CN101775168A - Collagen-modified biodegradable plastic and preparation method thereof - Google Patents
Collagen-modified biodegradable plastic and preparation method thereof Download PDFInfo
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- CN101775168A CN101775168A CN201010039660A CN201010039660A CN101775168A CN 101775168 A CN101775168 A CN 101775168A CN 201010039660 A CN201010039660 A CN 201010039660A CN 201010039660 A CN201010039660 A CN 201010039660A CN 101775168 A CN101775168 A CN 101775168A
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Abstract
The invention discloses a collagen-modified biodegradable plastic and a preparation method thereof. The collagen-modified biodegradable plastic comprises the following components in percentage by weight: 60 percent to 80 percent of polymer polyolefin, 10 percent to 30 percent of collagen, 1 percent to 5 percent of plasticizer and 1 percent to 7 percent of functional additive, and the functional additive comprises caprolactam. The biodegradable plastic has the advantages of easy shaping, simple production technique, no pollution, good compatibility, good heat stability, high water resistance, high tensile strength and high elongation at break, and can be biodegraded under various environments after moulding, the degradation efficiency is high, and environment pollution is reduced.
Description
Technical field:
The invention belongs to biochemical field, particularly biodegradable plastic and fabricating technology field thereof.
Background technology
Along with improving constantly of human environment protection consciousness, more and more higher to the environmental consciousness requirement of plastics, therefore, the development work of degradable plastic product has obtained developing rapidly, and the degradative plastics kind is more and more many.Photodegradable plastics is arranged, chemical degradation plastics, biodegradable plastic etc.The investigative technique of photodegradable plastics is the most ripe.Photodegradable plastics has been carried out industrialization in Japan, is mainly used in plastic sheeting for farm use, foaming pallet, bottle, wrapping material etc.The degradation speed of photodegradable plastics depends on light application time and intensity, and therefore different in actual applications regions can be restricted.The Application Areas of chemical degradation plastics is also comparatively wide, Paro Ge An company as Britain succeeds in developing a kind of hydrolyzable plastics film, it has the mechanical property and the printing performance of general thin, can guarantee effectively that the agricultural chemicals smell in the packing bag does not leak, and the corrosion of the hydrocarbon class chemical of ability, and its maximum characteristics are with back hydrolyzable degraded, thereby range of application is subjected to certain restriction.Biodegradable plastic---refer under the effect of nature microorganism (as bacterium, mould and algae), can be decomposed into the plastics of low molecular compound fully.Be characterized in storing convenient transportation, as long as keep dry, do not need lucifuge, applied range not only can be used for agricultural mulching, packing bag, and is widely used in field of medicaments.Biodegradable plastic becomes the focus of new generation of research and development along with the development of modern biotechnology more and more comes into one's own.
The ideal biodegradable plastic is a kind of macromolecular material that has good use properties, can be decomposed, finally be become by inorganicization an integral part of occurring in nature Carbon cycle after discarded by environmental microorganism fully.At present, the research of biodegradable plastic mainly concentrates on two aspects: be the research of complete biodegradable plastics on the one hand.As, poly-3-hydroxyalkanoate (PHA), poly(lactic acid) (PLA), poly-epsilon-caprolactone (PCL) and poly butylene succinate (PBS) have good mechanical property and processing characteristics, mechanical property can satisfy the service requirements of general-purpose plastics between PE, polypropylene (PP).But because the price of complete biodegradable plastics product is higher relatively at present, demand strict technology, make the popularization of this class material be restricted.Be the modification of present general-purpose plastics on the other hand, main various natural biological degraded macromoleculars (as starch etc.) or the synthetic biodegradable polymer (as PCL, PLA etc.) of using carries out modification to general-purpose plastics, thereby gives the biodegradability of present general-purpose plastics.The natural biological degradative plastics that with starch is representative is abundant, cheap because of raw material sources, is a kind of inexhaustible renewable resources, and the back of going mouldy under multiple environment is by biological degradation, and eventual degradation becomes CO
2And H
2O can carry out recirculation by photosynthesis, can not produce any pollution to environment and has been subjected to people's extensive concern day by day.
