CN104877315A - Preparation method of high-barrier-property polylactic acid nano composite material - Google Patents
Preparation method of high-barrier-property polylactic acid nano composite material Download PDFInfo
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- CN104877315A CN104877315A CN201510234197.XA CN201510234197A CN104877315A CN 104877315 A CN104877315 A CN 104877315A CN 201510234197 A CN201510234197 A CN 201510234197A CN 104877315 A CN104877315 A CN 104877315A
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- lactic acid
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 38
- 230000004888 barrier function Effects 0.000 claims abstract description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 28
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 22
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 18
- 238000009830 intercalation Methods 0.000 claims abstract description 12
- 230000002687 intercalation Effects 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 241000446313 Lamella Species 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- -1 poly(lactic acid) Polymers 0.000 claims description 52
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- PXCROMSXSIITIF-UHFFFAOYSA-N C(C)C(=O)C(=O)C.[Sn] Chemical compound C(C)C(=O)C(=O)C.[Sn] PXCROMSXSIITIF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004032 porphyrins Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention discloses a preparation method of a high-barrier-property polylactic acid nano composite material. The preparation method comprises the following steps: (1) adding a caprolactone monomer and montmorillonite into a drying flask without oxygen, standing in a sealed way after ultrasonic vibration to ensure that the caprolactone monomer is fully inserted into lamellas of montmorillonite, adding an initiator into the flask, heating to perform intercalation polymerization reaction, dissolving an obtained product in methylbenzene, performing centrifugal separation after ultrasonic vibration, washing by using methylbenzene, and drying to obtain polycaprolactone modified montmorillonite; (2) mixing polylactic acid with silicon oil, adding polycaprolactone modified montmorillonite, performing high-speed mixing, and then performing extrusion granulation by using an extruder to obtain barrier master batches; and (3) uniformly mixing the barrier master batches with polylactic acid, and performing melt blending to obtain the high-barrier-property polylactic acid nano composite material. A caprolactone in-situ intercalation polymerization method is adopted to modify montmorillonite to ensure that nano lamellas of montmorillonite are effectively peeled off, and a master batch method is adopted to ensure that the nano lamellas of montmorillonite are uniformly distributed in a polylactic acid matrix to obtain relatively high barrier property.
Description
Technical field
The present invention relates to a kind of preparation method of high molecule nano material, particularly relate to a kind of preparation method of high barrier poly lactic acid nano composite material.
Background technology
Poly(lactic acid) is that research is at present the most extensive, the Biodegradable material of most potentiality to be exploited, it has good biological degradability and environment friendly, but, the resistance toheat of poly(lactic acid) is very poor, constrain its application, meanwhile, its gas barrier property also needs to be improved further, to meet different application requiring.
Because the defect that above-mentioned existing isolation-type poly(lactic acid) preparation exists, the present inventor is based on being engaged in the practical experience and expertise that this type of product design manufacture enriches for many years, and coordinate the utilization of scientific principle, actively in addition research and innovation, to founding a kind of preparation method of novel high-barrier poly lactic acid nano composite material, it is made to have more practicality.Through constantly research, design, and through repeatedly studying sample and after improving, finally creating the present invention had practical value.
Summary of the invention
Main purpose of the present invention is, overcome the defect that the preparation of existing isolation-type poly(lactic acid) exists, and a kind of preparation method of novel high-barrier poly lactic acid nano composite material is provided, improve the gas barrier property of poly(lactic acid), thus be more suitable for practicality, and there is the utility value in industry.
The object of the invention to solve the technical problems realizes by the following technical solutions.The preparation method of the high barrier poly lactic acid nano composite material proposed according to the present invention, comprises the steps:
(1) preparation of Polycaprolactone modified polynite: pass into nitrogen 30min to remove oxygen in the flask of drying, then in flask, caprolactone monomer and polynite is added, by dispersion liquid ultrasonic vibration 1h, room temperature lower seal places 24h, and caprolactone monomer is fully inserted in montmorillonite layer; In flask, add initiator, after heating, carry out intercalation polymeric reaction, the product obtained is dissolved in toluene, centrifugation after ultrasonic vibration, centrifugal product through toluene repeatedly wash centrifugal after be drying to obtain Polycaprolactone modified polynite.
(2) intercept the preparation of master batch: by high mixer, make poly(lactic acid) and the mixing of a small amount of silicone oil, then add Polycaprolactone modified polynite high-speed mixing 4min, then by twin screw extruder extruding pelletization, extrusion temperature 180 DEG C.
