CN106751628A - A kind of polylactic acid membrane and preparation method thereof - Google Patents
A kind of polylactic acid membrane and preparation method thereof Download PDFInfo
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- CN106751628A CN106751628A CN201710045278.4A CN201710045278A CN106751628A CN 106751628 A CN106751628 A CN 106751628A CN 201710045278 A CN201710045278 A CN 201710045278A CN 106751628 A CN106751628 A CN 106751628A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention relates to a kind of polylactic acid membrane, it is made up of PLA and oxygen-containing base co-polymer, wherein, PLA content is 99.5% ~ 99.9%, and copolymer level containing epoxy radicals is 0.1% ~ 0.5%.Base co-polymer containing epoxy is polymerized by trimethylol-propane trimethacrylate with GMA.The PLA can effectively improve the melt strength of PLA, it is ensured that PLA self character, and preparation process is simple, it is easy to accomplish.
Description
Technical field
The present invention relates to a kind of polylactic acid membrane and preparation method thereof, belong to polymeric material field.
Background technology
PLA be with the organic waste such as the natural plants such as corn, wheat and its lotus, leaf, root as raw material, it is fermented poly-
Conjunction is formed, therefore it has nontoxicity.And, discarded PLA manufactured goods can be degradable into titanium dioxide under field conditions (factors)
Carbon and water, can effectively reduce the pollution to ecological environment.
Although PLA has good biocompatibility, ventilative, transparent, mechanical performance and physical property are good, are very
There are one of renewable polymeric materials of application prospect, but PLA is easily hydrolyzed, and toughness is not enough, is easily damaged.So poly-
Lactic acid product is mostly that PLA is formed with reference to other high molecule plastic material combinations.As Luo Maochun et al. exists《PLA film packaging is right
The research of the fresh-keeping effect of white beech mushroom》（Chinese agronomy circular 2015,31（23）:64-69）The polylactic acid film of middle preparation,
And study its fresh-keeping effect to white beech mushroom, it is found that polylactic acid membrane is high to moisture-vapor transmission, to carbon dioxide and oxygen
Insulating is good, and the fresh-keeping effect to white beech mushroom is more preferable relative to polyethylene film；Wang Shuanshuan exists《The degradable multilayer of PLA base is answered
Close film and its application in cold fresh meat packaging》PLLA/PVA/PLLA MULTILAYER COMPOSITE polylactic acid membranes are prepared described in paper, and is ground
Study carefully its fresh-keeping effect to cold fresh meat, it is found that its fresh keeping property is substantially better than ordinary packing.
But polylactic acid melt intensity is not high, melt flow rate (MFR) is big, and machine-shaping is extremely difficult during blown film, because
This its receive certain limitation in application aspect.It is currently that to have certain methods be that poly- breast is improved by adding some additives
The melt strength of acid, such as Song Xia et al. exists《The research of E-MAH-GMA Blending Toughening Modifications PLA》(New Chemical Materials 2012
The 1st phase of volume 40：114-116) using E-MAH-GMA come toughening modified polylactic acid, disclosed in Chinese patent CN1027577627A
Polylactic acid film, but above prior art are prepared come toughening modified polylactic acid and successfully using more carboxyl polymer
In, because additive amount is excessive so that having influence on PLA characteristic in itself.
The content of the invention
It is an object of the invention to provide a kind of new polylactic acid membrane, it is set to have while PLA self character is ensured
Effect improves its melt strength, the characteristic with easy processing shaping, is more widely applied with being adapted to.
In order to realize the above object the technical solution adopted in the present invention is：A kind of polylactic acid membrane, it is characterised in that by gathering
Lactic acid and oxygen-containing base co-polymer are constituted.
Wherein, described PLA content is 99.5% ~ 99.9%, and copolymer level containing epoxy radicals is 0.1% ~ 0.5%.Its
In：
The base co-polymer containing epoxy is by trimethylol-propane trimethacrylate（TRIM）With methyl propenoic acid glycidyl
Ester（GMA）It is polymerized.
Described trimethylol-propane trimethacrylate（TRIM）With GMA（GMA）Mole
Than being 2：3~1：9；
Formula 1
Formula 2
The GMA contains double bond and epoxy radicals, terminal hydroxy group and end carboxyl is contained in PLA, such as formula 1, the copolymerization containing epoxy radicals of formula 2
There is ring-opening reaction in hydroxyl and carboxyl in epoxy radicals in thing and PLA, branch can be effectively introduced into PLA system
Chain structure, makes it be internally formed cross-linked structure, can effectively improve the melt strength of PLA, improves processing of the PLA during blown film
Processability.
