CN103865245A - Preparation method of hydrolysis-resistant polylactic resin - Google Patents
Preparation method of hydrolysis-resistant polylactic resin Download PDFInfo
- Publication number
- CN103865245A CN103865245A CN201410104915.7A CN201410104915A CN103865245A CN 103865245 A CN103865245 A CN 103865245A CN 201410104915 A CN201410104915 A CN 201410104915A CN 103865245 A CN103865245 A CN 103865245A
- Authority
- CN
- China
- Prior art keywords
- hydrolysis
- resin
- poly
- resistant
- polylactic
- 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
Abstract
The invention discloses novel hydrolysis-resistant polylactic resin and a preparation method thereof. The novel hydrolysis-resistant polylactic resin is formed by adding a 2.2',6.6'-tetraisopropyl diphenyl carbodiimide hydrolysis-resistant agent into polylactic acid, and performing melting and co-mixing. The hydrolysis-resistant polylactic resin basically consists of the following components in percentage by weight: 95%-99.99% of polylactic materials, and 0.01%-5% of 2.2',6.6'-tetraisopropyl diphenyl carbodiimide. The hydrolysis-resistant polylactic resin prepared by the preparation method disclosed by the invention has very good hydrolysis resistance, has lower weight-average molecular weight degradation rate after being treated by hot water of 65 DEG C, so that stability of the polylactic resin under conditions of high temperature and high humidity is improved, and wide application of the polylactic resin is promoted.
Description
One, technical field
The present invention relates to a kind of polylactic resin, be specifically related to a kind of fully biodegradable type polylactic resin that adds 2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide and have resistant to hydrolysis performance; Belong to biodegradable material field.
Two, background technology
Plastics are widely used in all respects of people's life as a kind of novel material, for people provide a lot of convenience.But most of plastics do not possess biodegradable characteristic; after discarded, cause serious problem of environmental pollution; again because most of plastics take Nonrenewable resources if oil etc. is for raw material synthesizes, therefore use in a large number petroleum-based plastics to bring serious crisis of resource to the mankind.In order to make the mankind no longer rely on Nonrenewable resources, and the problem of solution " white pollution ", the environmentally friendly biodegradable plastic searching out take renewable resources as raw material is just becoming current worldwide study hotspot.
Biodegradable plastic can not produced by the degradable one-tenth of natural microorganism inorganics capable of circulation the macromolecular material of a class of objectionable impurities after referring to and discarding, and this class material has good safe handling.Bio-based aliphatic polyester, for example: PLA, PBS, PHA, and their mixture is as a class bio-based degradation material, due to its excellent performance, is more and more paid close attention to recently.In environmentally friendly bio-based degradable plastics, poly(lactic acid) (PLA) has good biological degradability, compostability, biocompatibility and good thermomechanical property, in addition, poly(lactic acid) is the most cheap universally acknowledged bio-based degradable plastics, therefore becomes the most competitive bio-based degradable plastics of petroleum replacing base plastics.
But the resistance to hydrolysis of polylactic resin is poor, under hot and humid condition, store after certain hour, the ester linkage hydrolyzing chain rupture in polylactic acid molecule chain, causes the Mechanical Properties of Products of polylactic resin processing to decline to a great extent.Therefore, improve the hydrolytic resistance of polylactic resin and improve its application under hot and humid condition extremely important.
Japanese Patent JP9296097 discloses the resistant to hydrolysis preparation method that a kind of polyester (such as urethane, PET, poly(lactic acid) etc.) is matrix resin.Special carbodiimide is added to melt blending in polyester matrix resin by this patent, finally obtained the outstanding polyester material of resistant to hydrolysis performance.
The Chinese patent application 201180006421.X of Teijin Ltd of Japan discloses a kind of preparation method of resistance to hydrolysis composition of stereocomplex polylactic resin.This patent, by auxiliary agent and stereocomplex polylactic resin melt blendings such as ring-type carbodiimide, oxidation inhibitor, has made the stereocomplex polylactic acid resin composition with hydrolytic resistance excellence.
Toray Fiber Research Institute's Chinese patent 200910183185.3 discloses a kind of hydrolysis-resistant polylactic acid composition, it is mainly by 100 weight part polylactic resin, 0.1～5 weight part end-capping reagent, 0.01～0.5 weight part esterification promotor, 0.01～5 shares of metal buffer reagent forms, end-capping reagent has adopted the carbodiimide of Lay mattress chemistry Stabaxol1LF, Nisshinbo HMV-8CA, Nisshinbo LA-1 and Shanghai covalent chemical DCC, and the polylactic resin of preparation has excellent hydrolysis characteristic.
