CN110204876A - A kind of method of modifying of poly-lactic acid material activeness and quietness - Google Patents
A kind of method of modifying of poly-lactic acid material activeness and quietness Download PDFInfo
- Publication number
- CN110204876A CN110204876A CN201910619224.3A CN201910619224A CN110204876A CN 110204876 A CN110204876 A CN 110204876A CN 201910619224 A CN201910619224 A CN 201910619224A CN 110204876 A CN110204876 A CN 110204876A
- Authority
- CN
- China
- Prior art keywords
- ionomer
- sulfonation
- polystyrene
- poly
- segment
- 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
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of method of modifying of polylactic acid activeness and quietness.Using the sulfonated polystyrene class ionomer of the rigid chain segment containing sulfonation and thermoplastic elastic soft segment and polylactic acid melt blending, carry out modified polylactic acid material, while achieving the effect that activeness and quietness.Sulfonated polystyrene class ionomer is that polystyrene based block copolymer for example poly- (s-B-S) (SEBS) etc. is obtained by the sulfonation different degrees of to polystyrene chain segment, and soft segment therein plays the effect to lactic acid composite material toughening.
Description
Technical field
The invention belongs to composite modification fields, are related to the modification side that a kind of pair of poly-lactic acid material carries out activeness and quietness
Method.
Background technique
Polylactic acid is also referred to as polylactide, belongs to polyester-based polymer material.Polylactic acid is poly- by primary raw material of lactic acid
It closes obtained polymer, sufficient raw and can regenerate, therefore be ideal Green Polymer Material.Polylactic acid has
Excellent biodegradable and biocompatibility, can be degradable by microorganism in nature after use, ultimately generates dioxy
Change carbon and water, it is free from environmental pollution.The advantages such as polylactic acid intensity also with higher, modulus and good processability, are great cities
The environmentally friendly polymer material of field application prospect, has been widely used in bio-medical material, disposable degradable at present
The fields such as material, packaging material and textile.Polylactic acid belongs to hard material, and elasticity modulus is very high, but its poor toughness, fracture
Elongation is low with impact strength, it is difficult to apply the occasion high in the toughness reguirements to high molecular material, this disadvantage seriously restricts
The application progress of polylactic acid.Therefore, biology base polymeric material field is become to the toughening modifying research of poly-lactic acid material
Important subject is always the research emphasis of industry and academia.
The present invention is proposed using sulfonated polystyrene class ionomer come the method for activeness and quietness polylactic acid.Sulfonation is Xiang Youji
Sulfonic acid group is introduced in compound molecule, sulphur atom is allowed to be connected with carbon atom, obtains sulfoacid compound.Sulfur trioxide can be used,
It is prepared by the concentrated sulfuric acid, the sulfonating agents such as oleum.Sulfonated polystyrene class ionomer is a kind of special block copolymer, is referred to
A quasi polymer is formed by after carrying out sulfonation to the polystyrene in the copolymer containing polystyrene chain segment.It will be to polylactic acid
Toughening modifying is carried out, feasible method is that high molecular material flexible is introduced in polylactic acid matrix, improves the tough of composite material
Property.In the present invention, using the ionomer modified poly-lactic acid material containing rigid chain segment and soft segment, while reaching enhancing and increasing
Tough target.Rigid macromolecule segment is the polystyrene chain segment of sulfonation, can according to need the polyphenyl for selecting different sulfonation degrees
The intensity of lactic acid composite material can be enhanced in the polystyrene of ethylene segment, polystyrene and sulfonation.Flexible macromolecule segment
It is thermoplastic elastic segment, such as polybutadiene segments, polyisoprene segments, hydrogenated butadiene polymer segment.Flexible macromolecule
Segment plays the role of absorption impact energy in polylactic acid matrix, improves polylactic acid matrix toughness.
Summary of the invention
The purpose of the present invention is being directed to deficiency of the existing polylactic acid in terms of mechanical strength and toughness, provide a kind of using sulphur
Change the method that polystyrene type ionomer carrys out activeness and quietness poly-lactic acid material.