Formula 3
The TRIM is a kind of conventional crosslinking agent, and it is internal containing three carbon-carbon double bonds, and as shown in Equation 3, the three carbon carbon of TRIM are double
Bond structure can make a TRIM molecule connect the GMA of three molecules, it can be ensured that less in consumption in base co-polymer containing epoxy
In the case of just can to enough epoxide groups are introduced in PLA system, reach improve polylactic acid melt intensity effect.
Add after this contains epoxy base co-polymer, the melt strength of PLA can be effectively improved, make its during blown film easily
In machine-shaping.And because its consumption is less, influence is not constituted on PLA beneficial characteristics in itself still.Gained PLA can use
In the preparation of the plastic sheetings such as food package film, preservative film.
Described polylactic acid membrane, its preparation technology is：
（1）TRIM is polymerized with GMA by formula ratio, obtains base co-polymer containing epoxy；
（2）By step（1）In base co-polymer containing epoxy and PLA be placed in melting extrusion in parallel dual-screw extruding machine, pelletizing；
（3）By step（2）Gained pellet is through Single screw extrusion inflation film manufacturing machine Blown Film.
Wherein, step（2）Middle parallel dual-screw extruding machine expressing technique condition is：One 230 DEG C of area, 230 DEG C of 2nd area, 3rd area
230 DEG C, 240 DEG C of 4th area, 240 DEG C of 5th area, 240 DEG C of 6th area, 240 DEG C of 7th area, 245 DEG C of 8th area, 245 DEG C of 9th area, 245 DEG C of head,
Engine speed 110r/min, feeding rotating speed 50r/min, using water cooling bracing pelletizing.
Step（3）Middle Single screw extrusion inflation film manufacturing machine film-blowing process condition is：Three sections of temperature of extruder are respectively：230℃、
240 DEG C, 245 DEG C, head temperature is set as：240 DEG C ~ 250 DEG C, pulling speed is：5 m/min.
Beneficial effects of the present invention are as follows：
（1）A kind of polylactic acid membrane of new easy processing of the present invention, can effectively improve the melt strength of PLA, make its
Shaping easier to process during blown film；
（2）Polylactic acid membrane of the present invention, contained additive capacity is few, and shadow is not constituted still to PLA beneficial characteristics in itself
Ring；
（3）Preparation method of the present invention, process is simple, it is easy to accomplish.
Specific implementation method
With reference to example, the present invention will be further described.Embodiment is the embodiment of the present invention, not to of the invention
Technical scope does any limitation, aunt it is every according to technical spirit of the invention to any trickle amendment made for any of the above embodiments,
Equivalent variations and modification, still fall within the range of technical solution of the present invention.
Embodiment 1
Take 20.9g TRIM and 79.1g GMA（Mol ratio is 1：9）It is polymerized, is obtained base co-polymer containing epoxy；Then incite somebody to action
To base co-polymer containing epoxy and 99.9 kg PLA be placed in melting extrusion in parallel dual-screw extruding machine, pelletizing.Its process conditions
For：One 230 DEG C of area, 230 DEG C of 2nd area, 230 DEG C of 3rd area, 240 DEG C of 4th area, 240 DEG C of 5th area, 240 DEG C of 6th area, 240 DEG C of 7th area, 8th area
245 DEG C, 245 DEG C of 9th area, 245 DEG C of head, engine speed 110r/min, feeding rotating speed 50r/min, using water cooling bracing pelletizing；
Finally, by gained pellet through Single screw extrusion inflation film manufacturing machine Blown Film.Its process conditions is：Three sections of temperature of extruder are respectively：
230 DEG C, 240 DEG C, 245 DEG C, head temperature is set as：240 DEG C ~ 250 DEG C, pulling speed is：5 m/min.
Embodiment 2
Take 75g TRIM and 125g GMA g（Mol ratio is 1：4）It is polymerized, is obtained base co-polymer containing epoxy；Then will obtain
Base co-polymer containing epoxy and 99.8 kg PLA be placed in melting extrusion in parallel dual-screw extruding machine, pelletizing.Its process conditions
For：One 230 DEG C of area, 230 DEG C of 2nd area, 230 DEG C of 3rd area, 240 DEG C of 4th area, 240 DEG C of 5th area, 240 DEG C of 6th area, 240 DEG C of 7th area, 8th area
245 DEG C, 245 DEG C of 9th area, 245 DEG C of head, engine speed 110r/min, feeding rotating speed 50r/min, using water cooling bracing pelletizing；
Finally, by gained pellet through Single screw extrusion inflation film manufacturing machine Blown Film.Its process conditions is：Three sections of temperature of extruder are respectively：