(3) preparation of high barrier poly lactic acid nano composite material: obstruct master batch and poly(lactic acid) are mixed, melt blending 8min on torque rheometer, mixing temperature 190 DEG C, obtains high barrier poly lactic acid nano composite material.
Further, the preparation method of aforesaid high barrier poly lactic acid nano composite material, in described (1), polynite consumption is 5% ~ 10% of caprolactone monomer quality.
Further, the preparation method of aforesaid high barrier poly lactic acid nano composite material, in described (1), initiator amount is 0.2% ~ 0.8% of caprolactone monomer consumption.
Further, the preparation method of aforesaid high barrier poly lactic acid nano composite material, described initiator is the one in stannous octoate, tin protochloride, methyl ethyl diketone tin, stannous oxalate, aluminum isopropylate, triethyl aluminum, porphyrin aluminium, tetrabutyl titanate, metatitanic acid orthocarbonate or isobutyl-trisphenol titanium.
Further, the preparation method of aforesaid high barrier poly lactic acid nano composite material, in described (2), the mass ratio of poly(lactic acid) and Polycaprolactone modified polynite is 100:20 ~ 30.
Further, the preparation method of aforesaid high barrier poly lactic acid nano composite material, described (3) described poly(lactic acid) is 100:1 ~ 5 with the mass ratio of obstruct master batch.
Further, the preparation method of aforesaid high barrier poly lactic acid nano composite material, in described (1), the temperature of reaction of intercalation polymeric is 140 ~ 180 DEG C, and the reaction times is 8 ~ 12h.
By technique scheme, the preparation method of high barrier poly lactic acid nano composite material of the present invention at least has following advantages:
Polynite is the silicate minerals of the laminate structure of a quasi-representative, and its lamella is formed by clipping an alumina octahedral wafer between two silicon-oxy tetrahedron wafers, in " sandwich " structure.And general organic monomer or polymkeric substance are oleophyllie hydrophobic type, therefore effectively promote that polynite disperses in monomer or matrix polymer, intercalation or stripping, improve the bounding force at organic and inorganic interface, form intercal type or exfoliated structure, the montmorillonite layer be dispersed in poly(lactic acid) matrix increases the path of gas diffusion, is the effective measure of the gas barrier property improving poly(lactic acid).
The extent of exfoliation of montmorillonite layer and dispersion size are the important factors affecting matrix material barrier property, fusion intercalation is due to macromolecular dimensional effect, steric hindrance between interposed layer is larger, therefore the present invention adopts caprolactone in-situ intercalative polymerization modified montmorillonoid, obtain complete exfoliated modified montmorillonoid, adopt masterbatch method to improve the deployment conditions of polynite, then obtained the poly lactic acid nano composite material of high barrier by melt blending, obtain higher barrier property.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technique means of the present invention, and can be implemented according to the content of specification sheets, be described in detail as follows below with preferred embodiment of the present invention.
Embodiment
For further setting forth the present invention for the technique means reaching predetermined goal of the invention and take and effect, to its embodiment of preparation method of the high barrier poly lactic acid nano composite material proposed according to the present invention, feature and effect thereof, be described in detail as follows.
Embodiment 1
(1) preparation of Polycaprolactone modified polynite: pass into nitrogen 30min to remove oxygen in the flask of drying, then in flask, the caprolactone monomer that mass ratio is 100:5 and polynite is added, by dispersion liquid ultrasonic vibration 1h, room temperature lower seal places 24h, caprolactone monomer is fully inserted in montmorillonite layer, the initiator tetrabutyl titanate of caprolactone monomer quality 0.2% is added in flask, intercalation polymeric carries out 8h at 180 DEG C of lower seals, the product obtained is dissolved in toluene, centrifugation after ultrasonic vibration, centrifugal product through toluene repeatedly wash centrifugal after be drying to obtain Polycaprolactone modified polynite.
(2) intercept the preparation of master batch: by high mixer, make poly(lactic acid) and the mixing of a small amount of silicone oil, then add 10% Polycaprolactone modified polynite high-speed mixing 4min, then by twin screw extruder extruding pelletization, extrusion temperature 180 DEG C.
(3) preparation of high barrier poly lactic acid nano composite material: obstruct master batch and poly(lactic acid) are mixed with the proportioning of 1:100, melt blending 8min on torque rheometer, mixing temperature 190 DEG C, obtains high barrier poly lactic acid nano composite material.