Toray Fiber Research Institute's Chinese patent 200710133647.1 discloses a kind of hydrolysis resistant flexible polylactic acid orientation products and production method, the patented product is made take polylactic resin, softening agent, resistant to hydrolysis stablizer as raw material, wherein hydrolysis-resisting agent is glycidyl ether or three-glycidyl based isocyanate, production method comprises polylactic resin and softening agent is mixed into mixture, mixture and resistant to hydrolysis stablizer are mixed to form to blending resin, blending resin is carried out to heat treated, form melt and be shaped to orientation products.Hydrolysis resistant flexible polylactic acid composition in the present invention, compared with poly(lactic acid) as matrix resin, has excellent hydrolytic resistance.
United States Patent (USP) the 5763538th discloses a kind of manufacture method of resistant to hydrolysis stablizer modification oriented polyester article, and it is by the polyoxyethylene glycol of vibrin and methoxyl group end-blocking and polycarbodiimide compound melt blending, then machine-shaping orientation products.
YKK Co., Ltd's Chinese patent discloses a kind of manufacture method of fastener product of synthetic resins manufacture of hydrolysis, it is in polyester PET resin, add aromatic polycarbodiimide and realize, it is said that this fastener product has excellent resistance to hydrolysis, clasp does not produce the defect such as variable color and strength degradation.
But the research that adopts 2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide hydrolysis-resisting agent to improve polylactic resin hydrolytic resistance has no report.
Three, summary of the invention
The object of the present invention is to provide good polylactic resin of a kind of resistant to hydrolysis performance and preparation method thereof.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs: a kind of hydrolytic-resistant polylactic acid resin material, and this hydrolytic-resistant polylactic acid resin material is grouped into by the one-tenth of following weight percent substantially:
Poly-lactic acid material: 95%～99.99%
2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide: 0.01%～5%.
Because the resistance to hydrolysis of polylactic resin is poor, under hot and humid condition, store after certain hour, the ester linkage hydrolyzing chain rupture in polylactic acid molecule chain, causes the Mechanical Properties of Products of polylactic resin processing to decline to a great extent, and is difficult to adapt to daily use.The present invention is by add 2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide in poly-lactic acid material, thereby significantly improved the resistance to hydrolysis of polylactic resin under hot and humid condition.
The method of adding 2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide in poly(lactic acid) can realize by ordinary method.For example, by poly-lactic acid material and 2.2 ', after 6.6 '-tetra isopropyl phenylbenzene carbodiimide mixes with various mixing machines, employing single screw extrusion machine, twin screw extruder or Banbury mixer etc. are mixing all can.Melting temperature carries out conventionally at the temperature of 155～210 ℃ of left and right.In addition, also 2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide first can be made to the master batch that contains various compositions is added in poly-lactic acid material.In addition, also can be before poly lactic acid polymerized, in polymerization process or when polymerization discharging, sneak into.
In above-mentioned hydrolytic-resistant polylactic acid resin, as preferably, described hydrolytic-resistant polylactic acid resin is grouped into by the one-tenth of following weight percent substantially:
Poly-lactic acid material: 96%～99.8%
2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide: 0.2%～4%.
As more preferably, described hydrolysis polylactic resin is grouped into by the one-tenth of following weight percent substantially:
Poly-lactic acid material: 97%～99.5%
2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide: 0.5%～3%.
In above-mentioned hydrolytic-resistant polylactic acid resin, described poly(lactic acid) is Poly-L-lactide homopolymer, poly--D-ALPHA-Hydroxypropionic acid homopolymer, one or more of Poly-L-lactide and poly--D-ALPHA-Hydroxypropionic acid multipolymer and Poly-L-lactide and poly--D-ALPHA-Hydroxypropionic acid blend species.
In above-mentioned hydrolytic-resistant polylactic acid resin, this polylactic resin also can use the various coupling agents such as the known nucleator of prior art, antioxidant, pigment, tinting material, softening agent, compatilizer, thermo-stabilizer, photostabilizer, uv-absorbing agent, whipping agent, static inhibitor, impact modifying agent, essence, inorganic filler, fire retardant, titanium system, silane system, aluminium system, can adopt the various auxiliary agents that add in general plastics.
Hydrolytic-resistant polylactic acid resin of the present invention is in polylactic resin, to add 2.2 ' of certainweight per-cent, 6.6 '-tetra isopropyl phenylbenzene carbodiimide, to the carboxyl in polylactic resin, hydroxy-end capped modification, thereby obtain having the polylactic resin of resistant to hydrolysis performance under hot and humid condition.Hydrolytic-resistant polylactic acid resin of the present invention, only the existing ordinary skill technique of need employing just can be by 2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide is added in poly(lactic acid), technical process is simple, suitability for mass industrializedization is produced, and also can not change in addition the biodegradable characteristic of poly(lactic acid).In addition, hydrolytic-resistant polylactic acid resin of the present invention is through 65 ℃ of hot-water cure after 3～40 days, and its weight-average molecular weight still can retain more than 71%.
