CN105153652A - Husked-flaxseed-powder combined modified biomass-based polyester material and preparation method thereof - Google Patents
Husked-flaxseed-powder combined modified biomass-based polyester material and preparation method thereof Download PDFInfo
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- CN105153652A CN105153652A CN201510462663.XA CN201510462663A CN105153652A CN 105153652 A CN105153652 A CN 105153652A CN 201510462663 A CN201510462663 A CN 201510462663A CN 105153652 A CN105153652 A CN 105153652A
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Abstract
The invention belongs to the field of natural high-molecular materials, and concretely relates to a husked-flaxseed-powder combined modified biomass-based polyester material and a preparation method thereof. The husked-flaxseed-powder combined modified biomass-based polyester material is formed by combining husked flaxseed powder with poly(3-hydroxybutyrate-co-4-hydroxybutyrate) according to the weight ratio of 5-30:100. The preparation method comprises mixing poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and husked flaxseed powder, and putting into a banbury mixer for banburying and further for obtaining a solid mixer; and putting the solid mixer on a hot press for hot-press combination molding, and performing vacuum drying to obtain the husked-flaxseed-powder combined modified synthesized polyester material. After being subjected to husked-flaxseed-powder combination modification, the modified synthesized polyester material is substantially improved in tensile strength and elongation at break, and is increased in strength and toughness, and the application scope of materials is effectively expanded.
Description
Technical field
The invention belongs to natural macromolecular material field, be specifically related to one and shell linseed meal compound modified biomass base polyester material and preparation method thereof.
Background technology
The linseed meal that shells is the product after flex seed peeling after milling, sieving.There is inexpensive (flax easily grows, and can obtain better income), renewable, advantages of environment protection.Flax belongs to cress, it is a kind of continuable substitute energy crop had a high potential, it effectively can be processed into high-quality recyclable fuel (as close friends etc. such as biofuel), flax is except containing except oil, also containing multiple proteins and carbohydrate, can be used for developing value-added biological products.Along with petroleum resources growing tension, the prices of raw and semifnished materials rise steadily and environmental problem, and the investigation and application based on renewable resources natural macromolecular material is extensively paid attention to.At present, the research for flax mainly concentrates on their fuel applications aspect, but it is but rarely had as the research that proteinaceous starting material directly apply to material development aspect and relate to.
Biodegradable material is by various ways such as photodegradation, chemical degradation, biological degradations, material degradation is become the lower-molecular substance of environmental sound, has the material of good Practical Performance, is a kind of method solving environmental problem.Biodegradable material comprises natural materials and synthetic materials, and natural materials comprises starch, Mierocrystalline cellulose, chitin and their derivative thereof; Biodegradable synthetic materials contains hydrolyzable functional group (as: ester bond, urea key, amido linkage, ehter bond etc.) usually, as poly butyric ester, poly(lactic acid), poly butylene succinate, polycaprolactone etc.Poly(lactic acid) and poly butylene succinate are two kinds of degradable polyester synthetic materialss, industrially obtain mainly through Biological resources fermentation, but the fragility of these two kinds of polyester synthetic materialss is comparatively large, price is high, which has limited their ranges of application at Material Field.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, object is to provide one to shell linseed meal compound modified biomass base polyester material and preparation method thereof.
For achieving the above object, the technical solution adopted in the present invention is:
One is shelled linseed meal compound modified biomass base polyester material, it is characterized in that, by shelling, linseed meal and biomass-based polyester are composited, described in the shell weight part ratio of linseed meal and biomass-based polyester be 5 ~ 30:100.
By such scheme, described biomass-based polyester is poly butylene succinate or poly(lactic acid).
By such scheme, described in the linseed meal that shells be the powder that obtains after milling, sieve and clearing up after flex seed peeling, its protein content is not higher than 46wt%, and fat content is not higher than 24wt%, and carbohydrate content is not higher than 25wt%.
The preparation method of the above-mentioned linseed meal compound modified biomass base polyester material that shells, is characterized in that, comprises the steps: that (1) takes biomass-based polyester and the linseed meal that shells, obtains blend after mixing; Blend is placed in banburying in Banbury mixer and obtains solid mixture; (2) be placed in by solid mixture on thermocompressor and carry out hot pressing composite molding, shaping final vacuum drying removing moisture obtains the linseed meal compound modified biomass base polyester material that shells.
By such scheme, the processing condition of described banburying are: temperature is 120 ~ 200 DEG C, and rotating speed is 10 ~ 120rpm, and the time is 1 ~ 30 minute.
By such scheme, the processing condition of described hot pressing composite molding are: temperature is 120 ~ 160 DEG C, pressure is 10 ~ 60MPa, the time is 1 ~ 15 minute.
