CN103013071A - Biodegradable PHA (polyhydroxyalkanoate) breathable membrane and preparation method thereof - Google Patents
Biodegradable PHA (polyhydroxyalkanoate) breathable membrane and preparation method thereof Download PDFInfo
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- CN103013071A CN103013071A CN2012105497670A CN201210549767A CN103013071A CN 103013071 A CN103013071 A CN 103013071A CN 2012105497670 A CN2012105497670 A CN 2012105497670A CN 201210549767 A CN201210549767 A CN 201210549767A CN 103013071 A CN103013071 A CN 103013071A
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Abstract
A biodegradable PHA (polyhydroxyalkanoate) breathable membrane comprises the following components in part by weight: 100 parts of PHA resin, 10-15 parts of PBAT resin, 25-55.6 parts of inorganic additive masterbatch and 0.01-0.03 parts of antistatic agent, wherein the inorganic additive masterbatch comprises the following components in part by weight: 100 parts of PHA resin, 300-400 parts of inorganic filler, 10100.18 parts of antioxidant and1680.12 parts of antioxidant; and the inorganic filler is one or more of calcium carbonate, talc or kaolin. A preparation method of the biodegradable PHA breathable membrane comprises the following steps: firstly, preparing the inorganic additive masterbatch; secondly, sufficiently stirring and mixing the components according to the proportion; and finally, extruding a mixture by using a single screw extruder, casting, drawing, cooling, winding and slitting the mixture to obtain the biodegradable PHA breathable membrane. The breathable membrane is prepared from the biodegradable PHA, so that mechanical properties of the breathable membrane are excellent and using requirements of breathable membranes such as a hygienic membrane and a medical membrane can be completely met.
Description
Technical field
The invention belongs to the degradable films manufacture field, be specifically related to a kind of biological degradation PHA air-permeable envelope and preparation method thereof.
Background technology
Air-permeable envelope is a kind of novel thin-film material, and in the plastics film kind, air-permeable envelope is widely applied in health, medicine, building, automobile and sports industry.Along with the gradually maturation of complete processing, the usage quantity of air-permeable envelope increases gradually.Yet the increase of plastics air-permeating film usage quantity is accompanied by increasing the weight of of white pollution.
Polyhydroxyalkanoate (PHA) is a kind of natural polymeric biomaterial, has good ultraviolet stability etc.Under natural environmental condition, PHA can pass through microorganism (such as bacterium, fungi and algae etc.) degraded, and PHA can be hard such as duroplasts, also can be soft such as elastomerics, therefore have wide range of applications, and washability is stronger.Along with degradation material popularization socially, PHA has begun to be applied in the fields such as film, packing.
The biological degradation air-permeable envelope of existing market and patent report only has two kinds of PLA, PBS, and wherein the PLA crystallization rate is slow, and toughness and resistance to tearing are relatively poor, and the PBS mechanical property is relatively poor, and therefore hydrolysis is not used and be subject to certain limitation; PHA can regulate and control its tensile strength, fusing point, toughness, hardness etc. according to different monomeric species and monomer side chain length, so the development space of PHA is large, and using value is stronger.
There is no at present the report of biological degradation PHA air-permeable envelope.
Summary of the invention
The object of the present invention is to provide a kind of biological degradation PHA air-permeable envelope.This film environmental protection, can be degradable, mechanical property is excellent, the film porosity is even.
Another object of the present invention provides a kind of preparation method of biological degradation PHA air-permeable envelope.
To achieve these goals, the present invention adopts following technical scheme:
A kind of biological degradation PHA air-permeable envelope is characterized in that it comprises the component of following parts by weight:
100 parts of PHA resins
PBAT resin 10-15 part
Inorganic interpolation masterbatch 25-55.6 part
Static inhibitor 0.01-0.03 part;
Wherein, described PHA resin is that melting index is 190 ℃ in the 4-15g/10min(test condition, and 2.16Kg), fusing point is between 90 ℃-135 ℃, and degree of crystallinity is lower than 20% polyhydroxyalkanoate.
Described PBAT resin is German BASF ECOVIO type PBAT resin.
Described static inhibitor is one or more in the Entira AS of E.I.Du Pont Company permanent anti-static agent SD100 type, MK400 type and the AS500 type.
Described inorganic interpolation masterbatch comprises the component of following weight fraction:
100 parts of PHA resins
Mineral filler 300-400 part
0.18 part of antioxidant 1010
0.12 part of irgasfos 168
Wherein, described mineral filler is one or more in calcium carbonate, talcum powder or the kaolin.
Wherein, described antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Wherein, described irgasfos 168 is three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.
A kind of biological degradation PHA air-permeable envelope is characterized in that it may further comprise the steps:
(1) the inorganic interpolation masterbatch of preparation:
100 parts of PHA resins, the mineral filler of 300-400 part, 0.18 part of antioxidant 1010,0.12 part of irgasfos 168 through the twin screw extruder mixing granulation, are made inorganic interpolation masterbatch, dried for standby.
