CN106366596A - Polylactic acid/chemically modified natural rubber blend material and preparing method thereof - Google Patents
Polylactic acid/chemically modified natural rubber blend material and preparing method thereof Download PDFInfo
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- CN106366596A CN106366596A CN201610872934.3A CN201610872934A CN106366596A CN 106366596 A CN106366596 A CN 106366596A CN 201610872934 A CN201610872934 A CN 201610872934A CN 106366596 A CN106366596 A CN 106366596A
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- natural rubber
- polylactic acid
- chemical modification
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 93
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 84
- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 75
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 75
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 238000007385 chemical modification Methods 0.000 claims description 60
- 238000002156 mixing Methods 0.000 claims description 53
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000004073 vulcanization Methods 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000005060 rubber Substances 0.000 description 8
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a polylactic acid/chemically modified natural rubber blend material and a preparing method thereof. The polylactic acid/chemically modified natural rubber blend material is mainly prepared from 30.0-94.6 wt% of polylactic resin, 5.0-66.0 wt% of glycidyl methacrylate chemically modified natural rubber, 0.2-2.0 wt% of vulcanizing agent and 0.2-2.0 wt% of antioxygen. According to the glycidyl methacrylate chemically modified natural rubber, the interfacial adhesive action between the polylactic acid and the modified natural rubber is improved through reactive compatibilization, and the polylactic acid is subjected to toughening modification through dynamic vulcanization of the modified natural rubber, thus tenacity and ductility of polylactic acid material can be improved greatly and the polylactic acid/chemically modified natural rubber blend material is obtained. The polylactic acid/chemically modified natural rubber blend material has an excellent mechanical property, which shows not only excellent impact strength but also excellent elongation at break, and thus the polylactic acid/chemically modified natural rubber blend material can be applied to the field of high polymer materials of packaging, electronic appliances, automobile industry and the like.
Description
Technical field
The present invention relates to a kind of modified polylactic acid material is and in particular to arrive a kind of polylactic acid/chemical modification natural rubber
Blend material and preparation method thereof.
Background technology
The increasingly enhancing of 21st century, the aggravation with human society energy crisis and environmental protection consciousness, biology can
Degradable material and bio-based polymers are gradually taken seriously in the application of field of polymer technology.Polylactic acid (pla) is that one kind can be biological
The polyester-based polymer material of degraded, has excellent biocompatibility.Polylactic acid has been widely used in biological doctor at present
Medicine, such as surgical cable, delivery system etc..Polylactic acid is the material of totally biodegradable, meets both at home and abroad to environment
The needs of sustainable development.Polylactic acid has good mechanical performance and processability, with polylactic acid price day commercially
Become reasonable, polylactic acid can as a kind of may replace in petroleum-based plastics the most potential and development prospect plastics, but its
Impact property is excessively poor.The toughness of polylactic acid difference and low heat distortion temperature are to hinder it to send out in the application of packaging and automotive field
The bottleneck of exhibition.So the task first developing preferable pla material is to improve the toughness of pla material.In recent years, high tenacity is poly-
Lactic acid (pla) sill has attracted the attention of Many researchers, is especially badly in need of developing a kind of ultra-toughness polylactic acid elastomeric material,
It has very important potential using value in the plastics industry field such as packaging and automotive interior material.
The toughness of polylactic acid improves typically can be by several approach such as copolymerization, plasticizing and physical blendings.Wherein physics is common
Mixed is most economical effective method of modifying, and result of study shows: by can be with polylactic acid blend with the modification of elastomeric polymer
Toughness, these modified polymer include polyethylene, polyurethane, polyamide, thermoplastic polyolefin elastomer, rubber, poly- in oneself
The bio-based such as ester, Polyethylene Glycol or abiotic based polyalcohol.But, due to the polymer-modified interface of pla and the overwhelming majority
Poor compatibility, the raising limitation of the notch impact strength of toughening polylactic acid coblended matter, hardly result in the polylactic acid of good toughness
Material.Therefore poly-lactic acid material is still subject to certain restrictions in the application of plastic applications.
A kind of simple and inexpensive reaction melt blending mode is utilized, by polylactic acid and chemical modification sky in the present invention
So the reaction melt blending of rubber, while melt blending, on the one hand realizes the sulfuration of natural rubber, on the other hand passes through to change
Property natural rubber and polylactic acid reactive compatibilization improve the interface adhesion of polylactic acid and natural rubber.Prepare mechanicalness
Excellent polylactic acid/modified natural rubber the blend material of energy, increases substantially impact property and the ductility of polylactic acid, can use
In fields such as packaging, electronic apparatus, auto industrys.