Summary of the invention
The object of the present invention is to provide that a kind of production technique is simple, with low cost, the biodegradable plastic that uses wide, a kind of collagen-modified preparation of being convenient to realize that large-scale industrial is produced and preparation method thereof.
For achieving the above object, the present invention takes following technical proposals:
The biodegradable plastic of this a kind of collagen-modified preparation comprises following component by percentage to the quality:
High molecular polymer polyolefine 60～80%,
Softening agent 1～5%,
Functional additive 1～7%,
Described functional additive comprises hexanolactam.
Further, high molecular polymer polyolefine of the present invention be in new LDPE (film grade), high density polyethylene(HDPE), the polyvinyl chloride any or any two more than.
Further, functional additive of the present invention comprises macromolecule wax and/or white dyes, and the quality percentage composition of described white dyes is 1～2%.
Further, softening agent of the present invention be in diacetyl oxide, succinyl oxide, the Tetra hydro Phthalic anhydride any or any two more than.
The collagen-modified method for preparing biodegradable plastic of the present invention comprises the steps:
(1) with collagen protein and softening agent by 10～30: 1～5 mass ratio mixed 20～30 minutes;
(2) mixture that step (1) is obtained and high molecular polymer polyolefine, functional additive adopt the high speed mixing roll 120～140 ℃ of blend, mass ratio between described high molecular polymer polyolefine, functional additive and the collagen protein is 60～80: 1～7: 10～30, and described functional additive comprises hexanolactam;
(3) mixture with step (2) gained adopts the high speed mixing roll at 120-160 ℃ of following blend extruding pelletization, makes described biodegradable plastic.
Further, collagen protein described in the preparation method of the present invention obtains by extracting in the leather industry waste.
Further, high molecular polymer polyolefine described in the preparation method of the present invention be in new LDPE (film grade), high density polyethylene(HDPE), the polyvinyl chloride any or any two more than.
Further, functional additive comprises macromolecule wax and/or white dyes described in the preparation method of the present invention, and the quality percentage composition of described white dyes is 1～2%.
Further, softening agent described in the preparation method of the present invention be in diacetyl oxide, succinyl oxide, the Tetra hydro Phthalic anhydride any or any two more than.
Compared with prior art, advantage of the present invention is:
(1) biodegradable plastic of the present invention adopts collagen protein earlier with an amount of anhydride modified, has greatly improved the water repelling property of plastics, has practicality;
(2) biodegradable plastic of the present invention, machine-shaping easily, but adopt the tensile strength and the elongation at break of an amount of hexanolactam reinforced plastics to be improved, can obtain the material of different mechanical properties by the amount of regulating hexanolactam;
(3) the common plastics apparatus and method for is adopted in the processing of biodegradable plastic of the present invention, and production technique is simple, easily operation;
(4) biodegradable plastic of the present invention goes mouldy the back by biological degradation under multiple environment, accelerates the decomposition of plastics, has reduced contaminate environment;
(5) used collagen protein is for extracting from discarded leather, and the source is abundant, cheap, is a kind of inexhaustible renewable resources;
(6) product involved in the present invention is pollution-free, consistency good, and it is simple to have good thermostability, degradation efficiency height, preparation technology.
Description of drawings
Fig. 1. hexanolactam is to the influence (A: no hexanolactam of collagen-modified LDPE tensile strength; B: contain 2% hexanolactam).
Fig. 2. hexanolactam is to the influence (A: no hexanolactam of collagen-modified LDPE elongation at break; B: contain 2% hexanolactam).
Fig. 3. the biological degradability of collagen-modified LDPE (A:5% collagen protein; The B:10% collagen protein; The C:20% collagen protein; The D:30% collagen protein).
Fig. 4. the thermostability of collagen-modified LDPE (A: collagen protein; B:70%LDPE+20% collagen protein+10% softening agent and functional additive; C:LDPE).
