CN101747604A - Biodegradable elastomer material and preparation method thereof - Google Patents
Biodegradable elastomer material and preparation method thereof Download PDFInfo
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- CN101747604A CN101747604A CN200810216781A CN200810216781A CN101747604A CN 101747604 A CN101747604 A CN 101747604A CN 200810216781 A CN200810216781 A CN 200810216781A CN 200810216781 A CN200810216781 A CN 200810216781A CN 101747604 A CN101747604 A CN 101747604A
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Abstract
The invention discloses a biodegradable elastomer material, comprising a polyhydroxy alkanoate elastomer and an accessory ingredient; the polyhydroxy alkanoate elastomer is one of P3HB4HB, PHBV and PHBH or the mixture of two of P3HB4HB, PHBV and PHBH, and other elastomers can be added. The biodegradable elastomer material has good processing performance, is biodegradable, can replace the existing elastomer material and can be applied to various industries such as medicines, industry, toys, automobiles, home appliance and the like in a large scale. The invention further discloses a preparation method of the biodegradable elastomer material; the preparation method is simple and has high efficiency and can be mass-produced industrially.
Description
[technical field]
The invention belongs to the material field, specifically, relate to Biodegradable elastomer material and preparation method thereof.
[background technology]
Because traditional petroleum-based plastics is very stable at occurring in nature, is difficult to biological degradation, the petroleum-based energy that the consumption of conventional plastic industry is a large amount of and " white pollution " that bring have been subjected to increasing concern.Since eighties of last century 60, the seventies, people have begun the research and development to biodegradable plastic, have had multiple biodegradable material (Biodegradable material) to come out at present, after the biodegradable material biological degradation, become water and carbonic acid gas, can not produce harm environment.Wherein common biological degradation polyalcohol material has poly(lactic acid) (PLA), PHA (PHAs) etc.Wherein the PHAs kind is many, derives from the natural reproducible starting material, and performance is good, and utilization extensively has good physics, mechanical property, processing characteristics and good biodegradable and biocompatibility.
With the 3-hydroxybutyric acid is that the poly 3-hydroxy butyrate P (3HB) that monomer is formed is the polymkeric substance of modal a kind of crystal type among the PHAs, because of its physical properties more crisp, similar and be unwell to direct industrial applications with PLA.The rerum natura of some multipolymers of P (3HB) then can be become soft tough by original hard fragility, becomes a kind of semicrystalline polymer as PHBV, and its melt viscosity increases, thereby can improve hot workability, improves mechanical mechanics property simultaneously.Other multipolymers such as P3HB4HB are owing to introduce the flexible monomer 4HB of linear aliphatic, and toughness improves, ductility increases substantially, can be near the character of rubber.Along with the increase of flexible unit, multipolymer to whippy rubbery state transition, and has good thermostability concurrently by the duroplasts of crystal type, has become a kind of elastomerics.Change the physical and mechanical properties of polymkeric substance in the PHAs elastomerics by the content that changes flexible molecule in the polymkeric substance, to obtain having different rigidity, crystallinity, fusing point and sparkling temperature to be applicable to the material of different purposes.
Though traditional elastomer material good processability does not possess biodegradability, causes environmental problem easily, and it non-renewablely causes supply day to be becoming tight.And the biodegradable multipolymer of PHAs not only can be used for medical material, as some tissue engineering materials, medicine sustained release carrier, surgical repair material etc., still be used for daily polymkeric substance and food polymkeric substance (as chewing gum), and automobile component, building materials, instrument, toy, because it derives from reproducible Agricultural Materials, can not bring pressure to environment after use is discarded, be existing other elastomeric desirable alternatives, meets the trend and the trend of Materials science development.
But, though the multipolymer of PHAs is very good as the elastomer material performance, but the method that is to use conventional melt-processed has great difficulty, because this polymkeric substance has kept great viscosity after melted state cools down, for higher especially true of the flexible composition of multipolymer.After-tack can make goods itself bonding that processes or be bonded on the processing units, limited the forming process of product greatly, and because PHAS elastomerics cooling needs for a long time, this has also caused very big inconvenience to the PHAS elastomerics as the extensive utilization of elastomer material.
[summary of the invention]
The objective of the invention is to overcome the above-mentioned traditional elastomerics and the defective of PHAs elastomer material, disclose a kind of biodegradable, superior performance, processing characteristics good elasticity body material;
Another object of the present invention is to propose the preparation method of above-mentioned Biodegradable elastomer material.