Content of the invention
For the shortcoming solving poly-lactic acid material poor toughness, poor ductility in prior art.It is an object of the invention to provide one
Plant polylactic acid/chemical modification natural rubber blends material and preparation method thereof.Glycidyl methacrylate chemical modification
Natural rubber have can reactive group epoxy radicals, can be reacted with the terminal carboxyl group of polylactic acid or hydroxyl, by poly- breast
Add glycidyl methacrylate chemical modification natural rubber as toughener in acid, be blended by frit reaction and improve
Pla and the compatibility of rubber elastomer, and realize the sulfuration of modified natural rubber, the polylactic acid/chemical modification of preparation simultaneously
Natural rubber blends material, can increase substantially the toughness of poly-lactic acid material.
For reaching above-mentioned purpose, the technology used in the present invention means are: using glycidyl methacrylate chemistry
Modified rubber carries out toughness reinforcing to polylactic acid, prepares polylactic acid/modification sky by reacting melt blending and carrying out the dynamic vulcanization of rubber
So rubber blend material.
A kind of polylactic acid/chemical modification natural rubber blends material that the present invention provides, is mainly grouped by following group
Become:
Above component is all weight percentage.
Optimized proportion is:
Above component is all weight percentage.
Further, contained vulcanizing agent be cumyl peroxide, di-t-butyl peroxide, in isopropyl benzene hydroperoxide
Any one or several.
Further, contained antioxidant is one of antioxidant 1010, irgasfos 168 or two kinds.
Further, the preparation of polylactic acid/chemical modification natural rubber intermingling material is using the side of reaction melt blending
Method, specific technical process and work silver mixing part:
(1) polylactic acid, glycidyl methacrylate chemical modification natural rubber, antioxidant are pressed proportioning and are mixed；Directly
It is added to melt blending in banbury, temperature range 120-180 DEG C in each area of banbury, rotating speed is 30-100 rev/min, mixing
Time 5-20min, until poly-lactic acid mixture mix homogeneously；
(2) pressing proportioning adds vulcanizing agent to continue mixing, temperature range 120-180 DEG C of banbury, and rotating speed turns for 30-100/
Minute, mixing time 5-20min, prepare polylactic acid/chemical modification natural rubber blends material；
Further, the method that the preparation of polylactic acid/chemical modification natural rubber intermingling material adopts reactive extrursion, tool
The technical process of body and work silver mixing part: by polylactic acid and glycidyl methacrylate chemical modification natural rubber, antioxidant,
Vulcanizing agent is fed to melt blending extrusion, temperature range 170- that each section of double screw extruder in double screw extruder by proportioning
210 DEG C, rotating speed, at 40-100 rev/min, melt extrudes rear cooling granulation.
The method have the benefit that: by the use of glycidyl methacrylate chemical modification natural rubber as increasing
Tough dose carries out toughening modifying to polylactic acid；Improved between polylactic acid matrix and chemical modification natural rubber by reactive compatibilization
Interfacial adhesion acts on, and carries out the dynamic vulcanization of chemical modification natural rubber simultaneously, prepares the natural rubber of polylactic acid/chemical modification
Glue blend material.The polylactic acid of the present invention/chemical modification natural rubber blends material is not showed only as excellent impact resistance
Intensity, has excellent elongation at break simultaneously, can be used for packing, electronic apparatus, auto industry Polymer material field.
Specific embodiment
With reference to specific embodiment, the present invention is described in further details.
Embodiment 1
Glycidyl methacrylate chemical modification natural rubber (poly- first by the polylactic acid of 94.0wt%, 5.0wt%
Base glycidyl acrylate Grafting Content is 2.0wt%), 0.2wt% antioxidant 1010 is placed in mixing in high-speed mixer,
Add in hakke banbury, in 140-160 DEG C of melt blending, rotating speed 40rpm, mixing time 10min, be subsequently adding 0.2wt%
Vulcanizing agent cumyl peroxide, rotating speed 30rpm, takes out, at 160-180 DEG C by molding system after continuing mixing time 10min
The standard sample of standby polylactic acid/chemical modification natural rubber blends material, the mechanics mechanical performance of determination sample.Tensile strength
For 50.7mpa, elongation at break be 52%, notch impact strength be 15.6mpa, unnotched impact strength 34.4mpa.