The present invention for achieving the above object used by technical solution are as follows:
A certain amount of sulfonated polystyrene class ionomer powder and polylactic acid powder elder generation physical blending are uniform, then exist
190oC-220oMelt blending is uniform at a temperature of C, prepares lactic acid composite material.
The melt blending can carry out in extruder or mixer.Melting temperature is according to sulfonated polystyrene class
The type and sulfonation degree of ionomer determine.
In the above technical solution:
The sulfonated polystyrene class ionomer is the polystyrene chain segment in copolymer of the sulfonation containing polystyrene chain segment and
It obtains.The sulfonation degree of polystyrene chain segment is between 5% to 60%.Sulfonation degree is hydrogen on polystyrene structural unit by sulfonate radical
Group replace degree, reflect polymer contain sulfonic acid group number, structure and performance to sulfonated polymer have important
Influence.Sulfonation degree can be measured with the methods of the precipitation method, elemental microanalysis method, acid-base titration.
The type of the sulfonated polystyrene class ionomer includes but are not limited to poly- (styrene-isoamyl two of sulfonation
Alkene-styrene) ionomer (SSIS)；Poly- (s-B-S) ionomer (SSBS) of sulfonation；Poly- (the benzene of sulfonation
Ethylene-vinyl-butylene-styrene) ionomer (SSEBS)；Poly- (styrene ethylene-propylene-styrene) ionomer of sulfonation
(SSEPS) etc..It further include the polystyrene that other hard segments are sulfonation, soft segment is the ionomer of thermoplastic elastic segment.
The quality of the polystyrene chain segment before sulfonation in the sulfonated polystyrene class ionomer accounts for total copolymer
Mass fraction is between 20% to 80%.
The sulfonated polystyrene class ionomer is between 1% to 40% in the mass fraction in lactic acid composite material.
Sulfonated polystyrene class ionomer used in the modification can be single variety, be also possible to any two
Or it is several.
The invention has the following beneficial effects:
1, the present invention is ionomer modified using the sulfonated polystyrene class simultaneously containing rigid segment and thermoplastic elastic soft chain segment
Polylactic acid has the function of while improving the mechanical strength and toughness of lactic acid composite material；
2, blending modification method of the invention can reach poly-lactic acid material in the case where not changing prior art condition substantially
Modification purpose.
Specific embodiment
The present invention is elaborated combined with specific embodiments below, but these embodiments do not limit the scope of the invention.
Embodiment 1:
In the present embodiment, weighing the poly(styrene-isoprene-styrene) ionomer powder of 3 grams of sulfonation, (sulfonation degree is
5.6%) uniform with 30 grams of polylactic acid powder elder generation physical blendings, it is then added in mixer 200oC melt blending 15 minutes,
Then the sample that injection molding obtains lactic acid composite material carries out the test of mechanical property.Test result shows the drawing of pure polylactic acid
Stretching intensity is 42MPa, and the tensile strength of prepared lactic acid composite material is 45MPa, improves 7%, while elongation at break
It has been increased to 11% from 6%, has improved 0.83 times.
Embodiment 2:
In the present embodiment, weighing the poly(styrene-isoprene-styrene) ionomer powder of 4 grams of sulfonation, (sulfonation degree is
14.7%) uniform with 30 grams of polylactic acid powder elder generation physical blendings, it is then added in mixer 200oC melt blending 15 minutes,
Then the sample that injection molding obtains lactic acid composite material carries out the test of mechanical property.Test result shows prepared poly- cream
The tensile strength of sour composite material is 48MPa, improves 14%, while elongation at break is increased to 10%.
Embodiment 3:
In the present embodiment, weighing poly- (styrene-ethylene-butylene-styrene) the ionomer powder of 9 grams of sulfonation, (sulfonation degree is
4.8%) uniform with 60 grams of polylactic acid powder elder generation physical blendings, it is then added in miniature extruder 200oC is total with circulation melting
Mixed mode is blended 10 minutes, and the sample that then injection molding obtains lactic acid composite material carries out the test of mechanical property.Test knot
Fruit shows that the tensile strength of prepared lactic acid composite material is 49MPa, improves 17%, elongation at break is increased to from 6%
17%, improve 1.83 times.