The present invention is achieved in that a kind of Biodegradable elastomer material, comprises PHAs elastomerics, auxiliary agent, and described PHAs elastomerics is an a kind of or mixture more than 2 kinds among P3HB4HB, PHBV, the PHBH.
Described PHAs elastomerics is P3HB4HB, and 4HB monomer molar content is 5%～99.9% among the described P3HB4HB.Preferably, 4HB monomer molar content is 20%～99% among the described P3HB4HB, and more preferably, 4HB monomer molar content is 30%～99% among the described P3HB4HB.
Mixture that described PHAs elastomerics is P3HB4HB and PHBV or the mixture of P3HB4HB and PHBH.
Improvement to above-mentioned all technical schemes is: also can add other elastomericss, described PHAs elastomer content is 1%～99%, and other elastomer contents are 0%～98%, and auxiliary agent content is 0.01～40%.Preferably, described PHAs elastomer content is 70%～94%, and described other elastomer contents are 5%～15%, and described auxiliary agent content is 0.1%～15%.
Described other elastomericss are a kind of or mixture more than 2 kinds in SEBS, TPV, TPE, TPU and the natural elastomer.
Described auxiliary agent is an a kind of or mixture more than 2 kinds in softening agent, tensio-active agent, tinting material, lubricant, heat-resisting stabilizing agent, antioxidant, fire retardant, the release agent.
Biodegradable elastomer material preparation method disclosed by the invention comprises the steps:
(1), weighing: the PHAs elastomerics of the corresponding weight of weighing, other elastomericss, auxiliary agent;
(2), blend: utilize high-speed mixer to carry out blend load weighted PHAs elastomerics, other elastomericss, auxiliary agent in the step (1);
(3), plasticizing: blend is plastified;
(4), granulation: after the cooling of plastifying blend, by the dicing machine pelletizing.
Preferably, described step (2) high speed mixing machine churning time is set at 1～8 minute, plasticizing equipment is Banbury mixer in the step (3), the plasticization temperature of described Banbury mixer is 70 ℃～150 ℃, prilling temperature is 70 ℃～150 ℃ in the described step (4), also increases to have between described step (2) and step (3) blend is carried out the exsiccant step, and described drying plant is an electric drying oven with forced convection, drying temperature is set at 60 ℃～100 ℃, is set at 6～12 hours time of drying.
Wherein, described P3HB4HB is meant poly-(3-butyric ester-co-4-butyric ester), and PHBV is meant poly-(3-butyric ester-co-3-hydroxyl valerate), and PHBH is meant poly-(3-butyric ester-co-3-hydroxycaproic ester).
Described SEBS is to be end segment with the polystyrene, and the ethylene-butene copolymer that obtains with the polyhutadiene hydrogenation is the linearity three embedding multipolymers of middle elastomeric block, and SEBS does not contain unsaturated double-bond, therefore has satisfactory stability and ageing resistance; TPV is meant Thermoplastic Vulcanizate, and physicals and function class under its normal temperature are similar to thermoset rubber, at high temperature show as the characteristic of thermoplastics, can fast, economical and machine-shaping easily; TPE is meant thermoplastic elastomer, has traditional hot simultaneously and returns the function of type rubber and character (softness, elasticity, sense of touch are good), and is simple and easy with the processing of general thermoplastics, reaches the recyclable two-fold advantage that re-uses fast; TPU is meant Polyurethane Thermoplastic Elastomer, and remarkable high tensile, high-tensile strength, tough and ageing-resistant characteristic are arranged, and is a kind of sophisticated environment-friendly materials; Described natural elastomer material can be materials such as natural rubber.
Beneficial effect of the present invention is: (1) the present invention select among P3HB4HB, PHBV, the PHBH a kind of or more than 2 kinds PHAs elastomerics such as mixture as biodegradable main unit, add other auxiliary agents, improve its processing characteristics, also solved the non-biodegradable problem of ball gonosome; (2) the present invention also changes the biodegradability of blend by the content of control PHAs elastomerics in blend; (3) change its fusing point, processing temperature, physical and mechanical properties and processing characteristics by the co-monomer content that changes in the PHAs elastomerics, and by adding auxiliary agent enhancing toughness, improve processing characteristics, make this blend can be on conventional plastic processing machinery suitability for industrialized production; (4) can also add existing other elastomer materials, the PHAs elastomerics is carried out further modification, and has good consistency each other, form biodegradable blend, can large-scale application arrive multiple industries such as medicine, industry, toy, automobile, household electrical appliances, replace existing elastomer material; (5) preparation method of Biodegradable elastomer material of the present invention is simple, efficient, in a large number suitability for industrialized production.
[embodiment]
The present invention is described in detail below in conjunction with a plurality of embodiment.