By such scheme, described vacuum-drying is: vacuum-drying 12 ~ 72 hours under 40 ~ 60 DEG C of conditions.
Beneficial effect of the present invention is as follows: (1) the present invention adopts the linseed meal that shells to carry out composite modified to biomass-based polyester, has the advantages such as with low cost, environmental friendliness, consistency are good; Adopt hot pressing composite molding after banburying mixing, have that technique is simple, quick, efficient, the feature of environmental protection; (2) the linseed meal compound modified biomass base polyester material that shells of the present invention is a kind of degradable environment-friendly material; After the linseed meal that shells is composite modified, the elongation at break of biomass-based polyester material is improved significantly, the fragility of material reduces greatly, toughness increases greatly, this has expanded the range of application of material effectively, the described linseed meal compound modified biomass base polyester that shells can be processed as film, sheet material, section bar or container etc. by straight forming, also can be used as wrapping material or engineering plastics etc.
Accompanying drawing explanation
Fig. 1 is biomass-based polyester material pictorial diagram, is from left to right wherein comparative example 1, the biomass-based polyester material of embodiment 1 ~ 6 gained successively.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
One is shelled linseed meal compound modified biomass base polyester material, prepares by the following method:
(1) by the linseed meal 5 parts that shells, poly butylene succinate 100 parts, chooses the linseed meal that shells, poly butylene succinate, and will shell linseed meal and poly butylene succinate tentatively mix, and obtain blend;
(2) blend be placed in Banbury mixer carry out banburying: temperature is 120 DEG C, rotating speed 20rpm (rev/min), 30 minutes time, obtain solid mixture;
(3) solid mixture after banburying is carried out hot pressing composite molding on thermocompressor: temperature is 120 DEG C, pressure is 10MPa, the time is 15 minutes; After shaping, under 40 DEG C of conditions, vacuum-drying removes moisture in 72 hours, obtains the linseed meal compound modified biomass base polyester material that shells.
The CMT6503 instrument newly thinking carefully testing tool company in Shenzhen according to GB4456-84 carries out Mechanics Performance Testing to the linseed meal compound modified biomass base polyester material that shells prepared by the present embodiment, rate of extension is 10mm/min, test result shows: after the linseed meal that shells is composite modified, the performance of biomass-based polyester material in elongation at break obtains effective raising, and concrete numerical value is in table 1.
Embodiment 2
One is shelled linseed meal compound modified biomass base polyester material, prepares by the following method:
(1) by the linseed meal 10 parts that shells, poly butylene succinate 100 parts, chooses the linseed meal that shells, poly butylene succinate, and will shell linseed meal and poly butylene succinate tentatively mix, and obtain blend;
(2) blend be placed in Banbury mixer carry out banburying: temperature is 130 DEG C, rotating speed 10rpm (rev/min), 15 minutes time, obtain solid mixture;
(3) solid mixture after banburying is carried out hot pressing composite molding on thermocompressor: temperature is 130 DEG C, pressure is 20MPa, the time is 12 minutes; After shaping, under 50 DEG C of conditions, vacuum-drying removes moisture in 60 hours, obtains the linseed meal compound modified biomass base polyester material that shells.
The CMT6503 instrument newly thinking carefully testing tool company in Shenzhen according to GB4456-84 carries out Mechanics Performance Testing to the linseed meal compound modified biomass base polyester material that shells prepared by the present embodiment, rate of extension is 10mm/min, test result shows: after the linseed meal that shells is composite modified, the performance of biomass-based polyester material in elongation at break obtains effective raising, and concrete numerical value is in table 1.
Embodiment 3
One is shelled linseed meal compound modified biomass base polyester material, prepares by the following method:
(1) by the linseed meal 15 parts that shells, poly butylene succinate 100 parts, chooses the linseed meal that shells, poly butylene succinate, and will shell linseed meal and poly butylene succinate tentatively mix, and obtain blend;
(2) blend be placed in Banbury mixer carry out banburying: temperature is 150 DEG C, rotating speed 48rpm (rev/min), 18 minutes time, obtain solid mixture;
(3) solid mixture after banburying is carried out hot pressing composite molding on thermocompressor: temperature is 140 DEG C, pressure is 20MPa, the time is 8 minutes; After shaping, under 60 DEG C of conditions, vacuum-drying removes moisture in 12 hours, obtains the linseed meal compound modified biomass base polyester material that shells.
The CMT6503 instrument newly thinking carefully testing tool company in Shenzhen according to GB4456-84 carries out Mechanics Performance Testing to the linseed meal compound modified biomass base polyester material that shells prepared by the present embodiment, rate of extension is 10mm/min, test result shows: after the linseed meal that shells is composite modified, the performance of biomass-based polyester material in elongation at break obtains effective raising, and concrete numerical value is in table 1.