Four, embodiment
Below by embodiment; technical scheme to this technological invention is described in further detail; but the present invention is not limited to these embodiment; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
Embodiment 1
Get the polylactic resin (4032D of 10Kg after vacuum-drying, NatureWorks company), 1g2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide mixes, and extrudes by twin screw extruder melt blending, melt is tie rod pelletizing after tank is cooling, forcing machine feed zone temperature is 170 ℃, 180 ℃ of second segments, the 3rd section 190 ℃, 200 ℃ of all the other sections, screw speed is 250rpm.By particle 90 ℃ of vacuum-dryings after 4 hours, then by particle through 65 ℃ of hot-water cure, the weight-average molecular weight degradation rate after hydrolysis in 3 days is lower than 29%.
Embodiment 2
Get the polylactic resin (3051D of 10Kg after vacuum-drying, NatureWorks company), 100g2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide mixes, and carries out mixing with Banbury mixer, melting temperature is 200 ℃, and rotor frequency is 20Hz.After this resin is pulverized, 90 ℃ of vacuum-dryings after 4 hours, then by this resin through 65 ℃ of hot-water cure, the weight-average molecular weight degradation rate after hydrolysis in 9 days is lower than 8%.
Embodiment 3
Get the polylactic resin (6201D of 10Kg after vacuum-drying, NatureWorks company), 200g2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide mixes, extrude by single screw extrusion machine melt blending, melt is tie rod pelletizing after tank is cooling, and forcing machine feed zone temperature is 170 ℃, 180 ℃ of second segments, the 3rd section 190 ℃, 200 ℃ of all the other sections, screw speed is 250rpm.By particle 90 ℃ of vacuum-dryings after 4 hours, then by particle through 65 ℃ of hot-water cure, the weight-average molecular weight degradation rate after hydrolysis in 20 days is lower than 9%.
Embodiment 4
Get the polylactic resin (8052D of 10Kg after vacuum-drying, NatureWorks company), 500g2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide mixes, extrude by twin screw extruder melt blending, melt is tie rod pelletizing after tank is cooling, and forcing machine feed zone temperature is 170 ℃, 180 ℃ of second segments, the 3rd section 190 ℃, 200 ℃ of all the other sections, screw speed is 250rpm.By particle 90 ℃ of vacuum-dryings after 4 hours, then by particle through 65 ℃ of hot-water cure, the weight-average molecular weight degradation rate after hydrolysis in 40 days is lower than 15%.
Comparative example 1
Get the polylactic resin (3051D, NatureWorks company) of 10Kg after vacuum-drying through 65 ℃ of hot-water cure, the weight-average molecular weight degradation rate after hydrolysis in 3 days reaches 41%.
Claims (4)
1. a hydrolytic-resistant polylactic acid resin, is characterized in that: this polylactic resin is grouped into by the one-tenth of following weight percent substantially:
Poly-lactic acid material: 95%～99.99%
2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide: 0.01%～5%.
2. hydrolytic-resistant polylactic acid resin according to claim 1, is characterized in that: described carbodiimide is: 2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide.
3. according to the hydrolytic-resistant polylactic acid resin described in claims 1, as preferably, described hydrolytic-resistant polylactic acid resin is grouped into by the one-tenth of following weight percent substantially:
Poly-lactic acid material: 96%～99.8%
2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide: 0.2%～4%.
As more preferably, described hydrolysis polylactic resin is grouped into by the one-tenth of following weight percent substantially:
Poly-lactic acid material: 97%～99.5%
2.2 ', 6.6 '-tetra isopropyl phenylbenzene carbodiimide: 0.5%～3%.