Embodiment 4:
In the present embodiment, weighing poly- (styrene-ethylene-butylene-styrene) the ionomer powder of 9 grams of sulfonation, (sulfonation degree is
21.6%) uniform with 60 grams of polylactic acid powder elder generation physical blendings, it is then added in miniature extruder 200oC circulation melting
The mode of blending is blended 15 minutes, and the sample that then injection molding obtains lactic acid composite material carries out the test of mechanical property.Test
The result shows that the tensile strength of prepared lactic acid composite material is 57MPa, 36% is improved, elongation at break is improved from 6%
To 21%, 2.5 times are improved.
Claims (6)
1. the present invention provides a kind of method of modifying of polylactic acid activeness and quietness, it is characterized in that: using simultaneously containing the rigid of sulfonation
Property segment and thermoplastic elastic soft segment sulfonated polystyrene class ionomer and polylactic acid melt blending, carry out polydactyl acid
Material, while achieving the effect that activeness and quietness.
2. sulfonated polystyrene class ionomer as described in claim 1 is the copolymer by sulfonation containing polystyrene chain segment
In polystyrene chain segment and obtain, the sulfonation degree of polystyrene chain segment is between 5% to 60%.
3. the type of sulfonated polystyrene class ionomer as described in claim 1 includes but are not limited to poly- (the benzene second of sulfonation
Alkene-isoprene styrene) ionomer (SSIS)；Poly- (s-B-S) ionomer (SSBS) of sulfonation；Sulphur
Poly- (styrene-ethylene-butylene-styrene) ionomer (SSEBS) changed；Poly- (the styrene ethylene-propylene-benzene second of sulfonation
Alkene) ionomer (SSEPS) etc., it further include the polystyrene that other hard segments are sulfonation, soft segment is thermoplastic elastic segment
Ionomer.
4. the quality Zhan of the polystyrene chain segment (before sulfonation) in sulfonated polystyrene class ionomer as described in claim 1 is total
The mass fraction of copolymer is between 20% to 80%.
5. mass fraction of the sulfonated polystyrene class ionomer as described in claim 1 in lactic acid composite material arrives for 1%
Between 40%.
6. sulfonated polystyrene class ionomer used in modified polylactic acid composite material as described in claim 1 can be list
One kind, be also possible to any two or it is a variety of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910619224.3A CN110204876A (en) | 2019-07-10 | 2019-07-10 | A kind of method of modifying of poly-lactic acid material activeness and quietness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910619224.3A CN110204876A (en) | 2019-07-10 | 2019-07-10 | A kind of method of modifying of poly-lactic acid material activeness and quietness |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110204876A true CN110204876A (en) | 2019-09-06 |
Family
ID=67797056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910619224.3A Pending CN110204876A (en) | 2019-07-10 | 2019-07-10 | A kind of method of modifying of poly-lactic acid material activeness and quietness |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110204876A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111789285A (en) * | 2020-06-07 | 2020-10-20 | 湖北中烟工业有限责任公司 | Preparation method of polylactic acid cooling modified tow filter stick |
| CN112876588A (en) * | 2021-01-18 | 2021-06-01 | 浙大宁波理工学院 | Sulfonated SEBS-based rare earth ionomer and preparation method and application thereof |
| CN114213826A (en) * | 2022-01-13 | 2022-03-22 | 广东迪艾龙新材料科技有限公司 | Antistatic modified polyethylene-polylactic acid-based material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377910A (en) * | 2001-04-04 | 2002-11-06 | 中国石油化工股份有限公司 | Syndiotactic polyphenylethylene/polyester composite material |
| CN102911471A (en) * | 2012-10-17 | 2013-02-06 | 中科院广州化学有限公司 | PET (Polyethylene Terephthalate) sulfonate ionomer nucleating agent and preparation method as well as application thereof |
-
2019
