature, mould
50 DEG C of temperature, injection speed 50cm3/ s, supercritical CO2Fluid accounts for the 1% of polymer quality, and injection molding obtains polylactic acid porous material.
The polylactic acid that 1 embodiment of the present invention of table and comparative example obtain/natural rubber porous material test result
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of prepare polylactic acid-natural rubber porous material method, which comprises the steps of:
Step 1: glycidyl methacrylate-natural rubber graft is prepared by emulsion polymerization, the increasing as polylactic acid
Tough modifying agent；
Step 2: polylactic acid and glycidyl methacrylate-natural rubber graft are melted using double screw extruder
Micropore injection moulding foaming is carried out after blending, with supercritical CO2Fluid is foaming agent, obtains polylactic acid/natural rubber porous material,
Middle polylactic acid and glycidyl methacrylate-natural rubber graft weight ratio are 95/5,90/10,85/15,80/
20, screw speed is 60~100 turns/min when extrusion.
2. preparation polylactic acid-natural rubber porous material method as described in claim 1, which is characterized in that in step 1,
Glycidyl methacrylate-natural rubber graft prepared by emulsion polymerization, 40 DEG C of dryings are extremely in a vacuum drying oven
Constant weight shreds spare.
3. preparation polylactic acid-natural rubber porous material method as described in claim 1, which is characterized in that in step 2
Polylactic acid using preceding 80 DEG C of dry 4h in a vacuum drying oven with spare.
4. preparation polylactic acid-natural rubber porous material method as described in claim 1, which is characterized in that in step 2,
Extrusion temperature is 160~190 DEG C.
5. preparation polylactic acid-natural rubber porous material method as described in claim 1, which is characterized in that in step 2,
170~200 DEG C of injection temperature, 10~50 DEG C of mould temperature, 30~50cm of injection speed3/ s, supercritical CO2Fluid accounts for polymer quality
0.5~2%.
6. preparation polylactic acid-natural rubber porous material method as described in claim 1, which is characterized in that the step
It is 60% that glycidyl methacrylate-natural rubber graft preparation method, which includes: first by dry glue quality content, in one
100 parts of Heveatex be added in three-necked bottle, add distilled water 100ml and be diluted, in whipping process be added 10 parts
Potassium hydroxide and 1 part of lauryl sodium sulfate；10 parts of isopropanol are added after leading to nitrogen 30min at room temperature, is continued after stirring 30min
50 parts of glycidyl methacrylate are added dropwise again；60 DEG C are warming up to after latex particle is sufficiently swollen, adds initiation
2 parts of agent isopropyl benzene hydroperoxide, stirring 15min is added 2 parts of catalyst TEPA tetraethylene pentamine later；React 8h after, by reaction solution in
Volatilization forms dry glue film under room temperature, dries in 40 DEG C of vacuum drying ovens to constant weight after embathing 5 times with deionized water, obtains the first
Base glycidyl acrylate-natural rubber graft.
7. preparation polylactic acid-natural rubber porous material method as described in claim 1, which is characterized in that the poly- cream
The number-average molecular weight of acid is 12~180,000.
8. a kind of using preparation polylactic acid-natural rubber porous material method preparation described in any one of claim 1~7
Polylactic acid-natural rubber porous material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710891259.3A CN107599296B (en) | 2017-09-27 | 2017-09-27 | Micropore injection moulding foaming preparation polylactic acid-natural rubber porous material method and material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710891259.3A CN107599296B (en) | 2017-09-27 | 2017-09-27 | Micropore injection moulding foaming preparation polylactic acid-natural rubber porous material method and material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107599296A CN107599296A (en) | 2018-01-19 |
| CN107599296B true CN107599296B (en) | 2019-06-07 |
Family
ID=61058948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710891259.3A Active CN107599296B (en) | 2017-09-27 | 2017-09-27 | Micropore injection moulding foaming preparation polylactic acid-natural rubber porous material method and material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107599296B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110885471B (en) * | 2019-11-28 | 2022-05-10 | 广东祥雄科学器材实业有限公司 | Production process of SEBS rubber bra pad foaming material |
| CN112544694B (en) * | 2020-10-16 | 2022-05-27 | 浙江杭化新材料科技有限公司 | Preservative paper for curing picked kiwi fruits and curing method of picked kiwi fruits |
| CN114874506B (en) * | 2021-02-05 | 2024-06-04 | 中国石油化工股份有限公司 | Composition for preparing thermoplastic vulcanized rubber microporous foam material, preparation method and application thereof |
| CN113527853B (en) * | 2021-07-30 | 2022-02-15 | 宁波昌亚新材料科技股份有限公司 | Bionic porous polylactic acid composite material and preparation method and application thereof |