Embodiment
Embodiment 1:
The collagen-modified biodegradable plastic for preparing of present embodiment contains following component (content meter by mass percentage):
New LDPE (film grade) (LDPE) 80%
Macromolecule wax 2%
Hexanolactam 2%
White dyes 1%
The preparation technology of above-mentioned biodegradable plastic carries out according to following steps in sequence:
The first step is sent into kneading machine kneading 20 minutes with collagen protein and diacetyl oxide by 10: 5 mass ratio, realizes elementary mixing;
Second step, raw material that the first step is kneaded and LDPE, macromolecule wax, hexanolactam, white dyes adopt the high speed mixing roll 120 ℃ of following blend, carry out the secondary blend, make compound, wherein the mass ratio of collagen protein, diacetyl oxide, LDPE, macromolecule wax, hexanolactam, white dyes corresponds to 10: 5: 80: 2: 2: 1.
The 3rd step, the compound of the second step gained is sent into twin screw extruder, under 120 ℃, carry out three grades of blend, behind the blend extruding pelletization, promptly make biodegradable plastic.
Collagen-modified mechanical property to LDPE has remarkably influenced, and Fig. 1 result shows that the adding of collagen protein can reduce the tensile strength of LDPE, and along with the increase of collagen content, the tensile strength of LDPE reduces gradually.The adding of functional additive hexanolactam can obviously improve the tensile strength of collagen-modified LDPE, and its major cause is that the adding of hexanolactam has promoted the crosslinked of collagen protein.
Embodiment 2:
The collagen-modified biodegradable plastic for preparing of this example contains following component (content meter by mass percentage):
New LDPE (film grade) (LDPE) 65%
Tetra hydro Phthalic anhydride 3%
Succinyl oxide 2%
Macromolecule wax 1.5%
Hexanolactam 2.5%
White dyes 1%
Preparation technology's characteristics of above-mentioned biodegradable plastic, carry out according to following steps in sequence:
The first step is sent collagen protein, Tetra hydro Phthalic anhydride and succinyl oxide into kneading machine by above-mentioned quality proportioning and was mediated 25 minutes, realizes elementary mixing;
In second step, raw material that the first step is kneaded and PVC, macromolecule wax, hexanolactam adopt the high speed mixing roll to press above-mentioned quality proportioning 140 ℃ of following blend, make compound;
The 3rd step, the compound of the second step gained is sent into twin screw extruder, at 150 ℃ of following blend extruding pelletizations, make biodegradable plastic.
Collagen protein also has remarkably influenced to the elongation at break of LDPE, shows that as Fig. 2 result the adding of collagen protein can reduce the elongation at break of LDPE, and along with the increase of collagen content, the elongation at break of LDPE reduces gradually.The adding of functional additive hexanolactam can obviously improve the elongation at break of collagen-modified LDPE, at collagen content about 5～15%, collagen-modified LDPE elongation at break is close with pure LDPE, and collagen content surpasses 30%, and elongation at break obviously reduces.
Embodiment 3:
The collagen-modified biodegradable plastic for preparing of this example contains following component (content meter by mass percentage):
New LDPE (film grade) (LDPE) 65%
Tetra hydro Phthalic anhydride 2%
White dyes 1%
Hexanolactam 1%
Macromolecule wax 1%
Preparation technology's characteristics of above-mentioned biodegradable plastic, carry out according to following steps in sequence:
The first step is sent collagen protein, Tetra hydro Phthalic anhydride, succinyl oxide and diacetyl oxide into kneading machine by above-mentioned quality proportioning and was mediated 25 minutes, realizes elementary mixing;
In second step, raw material that the first step is kneaded and PVC, white dyes, hexanolactam adopt the high speed mixing roll to press above-mentioned quality proportioning 140 ℃ of following blend, make compound;
The 3rd step, the compound of the second step gained is sent into twin screw extruder, at 160 ℃ of following blend extruding pelletizations, make biodegradable plastic.
By 37 ℃ of steady temperatures in incubator, measure the biological degradation of collagen-modified LDPE under humidity 80% condition with the soil method of burying, collagen-modified LDPE sample shear becomes the small-particle of 2 * 3mm.The biological degradability result as shown in Figure 3, biological degradability is accelerated with the content of collagen protein, the content of general collagen protein is 10～30%, its biological degradability is apparent in view, after 60 days, collagen protein is degraded substantially fully.