Embodiment 2
Glycidyl methacrylate chemical modification natural rubber (poly- first by the polylactic acid of 90.0wt%, 9.0wt%
Base glycidyl acrylate Grafting Content is 2.5wt%), 0.5wt% antioxidant 1010 is placed in mixing in high-speed mixer,
Add in hakke banbury, in 140-160 DEG C of melt blending, rotating speed 40rpm, mixing time 10min, be subsequently adding 0.5wt%
Vulcanizing agent cumyl peroxide, rotating speed 30rpm, takes out, at 160-180 DEG C by molding system after continuing mixing time 10min
The standard sample of standby polylactic acid/chemical modification natural rubber blends material, the mechanics mechanical performance of determination sample.Tensile strength
For 47.5mpa, elongation at break be 116%, notch impact strength be 30.7mpa, unnotched impact strength 112.8mpa.
Embodiment 3
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 85.0wt%, 13.5wt%
Glycidyl methacrylate graft content is 4.5wt%), 0.5wt% antioxidant 1010 is placed in high-speed mixer mixed
Close, add in hakke banbury, in 130-160 DEG C of melt blending, rotating speed 100rpm, mixing time 10min, be subsequently adding
1.0wt% vulcanizing agent cumyl peroxide, rotating speed 45rpm, takes out after continuing mixing time 10min, passes through at 160-180 DEG C
The standard sample of polylactic acid/chemical modification natural rubber blends material is prepared in molding, measures its mechanics mechanical performance.Stretching is strong
Spend for 42.6mpa, elongation at break be 142%, notch impact strength be 43.4mpa, unnotched impact strength 117.3mpa.
Embodiment 4
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 80.0wt%, 18.0wt%
Glycidyl methacrylate graft content is 7.0wt%), 0.5wt% antioxidant 1010 is placed in high-speed mixer mixed
Close, add in hakke banbury, in 150-180 DEG C of melt blending, rotating speed 100rpm, mixing time 10min, be subsequently adding
1.5wt% vulcanizing agent cumyl peroxide, rotating speed 70rpm, takes out after continuing mixing time 10min, passes through at 160-180 DEG C
The standard sample of polylactic acid/chemical modification natural rubber blends material is prepared in molding, measures its mechanics mechanical performance.Stretching is strong
Spend for 32.6mpa, elongation at break be 158%, notch impact strength be 53.4mpa, unnotched impact strength 157.3mpa.
Embodiment 5
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 85.0wt%, 13.0wt%
Glycidyl methacrylate graft content is 9.0wt%), 0.5wt% antioxidant 1010 is placed in high-speed mixer mixed
Close, add in hakke banbury, in 130-160 DEG C of melt blending, mixing time 10min, be subsequently adding 1.5wt% vulcanizing agent
Cumyl peroxide, rotating speed 50rpm, takes out after continuing mixing time 10min, passes through the poly- breast of molding preparation at 160-180 DEG C
The standard sample of acid/chemical modification natural rubber blends material, measures its mechanics mechanical performance.Tensile strength be 40.6mpa,
Elongation at break is 160%, notch impact strength is 55.6mpa, unnotched impact strength 121.2mpa.
Embodiment 6
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 80.0wt%, 18.0wt%
Glycidyl methacrylate graft content is 9.3wt%), 1.0wt% antioxidant 1010 is placed in high-speed mixer mixed
Close, add in hakke banbury, in 150-160 DEG C of melt blending, rotating speed 100rpm, mixing time 10min, be subsequently adding
1.0wt% vulcanizing agent cumyl peroxide, rotating speed 50rpm, takes out after continuing mixing time 10min, passes through at 160-180 DEG C
The standard sample of polylactic acid/chemical modification natural rubber blends material is prepared in molding, measures its mechanics mechanical performance.Stretching is strong
Spend for 33.8mpa, elongation at break is 172%, notch impact strength is 71.6mpa, unnotched impact strength 156.4mpa.
Embodiment 7
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 80.0wt%, 17.5wt%
Glycidyl methacrylate graft content is 11.7wt%), 1.0wt% antioxidant 1010 is placed in high-speed mixer mixed
Close, add in hakke banbury, in 150-160 DEG C of melt blending, rotating speed 80rpm, mixing time 10min, be subsequently adding
1.5wt% vulcanizing agent cumyl peroxide, rotating speed 80rpm, takes out after continuing mixing time 10min, passes through at 160-180 DEG C
The standard sample of polylactic acid/chemical modification natural rubber blends material is prepared in molding, measures its mechanics mechanical performance.Stretching is strong
Spend for 30.7mpa, elongation at break is 189%, notch impact strength is 65.8mpa, unnotched impact strength 160.5mpa.