Embodiment 1:
P3HB4HB in the elastomer material of present embodiment (4HB monomer content 8%) content is 91.0%, and TPU content is 5.0%, and the oxidic polyethylene wax content is 0.3%, and the stearic acid salts contg is 2.5%, and oxidation preventive content is 0.2%, and organotin content is 1.0%,
The preparation method of the elastomer material of present embodiment is as described below: the P3HB4HB of the corresponding weight of weighing, TPU, oxidized polyethlene wax, hard hydrochlorate, antioxidant, organotin; Utilize high-speed mixer to carry out blend to weighed object, churning time is set at 5 minutes; Blend is carried out drying in electric drying oven with forced convection, drying temperature is set at 70 ℃, is set at 10 hours time of drying; The blend that drying is good plastifies, and plasticizing equipment is Banbury mixer, and the plasticization temperature of described Banbury mixer is 120 ℃; After the cooling of plastifying blend, by the dicing machine pelletizing.
Wherein, in the present embodiment, oxidized polyethlene wax is a lubricant, hard hydrochlorate, organotin are heat-resisting stabilizing agents, also be added with the antioxidant of a little simultaneously, be added with 4 kinds of auxiliary components in the elastomer material of present embodiment altogether, have very good processing properties.
Embodiment 2:
P3HB4HB in the elastomer material of present embodiment (the 4HB monomer content is 20%) content is 96.8%, and oxidation preventive content is 0.2%, and organotin content is 1%, and the stearic acid salts contg is 2%.
The preparation method is: the P3HB4HB of the corresponding weight of weighing, antioxidant, organotin, hard hydrochlorate; Utilize high-speed mixer to carry out blend to weighed object, churning time is set at 5 minutes; Blend is carried out drying in electric drying oven with forced convection, drying temperature is set at 85 ℃, is set at 7 hours time of drying; The blend that drying is good plastifies, and plasticizing equipment is Banbury mixer, and the plasticization temperature of described Banbury mixer is 150 ℃; After the cooling of plastifying blend, by the dicing machine pelletizing.
Embodiment 3:
In the elastomer material of present embodiment, P3HB4HB (the 4HB monomer content is 80%) content is 89.7%, and PVAC (Vinyl Acetate Copolymer) content is 10%, and PEW (polyethylene wax) is 0.3% as its content of lubricant, and wherein PVAC is a kind of thermoplastic elastomer.
The preparation method is: the P3HB4HB of the corresponding weight of weighing, PVAC, PEW; Utilize high-speed mixer to carry out blend to weighed object, churning time is set at 3 minutes; Blend is carried out drying in electric drying oven with forced convection, drying temperature is set at 70 ℃, is set at 9.5 hours time of drying; The blend that drying is good plastifies, and plasticizing equipment is Banbury mixer, and the plasticization temperature of described Banbury mixer is 105 ℃; After the cooling of plastifying blend, by the dicing machine pelletizing, described prilling temperature is 80 ℃.
Embodiment 4:
In the elastomer material of present embodiment, P3HB4HB (the 4HB monomer content is 30%) content is 50%, and SEBS content is 10%, and the rubber oil-contg is 35%, and antioxidant is 0.2%.
The preparation method is: the P3HB4HB of the corresponding weight of weighing, SEBS, rubber oil and antioxidant; Utilize high-speed mixer to carry out blend to weighed object, churning time is set at 6 minutes; Blend is carried out drying in electric drying oven with forced convection, drying temperature is set at 70 ℃, is set at 7.5 hours time of drying; The blend that drying is good plastifies, and plasticizing equipment is Banbury mixer, and plasticization temperature is 110 ℃; After the cooling of plastifying blend, by the dicing machine pelletizing, prilling temperature is 100 ℃.
Embodiment 5:
In the elastomer material of present embodiment, each composition and content thereof are respectively: P3HB4HB (the 4HB monomer content is 60%) content is 50%, and PHBH content is 25%, TPE content is 12%, plasticizer loading is 8.2%, and surfactant content is 3.4%, and colorant content is 1.4%.
The preparation method is: the P3HB4HB of the corresponding weight of weighing, PHBH, TPE, softening agent, tensio-active agent and tinting material; Utilize high-speed mixer to carry out blend to weighed object, churning time is set at 10 minutes; Blend is carried out drying in electric drying oven with forced convection, drying temperature is set at 80 ℃, is set at 8.5 hours time of drying; The blend that drying is good plastifies, and plasticizing equipment is Banbury mixer, and plasticization temperature is 140 ℃; After the cooling of plastifying blend, by the dicing machine pelletizing.