Embodiment 4:
The collagen-modified biodegradable plastic for preparing of this example contains following component (content meter by mass percentage):
New LDPE (film grade) (LDPE) 70%
Tetra hydro Phthalic anhydride 2%
Succinyl oxide 2%
Diacetyl oxide 1%
Hexanolactam 2%
Macromolecule wax 1.5%
White dyes 1.5%
Preparation technology's characteristics of above-mentioned biodegradable plastic, carry out according to following steps in sequence:
The first step is sent collagen protein, Tetra hydro Phthalic anhydride, succinyl oxide and diacetyl oxide into kneading machine by above-mentioned quality proportioning and was mediated 25 minutes, realizes elementary mixing;
In second step, raw material that the first step is kneaded and PVC, hexanolactam adopt the high speed mixing roll to press above-mentioned quality proportioning 130 ℃ of following blend, make compound;
The 3rd step, the compound of the second step gained is sent into twin screw extruder, at 150 ℃ of following blend extruding pelletizations, make biodegradable plastic.
Collagen-modified LDPE has a good thermostability, and shown in Fig. 4 thermogravimetric analysis, collagen-modified LDPE and pure LDPE have close thermostability.
Embodiment 5:
The collagen-modified biodegradable plastic for preparing of present embodiment contains following component (quality percentage composition):
High density polyethylene(HDPE) (HDPE) 74%
Succinyl oxide 1%
Macromolecule wax 2%
Hexanolactam 1.5%
White dyes 1.5%
Preparation technology's characteristics of above-mentioned biodegradable plastic, carry out according to following steps in sequence:
The first step is sent into kneading machine kneading 30 minutes with collagen protein and succinyl oxide by above-mentioned mass ratio, realizes elementary mixing;
In second step, the raw material that the first step is kneaded and the HDPE, macromolecule wax, hexanolactam, the white dyes that have with the proportioning of improving quality adopt the high speed mixing roll 130 ℃ of following blend, make compound;
The 3rd step, the compound of the second step gained is sent into twin screw extruder, at 130 ℃ of following blend extruding pelletizations, make biodegradable plastic.
Embodiment 6:
The collagen-modified biodegradable plastic for preparing of this example contains following component (content meter by mass percentage):
Polyvinyl chloride (PVC) 60%
Tetra hydro Phthalic anhydride 3%
Macromolecule wax 2%
Hexanolactam 3%
White dyes 2%
Preparation technology's characteristics of above-mentioned biodegradable plastic, carry out according to following steps in sequence:
The first step is sent collagen protein and Tetra hydro Phthalic anhydride into kneading machine kneading 25 minutes by above-mentioned quality proportioning, realizes elementary mixing;
In second step, raw material that the first step is kneaded and PVC, macromolecule wax, hexanolactam, white dyes adopt the high speed mixing roll to press above-mentioned quality proportioning 135 ℃ of following blend, make compound;
The 3rd step, the compound of the second step gained is sent into twin screw extruder, at 140 ℃ of following blend extruding pelletizations, make biodegradable plastic.
Claims (9)
1. the biodegradable plastic of a collagen-modified preparation is characterized in that comprising the following component in the quality percentage composition:
High molecular polymer polyolefine 60～80%,
Collagen protein 10～30%,
Softening agent 1～5%,
Functional additive 1～7%,
Described functional additive comprises hexanolactam.
2. the biodegradable plastic of collagen-modified preparation according to claim 1 is characterized in that: described high molecular polymer polyolefine be in new LDPE (film grade), high density polyethylene(HDPE), the polyvinyl chloride any or any two more than.
3. the biodegradable plastic of collagen-modified preparation according to claim 1, it is characterized in that: described functional additive comprises macromolecule wax and/or white dyes, the quality percentage composition of described white dyes is 1～2%.
4. the biodegradable plastic of collagen-modified preparation according to claim 1 is characterized in that: described softening agent be in diacetyl oxide, succinyl oxide, the Tetra hydro Phthalic anhydride any or any two more than.