Embodiment 8
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 75.0wt%, 22.5wt%
Glycidyl methacrylate graft content is 11.5wt%), 1.0wt% antioxidant 1010 is placed in high-speed mixer mixed
Close, add in hakke banbury, in 140-170 DEG C of melt blending, rotating speed 100rpm, mixing time 10min, be subsequently adding
1.5wt% vulcanizing agent cumyl peroxide, rotating speed 80rpm, take out after continuing mixing time 10min, poly- by molding preparation
The standard sample of lactic acid/chemical modification natural rubber blends material, measures its mechanics mechanical performance.Tensile strength is
28.6mpa, elongation at break are 147%, notch impact strength is 66.7mpa, unnotched impact strength 149.5mpa.
Embodiment 9
By the polylactic acid of 70.0wt%, 28.0wt% glycidyl methacrylate chemical modification natural rubber (poly- first
Base glycidyl acrylate Grafting Content is 9.0wt%), 0.5wt% antioxidant 1010 mix homogeneously, add hakke banburying
In machine, in 150-180 DEG C of melt blending, rotating speed 100rpm, mixing time 10min, it is subsequently adding 1.5wt% vulcanizing agent peroxidating
Diisopropylbenzene (DIPB), rotating speed 100rpm, take out after continuing mixing time 10min, polylactic acid/chemical modification is prepared by molding natural
The standard sample of rubber blend material, measures its mechanics mechanical performance.Tensile strength is 25.6mpa, elongation at break is
175%th, notch impact strength is 60.3mpa, unnotched impact strength 133.8mpa.
Embodiment 10
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 60.0wt%, 38.0wt%
Glycidyl methacrylate graft content is 13.5wt%), 0.5wt% antioxidant 1010 is placed in high-speed mixer mixed
Close, add in hakke banbury, in 150-180 DEG C of melt blending, rotating speed 100rpm, mixing time 10min, be subsequently adding
1.5wt% vulcanizing agent cumyl peroxide, rotating speed 100rpm, take out after continuing mixing time 10min, poly- by molding preparation
The standard sample of lactic acid/chemical modification natural rubber blends material, measures its mechanics mechanical performance.Tensile strength is
23.8mpa, elongation at break are 180%, notch impact strength is 62.3mpa, unnotched impact strength 130.4mpa.
Embodiment 11
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 50.0wt%, 47.0wt%
Glycidyl methacrylate graft content is 9.0wt%), 1.0wt% antioxidant 1010 and 2.0wt% vulcanizing agent peroxidating
Diisopropylbenzene (DIPB) mix homogeneously, is added to double screw extruder, temperature range 170-210 DEG C that each section of double screw extruder, rotating speed
100rpm, melt extrudes rear cooling granulation.Prepare the standard of polylactic acid/chemical modification natural rubber blends material by injection
Sample, measures its mechanics mechanical performance.Tensile strength is 21.3mpa, elongation at break is that 156%, notch impact strength is
60.4mpa, unnotched impact strength 123.6mpa.
Embodiment 12
Will be (poly- for the glycidyl methacrylate chemical modification natural rubber of the polylactic acid of 40.0wt%, 56.0wt%
Glycidyl methacrylate graft content is 18.0wt%), 2.0wt% antioxidant 1010 and 2.0wt% vulcanizing agent peroxide
Change diisopropylbenzene (DIPB) mix homogeneously, be added to melt blending extrusion, the temperature model of each section of double screw extruder in double screw extruder
Enclose 170-210 DEG C, rotating speed, at 50 revs/min, melt extrudes rear cooling granulation.Polylactic acid/chemical modification is prepared by injection natural
The standard sample of rubber blend material, measures its mechanics mechanical performance.Tensile strength is 18.7mpa, elongation at break is
182%th, notch impact strength is 42.7mpa, unnotched impact strength 105.2mpa.
A kind of polylactic acid of the present invention/chemical modification natural rubber blends material, poly-lactic acid material is pressed standard size and is noted
Being moulded pla resin in the standard batten of test, wherein reference examples and embodiment is German BASF natureworks.Its thing
Rationality can press CNS test respectively, as shown in table 1.In modified polylactic acid material, each component and its parts by weight are shown in Table
2, corresponding physical property is shown in Table 3.