- 2019-07-10 CN CN201910619224.3A patent/CN110204876A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377910A (en) * | 2001-04-04 | 2002-11-06 | 中国石油化工股份有限公司 | Syndiotactic polyphenylethylene/polyester composite material |
| CN102911471A (en) * | 2012-10-17 | 2013-02-06 | 中科院广州化学有限公司 | PET (Polyethylene Terephthalate) sulfonate ionomer nucleating agent and preparation method as well as application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ORNELIA VASILE主编；李杨，乔金梁，陈伟等译: "《聚烯烃手册 第2版》", 31 December 2005, 中国石化出版社 * |
| 洪定一: "《塑料工业手册 聚烯烃》", 31 December 1999, 化学工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111789285A (en) * | 2020-06-07 | 2020-10-20 | 湖北中烟工业有限责任公司 | Preparation method of polylactic acid cooling modified tow filter stick |
| CN112876588A (en) * | 2021-01-18 | 2021-06-01 | 浙大宁波理工学院 | Sulfonated SEBS-based rare earth ionomer and preparation method and application thereof |
| CN112876588B (en) * | 2021-01-18 | 2022-04-22 | 浙大宁波理工学院 | Sulfonated SEBS-based rare earth ionomer and preparation method and application thereof |
| CN114213826A (en) * | 2022-01-13 | 2022-03-22 | 广东迪艾龙新材料科技有限公司 | Antistatic modified polyethylene-polylactic acid-based material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110204876A (en) | A kind of method of modifying of poly-lactic acid material activeness and quietness | |
| KR20070095318A (en) | Impact-resistant modified thermoplastic moulding compounds based on vinyl aromatic copolymers and polyamide | |
| CN109535670A (en) | A kind of Wholly-degradable emulation material and preparation method thereof | |
| CN101812191A (en) | Method for preparing polyurethane/rubber interpenetrating network type water-swellable rubber | |
| CN104628895A (en) | Method for thermally reversibly crosslinking styrenic thermoplastic elastomer material | |
| Niu et al. | Superior toughened bio-compostable Poly (glycolic acid)-based blends with enhanced melt strength via selective interfacial localization of in-situ grafted copolymers | |
| CN107778852A (en) | A kind of LCP and nylon 6 mixing composite and preparation method thereof | |
| CN107141744A (en) | A kind of PLA/polyamide boiomacromolecule alloy material and preparation method thereof | |
| CN102731921A (en) | Weatherproof polymer alloy used for replacing ABS | |
| JP2012077158A (en) | Method for producing polymer composition | |
| Hu et al. | Toughening biosourced poly (lactic acid) and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) blends by a renewable poly (epichlorohydrin-co-ethylene oxide) elastomer | |
| Lei et al. | Synthesis and evaluation of bio-based elastomer based on diethyl itaconate for oil-resistance applications | |
| KR0149490B1 (en) | Thermoplastic resin composition | |
| Chen et al. | Modification of polylactide by poly (ionic liquid)-b-polylactide copolymer and bio-based ionomers: Excellent toughness, transparency and antibacterial property | |
| CN109206612B (en) | Bionic spider silk polyamino acid biological elastomer material and preparation method thereof | |
| CN102424717A (en) | Preparation method for reinforced and toughened polymer material | |
| Wang et al. | Combining novel polyether-based ionomers and polyethylene glycol as effective toughening agents for polylactide | |
| CN105949701A (en) | Fullerene and modified TPE (thermoplastic elastomer) composite adopting reversible crosslinking and preparation method of fullerene and modified TPE composite | |
| CN103374222A (en) | Composite toughened reinforced nylon and preparation method thereof | |
| JP2013163757A (en) | Thermoplastic resin composition and molded article | |
| CN107915965A (en) | A kind of high tenacity flame retardant PBT composition | |
| Wirasaputra et al. | Application of bis (glycidyloxy) phenylphosphine oxide as a chain extender for polyamide-6 | |
| CN104710744A (en) | Toughened modified PC/PET alloy material with high impact resistant performance and preparation method thereof | |
| CN109851973A (en) | A kind of ionomer ethylene propylene diene rubber and preparation method thereof | |
| CN104292815A (en) | High-rigidity super-tough nylon composite material and preparation method thereof |
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 |