Embodiment 2
(1) preparation of Polycaprolactone modified polynite: pass into nitrogen 30min to remove oxygen in the flask of drying, then in flask, the caprolactone monomer that mass ratio is 100:6 and polynite is added, by dispersion liquid ultrasonic vibration 1h, room temperature lower seal places 24h, caprolactone monomer is fully inserted in montmorillonite layer, in flask, add the initiator stannous octoate of caprolactone monomer quality 0.4%, intercalation polymeric carries out 9h at 170 DEG C of lower seals.The product obtained is dissolved in toluene, centrifugation after ultrasonic vibration, centrifugal product through toluene repeatedly wash centrifugal after be drying to obtain Polycaprolactone modified polynite.
(2) intercept the preparation of master batch: by high mixer, make poly(lactic acid) and the mixing of a small amount of silicone oil, then add 15% Polycaprolactone modified polynite high-speed mixing 4min, then by twin screw extruder extruding pelletization, extrusion temperature 180 DEG C.
(3) preparation of high barrier poly lactic acid nano composite material: obstruct master batch and poly(lactic acid) are mixed with the proportioning of 2:100, melt blending 8min on torque rheometer, mixing temperature 190 DEG C, obtains high barrier poly lactic acid nano composite material.
Embodiment 3
(1) preparation of Polycaprolactone modified polynite: pass into nitrogen 30min to remove oxygen in the flask of drying, then in flask, the caprolactone monomer that mass ratio is 100:8 and polynite is added, by dispersion liquid ultrasonic vibration 1h, room temperature lower seal places 24h, caprolactone monomer is fully inserted in montmorillonite layer, the initiator metatitanic acid orthocarbonate of caprolactone monomer quality 0.6% is added in flask, intercalation polymeric carries out 8h at 180 DEG C of lower seals, the product obtained is dissolved in toluene, centrifugation after ultrasonic vibration, centrifugal product through toluene repeatedly wash centrifugal after be drying to obtain Polycaprolactone modified polynite.
(2) intercept the preparation of master batch: by high mixer, make poly(lactic acid) and the mixing of a small amount of silicone oil, then add 12% Polycaprolactone modified polynite high-speed mixing 4min, then by twin screw extruder extruding pelletization, extrusion temperature 180 DEG C.
(3) preparation of high barrier poly lactic acid nano composite material: obstruct master batch and poly(lactic acid) are mixed with the proportioning of 5:100, melt blending 8min on torque rheometer, mixing temperature 190 DEG C, obtains high barrier poly lactic acid nano composite material.
Embodiment 4
(1) preparation of Polycaprolactone modified polynite: pass into nitrogen 30min to remove oxygen in the flask of drying, then in flask, the caprolactone monomer that mass ratio is 100:10 and polynite is added, by dispersion liquid ultrasonic vibration 1h, room temperature lower seal places 24h, caprolactone monomer is fully inserted in montmorillonite layer, the initiator tin protochloride of caprolactone monomer quality 0.8% is added in flask, intercalation polymeric carries out 10h at 150 DEG C of lower seals, the product obtained is dissolved in toluene, centrifugation after ultrasonic vibration, centrifugal product through toluene repeatedly wash centrifugal after be drying to obtain Polycaprolactone modified polynite.
(2) intercept the preparation of master batch: by high mixer, make poly(lactic acid) and the mixing of a small amount of silicone oil, then add 10% Polycaprolactone modified polynite high-speed mixing 4min, then by twin screw extruder extruding pelletization, extrusion temperature 180 DEG C.
(3) preparation of high barrier poly lactic acid nano composite material: obstruct master batch and poly(lactic acid) are mixed with the proportioning of 5:100, melt blending 8min on torque rheometer, mixing temperature 190 DEG C, obtains high barrier poly lactic acid nano composite material.