Table 1 reference examples pla of the present invention and the material modified physical and mechanical propertiess testing standard of embodiment 1-12
| Performance | Method of testing | Unit |
| Tensile strength | gb/t1040-1992 | mpa |
| Elongation at break | gb/t1040-1992 | % |
| Notch impact strength | gb/t1043.1-2008 | kj/m2 |
The formula of table 2 pla of the present invention, reference examples and polylactic acid/chemical modification natural rubber blends embodiment
Table 3 pla, polylactic acid/chemical modification natural rubber blends materials Example and the mechanical performance of reference examples sample
Relatively
The present invention is carried out toughness reinforcing using the chemical modification natural rubber polylactic acid of different proportion, prepares polylactic acid/chemistry and changes
Property natural rubber blends material, is the physics of polylactic acid/chemical modification natural rubber blends material and reference examples listed by table 3
Mechanical performance, by table it can be seen that the polylactic acid of the present invention/chemical modification natural rubber blends material is than polylactic acid/natural rubber
The toughness of glue blend material more preferably, is not showed only as excellent impact strength, also has excellent elongation at break.This
Bright polylactic acid/chemical modification natural rubber blends material shows as excellent mechanical performance, for poly-lactic acid material in height
General and in engineering material field the application of molecule is significant.
Claims (6)
1. a kind of polylactic acid/chemical modification natural rubber blends material is it is characterised in that be mainly grouped into by following group:
Polylactic resin 30.0-94.6wt%, glycidyl methacrylate chemical modification natural rubber 5.0-66.0wt%, sulfuration
Agent 0.2-2.0wt%, antioxidant 0.2-2.0wt%, above component is all weight percentage.
2. polylactic acid according to claim 1/chemical modification natural rubber blends material it is characterised in that main by
Following group is grouped into: polylactic resin 40.0-90.0wt%, glycidyl methacrylate chemical modification natural rubber
9.0-56.0wt%, vulcanizing agent 0.5-2.0wt%, antioxidant 0.5-2.0wt%, above component is all weight percentage.
3. polylactic acid according to claim 1 and 2/chemical modification natural rubber blends material is it is characterised in that contained
Vulcanizing agent be cumyl peroxide, di-t-butyl peroxide, any one or several in isopropyl benzene hydroperoxide.
4. polylactic acid according to claim 1 and 2/chemical modification natural rubber blends material is it is characterised in that contained
Antioxidant be one of antioxidant 1010, irgasfos 168 or two kinds.
5. the preparation method of the arbitrary described polylactic acid of claim 1-4/chemical modification natural rubber blends material, its feature
It is, the preparation of polylactic acid/chemical modification natural rubber blends material adopts the method reacting melt blending, specific technique mistake
Journey and blending condition are as follows: proportioning pressed by (1) polylactic acid, glycidyl methacrylate chemical modification natural rubber, antioxidant
Mixing；It is added directly into melt blending in banbury, temperature range 120-180 DEG C in each area of banbury, rotating speed turns for 30-100/
Minute, mixing time 5-20min, until poly-lactic acid mixture mix homogeneously；(2) pressing proportioning adds vulcanizing agent to continue mixing, close
Temperature range 120-180 DEG C of mill, rotating speed is 30-100 rev/min, and mixing time 5-20min prepares polylactic acid/change
Learn modified natural rubber blend material.
6. the polylactic acid described in claim 5/chemical modification natural rubber blends material preparation method it is characterised in that
Polylactic acid and glycidyl methacrylate chemical modification natural rubber, antioxidant, vulcanizing agent are fed to double spiral shells by proportioning
In bar extruder melt blending extrusion, temperature range 170-210 DEG C that each section of double screw extruder, rotating speed at 40-100 rev/min,
Melt extrude rear cooling granulation.
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| CN107459793A (en) * | 2017-08-28 | 2017-12-12 | 华南理工大学 | Strong and unyielding balanced ultra-tough PLA based nano composite material and preparation method thereof |
| CN107599296A (en) * | 2017-09-27 | 2018-01-19 | 贵阳学院 | Micropore injection moulding foaming prepares PLA natural rubber porous material method and material |
| CN108017889A (en) * | 2017-12-15 | 2018-05-11 | 华南理工大学 | A kind of strong and unyielding balanced polylactic acid/methyl methacrylate rubber composite material and preparation method thereof |
| CN109401243A (en) * | 2018-10-23 | 2019-03-01 | 青岛科技大学 | A kind of high-ductility biological poly lactic acid/response type modified rubber thermoplastic sulfurized rubber intermingling material and its secondary response squeeze out preparation method |
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