4. according to the hydrolytic-resistant polylactic acid resin described in claims 1 or 3, it is characterized in that: described poly(lactic acid) is poly (l-lactic acid) homopolymer, poly-D-ALPHA-Hydroxypropionic acid homopolymer, one or more of poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid multipolymer and poly (l-lactic acid) and poly-D-ALPHA-Hydroxypropionic acid blend species.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410104915.7A CN103865245A (en) | 2014-03-18 | 2014-03-18 | Preparation method of hydrolysis-resistant polylactic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410104915.7A CN103865245A (en) | 2014-03-18 | 2014-03-18 | Preparation method of hydrolysis-resistant polylactic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103865245A true CN103865245A (en) | 2014-06-18 |
Family
ID=50904288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410104915.7A Pending CN103865245A (en) | 2014-03-18 | 2014-03-18 | Preparation method of hydrolysis-resistant polylactic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103865245A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661187A (en) * | 2014-07-14 | 2017-05-10 | 莱茵化学莱瑙有限公司 | Method for stabilizing polyester-resin-based bioplastics |
| CN111040401A (en) * | 2019-12-28 | 2020-04-21 | 诺思贝瑞新材料科技（苏州）有限公司 | High-performance modified polylactic acid composite material and preparation method thereof |
| CN114960177A (en) * | 2022-06-13 | 2022-08-30 | 山东道恩高分子材料股份有限公司 | Biodegradable melt-spray material with long-acting static retention function |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101990565A (en) * | 2008-04-08 | 2011-03-23 | 花王株式会社 | Polylactic acid resin composite |
| CN102471564A (en) * | 2009-07-10 | 2012-05-23 | 尤尼吉可株式会社 | Polylactic acid-based resin composition and molded article |
-
2014
- 2014-03-18 CN CN201410104915.7A patent/CN103865245A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101990565A (en) * | 2008-04-08 | 2011-03-23 | 花王株式会社 | Polylactic acid resin composite |
| CN102471564A (en) * | 2009-07-10 | 2012-05-23 | 尤尼吉可株式会社 | Polylactic acid-based resin composition and molded article |
Non-Patent Citations (2)
| Title |
|---|
| 姚建文等: "碳化二亚胺抗水解剂的研究进展", 《精细与专用化学品》 * |
| 张杰等: "聚碳化二亚胺对聚乳酸抗水解性能的影响", 《塑料工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661187A (en) * | 2014-07-14 | 2017-05-10 | 莱茵化学莱瑙有限公司 | Method for stabilizing polyester-resin-based bioplastics |
| CN106661187B (en) * | 2014-07-14 | 2019-11-05 | 朗盛德国有限责任公司 | Method for stablizing the biological plastics based on polyester resin |
| CN111040401A (en) * | 2019-12-28 | 2020-04-21 | 诺思贝瑞新材料科技（苏州）有限公司 | High-performance modified polylactic acid composite material and preparation method thereof |
| CN114960177A (en) * | 2022-06-13 | 2022-08-30 | 山东道恩高分子材料股份有限公司 | Biodegradable melt-spray material with long-acting static retention function |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3404067B1 (en) | Plasticised biodegradable polyester film and preparation method therefor | |
| CN108822514B (en) | Completely biodegradable polylactic acid based blown film and preparation method thereof | |
| CN104072957B (en) | A kind of food grade biodegradable polylactic acid based composites and application thereof | |
| CN102618003A (en) | Polylactic acid composition and polylactic acid product | |
| CN101824211B (en) | Full-biodegradation high-tenacity heat-resistant type polylactic resin and preparation method thereof | |
| CN108929527B (en) | PBAT/modified starch full-biodegradable film with high ductility and high barrier property as well as preparation method and application thereof | |
| CN104109363A (en) | High-strength high-toughness transparent polylactic acid composition and preparation method thereof | |
| CN103146160A (en) | Fully-biodegradable composition and preparation method thereof | |
| CN105400165A (en) | Bio-based polyester modified polylactic resin, preparation method and processing forming method | |
| CN111978691B (en) | Biodegradable mulching film and preparation method thereof | |
| CN105038158A (en) | Preparation method of food-grade full-degradable high-temperature-resistant polylactic acid composite material | |
| CN104387732A (en) | Transparent, tear-resistant and biodegradable polylactic acid thin film and preparation method thereof | |
| CN106467657A (en) | High heat-resisting PLA/PHA composite and preparation method thereof | |
| KR100642289B1 (en) | Biodegradable resin composition, method of producing the same and biodegradable film | |
| CN103571166B (en) | Mierocrystalline cellulose, poly (propylene carbonate) composition | |
| CN106496962A (en) | Contain PLA/polyethylene terephthalate（PET）Alloy biodegradation material and preparation method thereof | |
| CN102250389B (en) | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof | |
| CN113956630A (en) | Completely biodegradable film and preparation method thereof | |
| WO2023245997A1 (en) | Marine degradable polyhydroxyalkanoate composition, molded body and preparation method therefor | |
| JP5509588B2 (en) | Resin composition and molded article using the same | |
| CN103865245A (en) | Preparation method of hydrolysis-resistant polylactic resin | |
| CN109867918B (en) | Contact antibacterial material with excellent performance and preparation method thereof | |
| CN112662143A (en) | PBT composition with high elongation at break and preparation method thereof | |
| CN103102661B (en) | Rapid nucleating agent for polylactic resin | |
| CN106893276A (en) | A kind of high-flexibility and heat-resistance polylactic acid are material modified and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140618 |