Embodiment 6:
In the elastomer material of present embodiment, each composition and content thereof are respectively: P3HB4HB (the 4HB monomer content is 80%) content is 60%, and PHBV content is 34%, and TPV content is 5.5%, and release agent content is 0.5%.
The preparation method is: the P3HB4HB of the corresponding weight of weighing, PHBV, TPV, release agent; Utilize high-speed mixer to carry out blend to weighed object, churning time is set at 15 minutes; Blend is carried out drying in electric drying oven with forced convection, drying temperature is set at 85 ℃, is set at 7 hours time of drying; The blend that drying is good plastifies, and plasticizing equipment is Banbury mixer, and plasticization temperature is 110 ℃; After the cooling of plastifying blend, by the dicing machine pelletizing.
Embodiment 7:
In the elastomer material of present embodiment, each composition and content thereof are respectively: P3HB4HB (the 4HB monomer content is 90%) content is 40%, PHBV content is 30%, PHBH content is 15%, TPV content is 5%, SEBS content is 6%, and antioxidant 1%, release agent content are 0.5%, fire retardant 1%, heat-resisting stabilizing agent 1.5%.
The preparation method is: the P3HB4HB of the corresponding weight of weighing, PHBV, PHBH, TPV, SEBS, antioxidant, release agent, fire retardant, heat-resisting stabilizing agent; Utilize high-speed mixer to carry out blend to weighed object, churning time is set at 5.5 minutes; Blend is carried out drying in electric drying oven with forced convection, drying temperature is set at 75 ℃, is set at 6 hours time of drying; The blend that drying is good plastifies, and plasticizing equipment is Banbury mixer, and plasticization temperature is 110 ℃; After the cooling of plastifying blend, by the dicing machine pelletizing.
To the prepared elastomer material biodegrade performance test in mud and seawater of above-mentioned all embodiment of the present invention, test-results shows: within 1 year, and except that other elastomericss that can not degrade, other composition all biological degradeds.
Simultaneously, the prepared elastomer material of above-mentioned all embodiment is carried out tensile strength and elongation at break test, test result shows, its tensile strength of all elastomer materials is all greater than 9MPa, elongation at break is all greater than 1000%, all having good physical and mechanical properties, is the ideal Biodegradable elastomer material.
Above embodiment just simply enumerates, and in the elastomer material of the present invention, the elastomeric selection of PHAs is multiple, as P3HB4HB mix with PHBV, PHBV mixes with PHBH or even the mixing of P3HB4HB, PHBV, three kinds of multipolymers of PHBH.Described other elastomericss can be for SEBS, TPV, TPE, TPU and natural elastomer wherein any one, and two or more mixing between them is not just enumerated one by one at this.Described auxiliary agent is an a kind of or mixture more than 2 kinds in softening agent, tensio-active agent, tinting material, lubricant, heat-resisting stabilizing agent, antioxidant, fire retardant, the release agent, use about auxiliary agent can be carried out combinations matches according to actual needs, 4 kinds of auxiliary components have been added as embodiment 1, be respectively oxidized polyethlene wax, hard hydrochlorate, organotin and the antioxidant of a little.Equally, persons skilled in the art can also be mixed antioxidant, release agent according to the practical application needs, or tinting material, tensio-active agent, antioxidant mix, or the like, do not enumerate one by one at this yet.
In a word, but the present invention is not limited to above-mentioned embodiment, and persons skilled in the art are in the disclosed technical scope of the present invention, and the variation that can expect easily is all within protection scope of the present invention.
Claims (11)
1. a Biodegradable elastomer material comprises poly (hydroxyalkanoate) ester elastomer, auxiliary agent, it is characterized in that: described poly (hydroxyalkanoate) ester elastomer is an a kind of or mixture more than 2 kinds among P3HB4HB, PHBV, the PHBH.
2. Biodegradable elastomer material as claimed in claim 1 is characterized in that: described poly (hydroxyalkanoate) ester elastomer is P3HB4HB, and 4HB monomer molar content is 5%～99.9% among the described P3HB4HB.
3. Biodegradable elastomer material as claimed in claim 2 is characterized in that: 4HB monomer molar content is 20%～99% among the described P3HB4HB.
4. Biodegradable elastomer material as claimed in claim 3 is characterized in that: 4HB monomer molar content is 30%～99% among the described P3HB4HB.
5. Biodegradable elastomer material as claimed in claim 1 is characterized in that: mixture that described poly (hydroxyalkanoate) ester elastomer is P3HB4HB and PHBV or the mixture of P3HB4HB and PHBH.