Embodiment 4
One is shelled linseed meal compound modified biomass base polyester material, prepares by the following method:
(1) by the linseed meal 20 parts that shells, poly butylene succinate 100 parts, chooses the linseed meal that shells, poly butylene succinate, and will shell linseed meal and poly butylene succinate tentatively mix, and obtain blend;
(2) blend be placed in Banbury mixer carry out banburying: temperature is 150 DEG C, rotating speed 60rpm (rev/min), 5 minutes time, obtain solid mixture;
(3) solid mixture after banburying is carried out hot pressing composite molding on thermocompressor: temperature is 150 DEG C, pressure is 30MPa, the time is 8 minutes; After shaping, under 60 DEG C of conditions, vacuum-drying removes moisture in 12 hours, obtains the linseed meal compound modified biomass base polyester material that shells.
The CMT6503 instrument newly thinking carefully testing tool company in Shenzhen according to GB4456-84 carries out Mechanics Performance Testing to the linseed meal compound modified biomass base polyester material that shells prepared by the present embodiment, rate of extension is 10mm/min, test result shows: after the linseed meal that shells is composite modified, the performance of biomass-based polyester material in elongation at break obtains effective raising, and concrete numerical value is in table 1.
Embodiment 5
One is shelled linseed meal compound modified biomass base polyester material, prepares by the following method:
(1) by the linseed meal 25 parts that shells, poly butylene succinate 100 parts, chooses the linseed meal that shells, poly butylene succinate, and will shell linseed meal and poly butylene succinate tentatively mix, and obtain blend;
(2) blend be placed in Banbury mixer carry out banburying: temperature is 180 DEG C, rotating speed 120rpm (rev/min), 5 minutes time, obtain solid mixture;
(3) solid mixture after banburying is carried out hot pressing composite molding on thermocompressor: temperature is 160 DEG C, pressure is 45MPa, the time is 5 minutes; After shaping, under 60 DEG C of conditions, vacuum-drying removes moisture in 12 hours, obtains the linseed meal compound modified biomass base polyester material that shells.
The CMT6503 instrument newly thinking carefully testing tool company in Shenzhen according to GB4456-84 carries out Mechanics Performance Testing to the linseed meal compound modified biomass base polyester material that shells prepared by the present embodiment, rate of extension is 10mm/min, test result shows: after the linseed meal that shells is composite modified, the performance of biomass-based polyester material in elongation at break obtains effective raising, and concrete numerical value is in table 1.
Embodiment 6
One is shelled linseed meal compound modified biomass base polyester material, prepares by the following method:
(1) by the linseed meal 30 parts that shells, poly butylene succinate 100 parts, chooses the linseed meal that shells, poly butylene succinate, and will shell linseed meal and poly butylene succinate tentatively mix, and obtain blend;
(2) blend be placed in Banbury mixer carry out banburying: temperature is 200 DEG C, rotating speed 80rpm (rev/min), 1 minute time, obtain solid mixture;
(3) solid mixture after banburying is carried out hot pressing composite molding on thermocompressor: temperature is 160 DEG C, pressure is 60MPa, the time is 1 minute; After shaping, under 60 DEG C of conditions, vacuum-drying removes moisture in 12 hours, obtains the linseed meal compound modified biomass base polyester material that shells.
The CMT6503 instrument newly thinking carefully testing tool company in Shenzhen according to GB4456-84 carries out Mechanics Performance Testing to the linseed meal compound modified biomass base polyester material that shells prepared by the present embodiment, rate of extension is 10mm/min, test result shows: after the linseed meal that shells is composite modified, the performance of biomass-based polyester material in elongation at break obtains effective raising, and concrete numerical value is in table 1.
Embodiment 7
One is shelled linseed meal compound modified biomass base polyester material, prepares by the following method:
(1) by the linseed meal 5 parts that shells, poly(lactic acid) 100 parts, chooses the linseed meal that shells, poly(lactic acid), and will shell linseed meal and poly(lactic acid) tentatively mix, and obtain blend;
(2) blend be placed in Banbury mixer carry out banburying: temperature is 160 DEG C, rotating speed 48rpm (rev/min), 15 minutes time, obtain solid mixture;
(3) solid mixture after banburying is carried out hot pressing composite molding on thermocompressor: temperature is 160 DEG C, pressure is 30MPa, the time is 15 minutes; After shaping, under 60 DEG C of conditions, vacuum-drying removes moisture in 12 hours, obtains the linseed meal compound modified biomass base polyester material that shells.