230 DEG C, 240 DEG C, 245 DEG C, head temperature is set as：240 DEG C ~ 250 DEG C, pulling speed is：5 m/min.
Embodiment 3
Take 112.5g TRIM and 187.5g GMA（Mol ratio is 1：4）It is polymerized, is obtained base co-polymer containing epoxy；Then will
The base co-polymer containing epoxy and 99.7 Kg PLA for obtaining are placed in melting extrusion in parallel dual-screw extruding machine, pelletizing.Its technique bar
Part is：One 230 DEG C of area, 230 DEG C of 2nd area, 230 DEG C of 3rd area, 240 DEG C of 4th area, 240 DEG C of 5th area, 240 DEG C of 6th area, 240 DEG C of 7th area, eight
245 DEG C of area, 245 DEG C of 9th area, 245 DEG C of head, engine speed 110r/min, feeding rotating speed 50r/min are cut using water cooling bracing
Grain；Finally, by gained pellet through Single screw extrusion inflation film manufacturing machine Blown Film.Its process conditions is：Three sections of temperature difference of extruder
For：230 DEG C, 240 DEG C, 245 DEG C, head temperature is set as：240 DEG C ~ 250 DEG C, pulling speed is：5 m/min.
Embodiment 4
Take 245.6g TRIM and 154.4g GMA（Mol ratio is 2：3）It is polymerized, is obtained base co-polymer containing epoxy；Then will
The base co-polymer containing epoxy and 99.6 Kg PLA for obtaining are placed in melting extrusion in parallel dual-screw extruding machine, pelletizing.Its technique bar
Part is：One 230 DEG C of area, 230 DEG C of 2nd area, 230 DEG C of 3rd area, 240 DEG C of 4th area, 240 DEG C of 5th area, 240 DEG C of 6th area, 240 DEG C of 7th area, eight
245 DEG C of area, 245 DEG C of 9th area, 245 DEG C of head, engine speed 110r/min, feeding rotating speed 50r/min are cut using water cooling bracing
Grain；Finally, by gained pellet through Single screw extrusion inflation film manufacturing machine Blown Film.Its process conditions is：Three sections of temperature difference of extruder
For：230 DEG C, 240 DEG C, 245 DEG C, head temperature is set as：240 DEG C ~ 250 DEG C, pulling speed is：5 m/min.
Embodiment 5
Take 306.7g TRIM and 193.3g GMA（Mol ratio is 2：3）It is polymerized, is obtained base co-polymer containing epoxy；Then will
The base co-polymer containing epoxy for obtaining is placed in melting extrusion in parallel dual-screw extruding machine, pelletizing with 99.5Kg PLA.Its technique bar
Part is：One 230 DEG C of area, 230 DEG C of 2nd area, 230 DEG C of 3rd area, 240 DEG C of 4th area, 240 DEG C of 5th area, 240 DEG C of 6th area, 240 DEG C of 7th area, eight
245 DEG C of area, 245 DEG C of 9th area, 245 DEG C of head, engine speed 110r/min, feeding rotating speed 50r/min are cut using water cooling bracing
Grain；Finally, by gained pellet through Single screw extrusion inflation film manufacturing machine Blown Film.Its process conditions is：Three sections of temperature difference of extruder
For：230 DEG C, 240 DEG C, 245 DEG C, head temperature is set as：240 DEG C ~ 250 DEG C, pulling speed is：5 m/min.
Embodiment 6
The polylactic acid membrane produced in Example 1-5 carries out melt strength measure, specifically determines melt flow rate (MFR), obtain as
Lower data：
For data above, compared to the PLA in itself melt flow rate (MFR) of 7 g/10min for, it will be evident that with
The increase of the content of oxygen-containing base co-polymer, polylactic acid melt flow rate reduces, and melt strength is dramatically increased.
Claims (7)
1. a kind of polylactic acid membrane, it is characterised in that be made up of PLA and oxygen-containing base co-polymer.
2. polylactic acid membrane as claimed in claim 1, it is characterised in that described PLA content is 99.5% ~ 99.9%, containing ring
Epoxide copolymer level is 0.1% ~ 0.5%.