6. as any described Biodegradable elastomer material of claim 1～5, it is characterized in that: also can add other elastomericss, the content of each composition is, the PHA elastomer content is 1%～99%, other elastomer contents are 0%～98%, and auxiliary agent content is 0.01%～40%.
7. Biodegradable elastomer material as claimed in claim 6 is characterized in that: described PHA elastomer content is 70%～94%, and described other elastomer contents are 5%～15%, and described auxiliary agent content is 0.1%～15%.
8. Biodegradable elastomer material as claimed in claim 6 is characterized in that: described other elastomericss are a kind of or mixture more than 2 kinds in SEBS, TPV, TPE, TPU and the natural elastomer.
9. Biodegradable elastomer material as claimed in claim 6 is characterized in that: described auxiliary agent is an a kind of or mixture more than 2 kinds in softening agent, tensio-active agent, tinting material, lubricant, heat-resisting stabilizing agent, antioxidant, fire retardant, the release agent.
10. Biodegradable elastomer material preparation method as claimed in claim 6 comprises the steps:
(1), weighing: the poly (hydroxyalkanoate) ester elastomer of the corresponding weight of weighing, other elastomericss, auxiliary agent;
(2), blend: utilize high-speed mixer to carry out blend load weighted poly (hydroxyalkanoate) ester elastomer, other elastomericss, auxiliary agent in the step (1);
(3), plasticizing: blend is plastified;
(4), granulation: after the cooling of plastifying blend, by the dicing machine pelletizing.
11. Biodegradable elastomer material preparation method as claimed in claim 10, it is characterized in that: described step (2) high speed mixing machine churning time is set at 1～8 minute, plasticizing equipment is Banbury mixer in the step (3), the plasticization temperature of described Banbury mixer is 70 ℃～150 ℃, prilling temperature is 70 ℃～150 ℃ in the described step (4), between described step (2) and step (3), also increase to have blend is carried out the exsiccant step, described drying plant is an electric drying oven with forced convection, drying temperature is set at 60 ℃～100 ℃, is set at 6～12 hours time of drying.
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| CN200810216781A CN101747604A (en) | 2008-10-24 | 2008-10-24 | Biodegradable elastomer material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146598A (en) * | 2011-04-22 | 2011-08-10 | 中国科学院宁波材料技术与工程研究所 | PHBV-containing biobased chemical fiber and preparation method thereof |
| CN102924888A (en) * | 2012-10-09 | 2013-02-13 | 山东省意可曼科技有限公司 | Full-biodegradation polyhydroxyalkanoate material with flame retardance |
| CN102924889A (en) * | 2012-10-09 | 2013-02-13 | 山东省意可曼科技有限公司 | Fully-biodegradable polyhydroxy alkanoate flame retardant material |
| CN103602047A (en) * | 2013-11-25 | 2014-02-26 | 大连路阳科技开发有限公司 | Polyhydroxyalkanoate composite and preparation method and application thereof |
| CN104130562A (en) * | 2014-07-28 | 2014-11-05 | 江苏嘉铂新材料有限公司 | Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof |
| CN105647163A (en) * | 2016-04-12 | 2016-06-08 | 苏州甫众塑胶有限公司 | Toughened-type composite plastic material and preparation method thereof |
-
2008
- 2008-10-24 CN CN200810216781A patent/CN101747604A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146598A (en) * | 2011-04-22 | 2011-08-10 | 中国科学院宁波材料技术与工程研究所 | PHBV-containing biobased chemical fiber and preparation method thereof |
| CN102146598B (en) * | 2011-04-22 | 2012-07-25 | 中国科学院宁波材料技术与工程研究所 | PHBV-containing biobased chemical fiber and preparation method thereof |
| CN102924888A (en) * | 2012-10-09 | 2013-02-13 | 山东省意可曼科技有限公司 | Full-biodegradation polyhydroxyalkanoate material with flame retardance |
| CN102924889A (en) * | 2012-10-09 | 2013-02-13 | 山东省意可曼科技有限公司 | Fully-biodegradable polyhydroxy alkanoate flame retardant material |
| CN103602047A (en) * | 2013-11-25 | 2014-02-26 | 大连路阳科技开发有限公司 | Polyhydroxyalkanoate composite and preparation method and application thereof |
| CN104130562A (en) * | 2014-07-28 | 2014-11-05 | 江苏嘉铂新材料有限公司 | Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof |
| CN105647163A (en) * | 2016-04-12 | 2016-06-08 | 苏州甫众塑胶有限公司 | Toughened-type composite plastic material and preparation method thereof |
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Application publication date: 20100623 |