The CMT6503 instrument newly thinking carefully testing tool company in Shenzhen according to GB4456-84 carries out Mechanics Performance Testing to the linseed meal compound modified biomass base polyester material that shells prepared by the present embodiment, rate of extension is 10mm/min, test result shows: after the linseed meal that shells is composite modified, the performance of biomass-based polyester material in elongation at break obtains effective raising, and concrete numerical value is in table 2.
Comparative example 1
A kind of biomass-based polyester material, prepares: get 100 parts of poly butylene succinate banburyings in Banbury mixer by the following method: temperature is 150 DEG C, rotating speed 48rpm (rev/min), 18 minutes time; Poly butylene succinate after banburying is carried out hot pressing composite molding in thermocompressor: temperature is 140 DEG C, pressure is 20MPa, the time is 8 minutes; After shaping, at 60 DEG C, vacuum-drying removes moisture in 12 hours, obtains biomass-based polyester material.Its mechanical property is in table 1.
Comparative example 2
A kind of biomass-based polyester material, prepares: get 100 parts of poly(lactic acid) banburyings in Banbury mixer by the following method: temperature is 180 DEG C, rotating speed 48rpm (rev/min), 15 minutes time; Poly(lactic acid) after banburying is carried out hot pressing composite molding in thermocompressor: temperature is 180 DEG C, pressure is 30MPa, the time is 80 minutes; After shaping, at 60 DEG C, vacuum-drying removes moisture in 12 hours, obtains biomass-based polyester material.Its mechanical property is in table 2.
Table 1 shells the mechanical property of linseed meal compound modified biomass base polyester material
Table 2 shells the mechanical property of linseed meal compound modified biomass base polyester material
As can be seen from table 1, table 2, after the linseed meal that shells is composite modified, the elongation at break of biomass-based polyester material is significantly improved, the fragility of material reduces greatly, toughness increases greatly, effectively expanded the range of application of material, described in the linseed meal compound modified biomass base polyester that shells can be processed as film, sheet material, section bar or container etc. by straight forming, also can be used as wrapping material or engineering plastics etc.Meanwhile, the realization of the linseed meal high-content that shells in matrix material, can reduce the cost of matrix material to a great extent, makes it to have better actual application prospect.
Obviously, above-described embodiment is only for the example done clearly is described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And therefore amplified apparent change or variation are still within the protection domain of the invention.
Claims (7)
1. the linseed meal compound modified biomass base polyester material that shells, it is characterized in that, by shelling, linseed meal and bacterium synthesizing polyester Material cladding form, described bacterium synthesizing polyester material is poly-(3-hydroxybutyrate ester-co-4-butyric ester), described in the shell weight part ratio of linseed meal and poly-(3-hydroxybutyrate ester-co-4-butyric ester) be 5 ~ 30:100.
2. the linseed meal compound modified biomass base polyester material that shells according to claim 1, is characterized in that, described in the shell weight part ratio of linseed meal and poly-(3-hydroxybutyrate ester-co-4-butyric ester) be 10 ~ 20:100.
3. the linseed meal compound modified biomass base polyester material that shells according to claim 1, it is characterized in that, the described linseed meal that shells is the powder obtained after milling, sieve and clearing up after flex seed peeling, its protein content is not higher than 46wt%, fat content is not higher than 24wt%, and carbohydrate content is not higher than 25wt%.
4. claim 1 ~ 3 arbitrary described in shell the preparation method of linseed meal compound modified biomass base polyester material, it is characterized in that, comprise the steps: that (1) takes poly-(3-hydroxybutyrate ester-co-4-butyric ester) and the linseed meal that shells, after mixing, obtain blend; Blend is placed in banburying in Banbury mixer and obtains solid mixture; (2) be placed in by solid mixture on thermocompressor and carry out hot pressing composite molding, shaping final vacuum drying removing moisture obtains the linseed meal composite modified bacterium synthesizing polyester material that shells.
5. preparation method according to claim 4, is characterized in that, the processing condition of described banburying are: temperature is 140 ~ 220 DEG C, and rotating speed is 10 ~ 120rpm, and the time is 1 ~ 30 minute.
6. preparation method according to claim 4, is characterized in that, the processing condition of described hot pressing composite molding are: temperature is 140 ~ 160 DEG C, pressure is 10 ~ 60MPa, the time is 1 ~ 15 minute.
7. preparation method according to claim 4, is characterized in that, described vacuum-drying is: vacuum-drying 12 ~ 72 hours under 40 ~ 60 DEG C of conditions.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
| CN104271330A (en) * | 2012-04-02 | 2015-01-07 | 绿色材料有限责任公司 | Injection molded articles from natural materials and methods for making them |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
| CN104271330A (en) * | 2012-04-02 | 2015-01-07 | 绿色材料有限责任公司 | Injection molded articles from natural materials and methods for making them |
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