| CN114747518B (en) * | 2022-03-25 | 2023-11-17 | 深圳市太丰东方海洋生物科技有限公司 | Breeding method of Chlamys nobilis |
| CN116063728B (en) * | 2023-01-12 | 2023-08-22 | 浙江赛阳密封件有限公司 | Preparation method of microporous foam rubber material and sealing strip |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1528079A1 (en) * | 2003-11-03 | 2005-05-04 | Coopbox Europe S.P.A. | Polylactic acid-based degradable foams and process for their production |
| CN102229744B (en) * | 2011-06-25 | 2013-06-12 | 四川大学 | Toughening polylactic acid blend with excellent biocompatibility and preparation method thereof |
| CN102321269B (en) * | 2011-09-26 | 2013-07-31 | 浙江工业大学 | Method for preparing meso-porous silica/polylactic acid foamed material by supercritical CO2 foaming |
| WO2014158014A1 (en) * | 2013-03-28 | 2014-10-02 | Synbra Technology B.V. | A method for the preparation of pla bead foams |
| CN105038164B (en) * | 2015-08-18 | 2017-06-06 | 华南理工大学 | PLA base intermingling material and preparation method thereof and the method that expanded material is prepared by it |
| CN106366596A (en) * | 2016-09-30 | 2017-02-01 | 青岛科技大学 | Polylactic acid/chemically modified natural rubber blend material and preparing method thereof |
-
2017
- 2017-09-27 CN CN201710891259.3A patent/CN107599296B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107599296A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107599296B (en) | Micropore injection moulding foaming preparation polylactic acid-natural rubber porous material method and material | |
| CN103160045B (en) | A kind of polyvinyl-chloride foam material and preparation method thereof | |
| CN106700287B (en) | A kind of foamed thermoplastic elastomers and preparation method thereof | |
| JP6351574B2 (en) | Foam molding | |
| CN104072881A (en) | Thermoplastic micro-foaming damping material and preparation method thereof | |
| CN112920501B (en) | Nylon elastomer composite material foam and preparation method thereof | |
| CN105038164B (en) | PLA base intermingling material and preparation method thereof and the method that expanded material is prepared by it | |
| CN103242632A (en) | Polylactic acid degradable foaming material and preparation method thereof | |
| CN103819885B (en) | A kind of polylactic acid foam material and preparation method thereof | |
| CN110343286B (en) | Poly (butylene succinate) ionomer foam and preparation method and application thereof | |
| CN109501107A (en) | A kind of low-density, polymer foams of high foamability and preparation method thereof | |
| CN108341986A (en) | A kind of preparation method of full open aperture polymeric foamable material and corresponding expanded material | |
| CN104448745A (en) | Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) foaming material and preparation method thereof | |
| CN107674406A (en) | A kind of supercritical CO2Expanded material bio-based porous carbon materials | |
| CN113072767B (en) | EVA/TPAE composite material foam and preparation method thereof | |
| CN112745623A (en) | Composition for preparing polypropylene plastic-wood composite material, composite material prepared from composition and application of composite material | |
| CN109666271A (en) | A kind of fretting map degradable mulch and preparation method thereof | |
| CN103289417A (en) | Multi-modified soy protein biodegradable plastic and preparation method thereof | |
| CN101225222B (en) | Polylactic acid as well as derivative composite material and preparation method thereof | |
| CN108530746A (en) | A kind of preparation method based on draft flowing deformation technology foaming polypropylene sheet | |
| WO2023109738A1 (en) | Hyperbranched ionic liquid/cnfs hybrid particles, microporous foamed flame-retardant tpv and preparation method therefor | |
| US20190127545A1 (en) | Process for producing expandable polylactic acid-containing pellets | |
| Lin et al. | A new strategy to fabricate polyvinyl alcohol (PVA) foam with low thermal conductivity using PVA-citric acid solution in supercritical carbon dioxide | |
| CN109734987A (en) | A kind of bamboo fibre microcellular foam material and its manufacturing method | |
| CN105291340A (en) | Water foaming injection method by using super absorbent resin as carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191204 Address after: 550005 No. D-15, Science Park, Guiyang University, No. 103, jianlongdong Road, Shuanglong Airport Economic Zone, Guiyang City, Guizhou Province Patentee after: Guizhou Doraemon Housekeeping Service Co.,Ltd. Address before: Nanming District of Guizhou city in Guiyang province 550005 see Longdong Road No. 103 Patentee before: guiyang university |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221205 Address after: D-39, University Science Park, Guiyang University, No. 103, Jianlongdong Road, Nanming District, Guiyang City, Guizhou Province 550005 [Shuanglong District] Patentee after: Guizhou Qiancheng Qiance Testing Technology Co.,Ltd. Address before: No. D-15, University Science Park, Guiyang University, No. 103, Jianlongdong Road, Shuanglong Airport Economic Zone, Guiyang City, Guizhou Province 550005 Patentee before: Guizhou Doraemon Housekeeping Service Co.,Ltd. |
|
| TR01 | Transfer of patent right |