5. a collagen-modified method for preparing biodegradable plastic is characterized in that comprising the steps:
(1) with collagen protein and softening agent by 10～30: 1～5 mass ratio mixed 20～30 minutes;
(2) mixture that step (1) is obtained and high molecular polymer polyolefine, functional additive adopt the high speed mixing roll 120～140 ℃ of blend, mass ratio between described high molecular polymer polyolefine, functional additive and the collagen protein is 60～80: 1～7: 10～30, and described functional additive comprises hexanolactam;
(3) mixture with step (2) gained adopts the high speed mixing roll at 120-160 ℃ of following blend extruding pelletization, makes described biodegradable plastic.
6. the collagen-modified method for preparing biodegradable plastic according to claim 5 is characterized in that: described collagen protein obtains by extracting in the discarded leather.
7. the collagen-modified method for preparing biodegradable plastic according to claim 5 is characterized in that: described high molecular polymer polyolefine be in new LDPE (film grade), high density polyethylene(HDPE), the polyvinyl chloride any or any two more than.
8. the collagen-modified method for preparing biodegradable plastic according to claim 5, it is characterized in that: described functional additive comprises macromolecule wax and/or white dyes, the quality percentage composition of described white dyes is 1～2%.
9. the collagen-modified method for preparing biodegradable plastic according to claim 5 is characterized in that: described softening agent be in diacetyl oxide, succinyl oxide, the Tetra hydro Phthalic anhydride any or any two more than.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351545A (en) * | 2013-05-30 | 2013-10-16 | 宁波工程学院 | Partially biodegradable polyvinyl chloride composite and preparation method thereof |
| CN103783257A (en) * | 2014-01-16 | 2014-05-14 | 内蒙古农业大学 | Preparation method for modified sheep muscle tendon collagen |
| CN104693575A (en) * | 2013-12-07 | 2015-06-10 | 招远鲁娃婴幼儿用品有限公司 | Biodegradable plastic toy |
| CN105949737A (en) * | 2016-05-31 | 2016-09-21 | 沧州沧硕塑业有限公司 | Degradable mulching film and preparation method thereof |
| CN106832964A (en) * | 2017-03-03 | 2017-06-13 | 唐爱兰 | A kind of hydrophobic microprotein/composite polyolefine material and preparation method |
| CN109384961A (en) * | 2018-10-31 | 2019-02-26 | 浙江盛瑞环保科技有限公司 | A kind of fiber foam amortizing packaging material and preparation method thereof |
| CN111763431A (en) * | 2019-04-02 | 2020-10-13 | 四川大学 | Method for preparing foamed plastic by using waste leather leftover materials |
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2010
- 2010-01-12 CN CN201010039660A patent/CN101775168A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351545A (en) * | 2013-05-30 | 2013-10-16 | 宁波工程学院 | Partially biodegradable polyvinyl chloride composite and preparation method thereof |
| CN103351545B (en) * | 2013-05-30 | 2015-08-26 | 宁波工程学院 | Polyvinyl chloride composite materials of a kind of partially biodegradable and preparation method thereof |
| CN104693575A (en) * | 2013-12-07 | 2015-06-10 | 招远鲁娃婴幼儿用品有限公司 | Biodegradable plastic toy |
| CN103783257A (en) * | 2014-01-16 | 2014-05-14 | 内蒙古农业大学 | Preparation method for modified sheep muscle tendon collagen |
| CN105949737A (en) * | 2016-05-31 | 2016-09-21 | 沧州沧硕塑业有限公司 | Degradable mulching film and preparation method thereof |
| CN106832964A (en) * | 2017-03-03 | 2017-06-13 | 唐爱兰 | A kind of hydrophobic microprotein/composite polyolefine material and preparation method |
| CN109384961A (en) * | 2018-10-31 | 2019-02-26 | 浙江盛瑞环保科技有限公司 | A kind of fiber foam amortizing packaging material and preparation method thereof |
| CN111763431A (en) * | 2019-04-02 | 2020-10-13 | 四川大学 | Method for preparing foamed plastic by using waste leather leftover materials |
| CN111763431B (en) * | 2019-04-02 | 2021-09-21 | 四川大学 | Method for preparing foamed plastic by using waste leather leftover materials |
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Open date: 20100714 |