Test one
Mechanics Performance Testing: the impact property of high barrier poly lactic acid nano composite material sample is carried out on radial-boom impact tester, specimen size is straight 80mm × 10mm × 3mm.Adopt the tensile property of universal electrical drawing machine test high barrier poly lactic acid nano composite material, size of sample is 80mm × 10mm × 3mm., experimental data is as shown in the table:
| Poly(lactic acid)/modified montmorillonoid | Tensile strength (MPa) | Elongation at break (%) | Shock strength (KJ/m 2) |
| 0 | 54.3 | 4.2 | 18.4 |
| 100/1 | 55.1 | 5.8 | 20.5 |
| 100/2 | 56.5 | 7.8 | 21.7 |
| 100/3 | 62.8 | 13.8 | 23.2 |
| 100/4 | 52.5 | 9.2 | 18.9 |
| 100/5 | 49.8 | 6.3 | 17.4 |
Test two
Barrier property is tested: adopt thermostat container according to GB1037-1988 standard at 38 DEG C, measure the barrier property WVTR value that thickness is 200 mum sample under 90% humidity, experimental data is as shown in the table:
| Poly(lactic acid)/modified montmorillonoid ratio | WVTR |
| 100/0 | 1.62×10 -14 |
| 100/1 | 1.31×10 -14 |
| 100/2 | 1.14×10 -14 |
| 100/3 | 1.02×10 -14 |
| 100/4 | 9.62×10 -15 |
| 100/5 | 8.32×10 -15 |
The present invention adopts caprolactone in-situ intercalative polymerization modified montmorillonoid, and montmorillonite-based nano lamella is effectively peeled off, then makes it be dispersed in poly(lactic acid) matrix with masterbatch method, obtains higher barrier property.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from technical solution of the present invention, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. a preparation method for high barrier poly lactic acid nano composite material, is characterized in that: comprise the steps,
(1) preparation of Polycaprolactone modified polynite: add caprolactone monomer and polynite in the dry flask of removal oxygen, sealing and standing after ultrasonic vibration, caprolactone monomer is fully inserted in the lamella of polynite, initiator is added in flask, intercalation polymeric reaction is carried out in heating, the product obtained is dissolved in toluene, centrifugation after ultrasonic vibration, centrifugal product through toluene repeatedly wash centrifugal after dry, obtain Polycaprolactone modified polynite;
(2) intercept the preparation of master batch: make poly(lactic acid) and silicone oil mixing by high mixer, then add Polycaprolactone modified polynite high-speed mixing, then by forcing machine extruding pelletization, obtain intercepting master batch;
(3) preparation of high barrier poly lactic acid nano composite material: obstruct master batch and poly(lactic acid) are mixed, namely obtains high barrier poly lactic acid nano composite material after melt blending.
2. the preparation method of high barrier poly lactic acid nano composite material according to claim 1, is characterized in that: in described (1), polynite consumption is 5% ~ 10% of caprolactone monomer quality.
3. the preparation method of high barrier poly lactic acid nano composite material according to claim 1, is characterized in that: in described (1), initiator amount is 0.2% ~ 0.8% of caprolactone monomer consumption.
4. the preparation method of the high barrier poly lactic acid nano composite material according to claim 1 or 3, is characterized in that: described initiator is the one in stannous octoate, tin protochloride, methyl ethyl diketone tin, stannous oxalate, aluminum isopropylate, triethyl aluminum, porphyrin aluminium, tetrabutyl titanate, metatitanic acid orthocarbonate or isobutyl-trisphenol titanium.
5. the preparation method of high barrier poly lactic acid nano composite material according to claim 1, is characterized in that: in described (2), the mass ratio of poly(lactic acid) and Polycaprolactone modified polynite is 100:20 ~ 30.
6. the preparation method of high barrier poly lactic acid nano composite material according to claim 1, is characterized in that: described (3) described poly(lactic acid) is 100:1 ~ 5 with the mass ratio of obstruct master batch.
7. the preparation method of high barrier poly lactic acid nano composite material according to claim 1, is characterized in that: in described (1), the temperature of reaction of intercalation polymeric is 140 ~ 180 DEG C, and the reaction times is 8 ~ 12h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114410087A (en) * | 2022-01-19 | 2022-04-29 | 广东奇德新材料股份有限公司 | Barrier polylactic acid composite material and preparation method thereof |
| CN114524958A (en) * | 2022-03-16 | 2022-05-24 | 万华化学集团股份有限公司 | Preparation method of degradable barrier film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760265A (en) * | 2005-10-13 | 2006-04-19 | 同济大学 | A kind of preparation method of Nano-composite material of poly lactic acid/montmorillonite |
| CN103374213A (en) * | 2012-04-26 | 2013-10-30 | 苏州达同新材料有限公司 | Preparation method of polylactic acid/montmorillonite nano composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760265A (en) * | 2005-10-13 | 2006-04-19 | 同济大学 | A kind of preparation method of Nano-composite material of poly lactic acid/montmorillonite |
| CN103374213A (en) * | 2012-04-26 | 2013-10-30 | 苏州达同新材料有限公司 | Preparation method of polylactic acid/montmorillonite nano composite material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114410087A (en) * | 2022-01-19 | 2022-04-29 | 广东奇德新材料股份有限公司 | Barrier polylactic acid composite material and preparation method thereof |
| CN114524958A (en) * | 2022-03-16 | 2022-05-24 | 万华化学集团股份有限公司 | Preparation method of degradable barrier film |
| CN114524958B (en) * | 2022-03-16 | 2023-05-30 | 万华化学集团股份有限公司 | Preparation method of degradable barrier film |
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