3. polylactic acid membrane as claimed in claim 1, it is characterised in that described base co-polymer containing epoxy is by trimethylolpropane
Trimethyl acrylic ester is polymerized with GMA.
4. polylactic acid membrane as claimed in claim 1, it is characterised in that described trimethylol-propane trimethacrylate with
GMA mol ratio is 2：3~1：9.
5. polylactic acid membrane preparation method as claimed in claim 1, it is characterised in that comprise the following steps：
（1）Trimethylol-propane trimethacrylate is polymerized with GMA by formula ratio, is contained
Epoxy base co-polymer；
（2）By step（1）In base co-polymer containing epoxy be placed in melting extrusion in parallel dual-screw extruding machine with PLA, cut
Grain；
（3）By step（2）Gained pellet is through Single screw extrusion inflation film manufacturing machine Blown Film.
6. polylactic acid membrane preparation method as claimed in claim 5, it is characterised in that step（2）Middle parallel dual-screw extruding machine is squeezed
Going out process conditions is：One 230 DEG C of area, 230 DEG C of 2nd area, 230 DEG C of 3rd area, 240 DEG C of 4th area, 240 DEG C of 5th area, 240 DEG C of 6th area, 7th area
240 DEG C, 245 DEG C of 8th area, 245 DEG C of 9th area, 245 DEG C of head, engine speed 110r/min, feeding rotating speed 50r/min, using water-cooled
Tie rod pelletizing.
7. polylactic acid membrane preparation method as claimed in claim 5, it is characterised in that step（3）Middle Single screw extrusion inflation film manufacturing machine blows
Membrane process condition is：Three sections of temperature of extruder are respectively：230 DEG C, 240 DEG C, 245 DEG C, head temperature is set as：240℃~250
DEG C, pulling speed is：5 m/min.
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| CN201710045278.4A CN106751628B (en) | 2017-01-22 | 2017-01-22 | A kind of polylactic acid membrane and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902258A (en) * | 2017-09-28 | 2018-04-13 | 武汉华丽生物股份有限公司 | Degradable paper-plastic composite film paper and preparation method thereof |
| CN108676335A (en) * | 2018-05-28 | 2018-10-19 | 安徽聚美生物科技有限公司 | A kind of preparation method of high transparency polylactic acid film |
| CN113402678A (en) * | 2021-06-17 | 2021-09-17 | 华南理工大学 | Method for preparing high-melt-strength polylactic resin through two-step reaction |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440165A (en) * | 2007-11-19 | 2009-05-27 | 上海华酝化工科技有限公司 | Biodegradable flexible polylactic acid alloy film and preparation thereof |
-
2017
- 2017-01-22 CN CN201710045278.4A patent/CN106751628B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440165A (en) * | 2007-11-19 | 2009-05-27 | 上海华酝化工科技有限公司 | Biodegradable flexible polylactic acid alloy film and preparation thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902258A (en) * | 2017-09-28 | 2018-04-13 | 武汉华丽生物股份有限公司 | Degradable paper-plastic composite film paper and preparation method thereof |
| CN108676335A (en) * | 2018-05-28 | 2018-10-19 | 安徽聚美生物科技有限公司 | A kind of preparation method of high transparency polylactic acid film |
| CN113402678A (en) * | 2021-06-17 | 2021-09-17 | 华南理工大学 | Method for preparing high-melt-strength polylactic resin through two-step reaction |
| CN113402678B (en) * | 2021-06-17 | 2022-04-22 | 华南理工大学 | Method for preparing high-melt-strength polylactic resin through two-step reaction |
| US11505646B1 (en) | 2021-06-17 | 2022-11-22 | South China University Of Technology | Method for producing high-melt-strength polylactide resin |
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Effective date of registration: 20200423 Address after: 255400, Hongda Road 17, Linzi District, Shandong, Zibo Patentee after: SHANDONG YONGJU MEDICAL TECHNOLOGY Co.,Ltd. Address before: 255400 No. 28, Renmin East Road, Linzi District, Shandong, Zibo Patentee before: SHANDONG QIDU PHARMACEUTICAL Co.,Ltd. |
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Address after: No.17 Hongda Road, Linzi District, Zibo City, Shandong Province Patentee after: Shandong Yongju Pharmaceutical Technology Co.,Ltd. Address before: No.17 Hongda Road, Linzi District, Zibo City, Shandong Province Patentee before: SHANDONG YONGJU MEDICAL TECHNOLOGY Co.,Ltd. |