(2) biological degradation PHA air-permeable envelope:
PHA resin, PBAT are fully dried, and temperature is 70 ℃, and the time is 3h; With 100 parts of PHA resins, 10-15 part PBAT resin, 25-55.6 part inorganic interpolation masterbatch, 0.01-0.03 a part static inhibitor fully mixes, then extrude through single screw extrusion machine, curtain coating, stretch, cooling, rolling, cut, extrusion temperature 170-195 ℃, first draws longitudinal stretching district temperature 50-75 ℃, draw ratio 2.5-3.0, setting temperature 90-115 ℃, the second longitudinal stretching district temperature 55-70 ℃, draw ratio 2.2-2.5, setting temperature 90-110 ℃, the first cross directional stretch district temperature 55-70 ℃, draw ratio 3.5-4.5, setting temperature 90-115 ℃, film is carried out rolling and cut, namely get biological degradation PHA air-permeable envelope.
Beneficial effect: the present invention provides biological degradation PHA air-permeable envelope and preparation method thereof first, and technical process is simple, the air-permeable envelope excellent heat resistance of preparation.This biological degradation PHA air-permeable envelope tensile strength scope is wider, and maximum can reach 150Mpa, and water tolerance is better, obviously is better than other biological degraded air-permeable envelope, can reach the service requirements of the air-permeable envelopes such as health film, medical films fully.
Embodiment
The described PHA resin of following examples is Shenzhen Yi Keman company limited film-grade, and the PBAT resin is German BASF ECOVIO type PBAT resin, and Entira AS permanent anti-static agent SD100 type, MK400 type and AS500 type are all available from E.I.Du Pont Company.Irgasfos 168 and antioxidant 1010 are all available from Beijing three Anhua Chemicals company limiteds.
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for further specifying of the present invention; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection domain of the present invention.
Example 1
100 parts of PHA resins, 300 parts of calcium carbonate, 0.18 part of antioxidant 1010,0.12 part of irgasfos 168 make inorganic interpolation masterbatch, dried for standby through the twin screw extruder mixing granulation.
With PHA resin, PBAT resin at 70 ℃ of abundant dry 3h; Get 100 parts of PHA resins, 10 parts of PBAT resins, 25 parts of inorganic interpolation masterbatch, 0.01 part abundant mix and blend of the Entira AS of E.I.Du Pont Company permanent SD100 type static inhibitor, extrude through single screw extrusion machine, curtain coating, stretch, cooling, 170 ℃ of extrusion temperatures, 180 ℃, 190 ℃, 195 ℃, first draws longitudinal stretching district temperature 50 C, draw ratio 2.5,90 ℃ of setting temperatures, 55 ℃ of the second longitudinal stretching district temperature, draw ratio 2.2,90 ℃ of setting temperatures, 65 ℃ of the first cross directional stretch district temperature, draw ratio 3.5,90 ℃ of setting temperatures carry out rolling with film and cut, namely get biological degradation PHA air-permeable envelope, its performance is as shown in table 1.
Example 2
100 parts of PHA resins, 350 parts of talcum powder, 0.18 part of antioxidant 1010,0.12 part of irgasfos 168 make inorganic interpolation masterbatch, dried for standby through the twin screw extruder mixing granulation.
With PHA resin, PBAT resin at 70 ℃ of abundant dry 3h; Get 100 parts of PHA resins, 10 parts of PBAT resins, 25 parts of inorganic interpolation masterbatch, 0.01 part SD100 type static inhibitor, 0.02 part abundant mix and blend of AS500 type static inhibitor, extrude through single screw extrusion machine, curtain coating, stretch, cooling, 175 ℃ of extrusion temperatures, 188 ℃, 190 ℃, 195 ℃, first draws longitudinal stretching district temperature 60 C, draw ratio 2.8,92 ℃ of setting temperatures, 65 ℃ of the second longitudinal stretching district temperature, draw ratio 2.2,98 ℃ of setting temperatures, 55 ℃ of the first cross directional stretch district temperature, draw ratio 4.2,90 ℃ of setting temperatures carry out rolling with film and cut, namely get biological degradation PHA air-permeable envelope, its performance is as shown in table 1.
Example 3
100 parts of PHA resins, 400 parts of calcium carbonate, 0.18 part of antioxidant 1010,0.12 part of irgasfos 168 make inorganic interpolation masterbatch, dried for standby through the twin screw extruder mixing granulation.
With PHA resin, PBAT resin at 70 ℃ of abundant dry 3h; Get 100 parts of PHA resins, 12 parts of PBAT resins, 40 parts of inorganic interpolation masterbatch, 0.01 part SD100 type static inhibitor, 0.02MK400 the abundant mix and blend of type static inhibitor, extrude through single screw extrusion machine, curtain coating, stretch, cooling, 182 ℃ of extrusion temperatures, 188 ℃, 192 ℃, 195 ℃, first draws 68 ℃ of longitudinal stretching district temperature, draw ratio 2.6,95 ℃ of setting temperatures, 68 ℃ of the second longitudinal stretching district temperature, draw ratio 2.2,98 ℃ of setting temperatures, 68 ℃ of the first cross directional stretch district temperature, draw ratio 4.0,115 ℃ of setting temperatures carry out rolling with film and cut, namely get biological degradation PHA air-permeable envelope, its performance is as shown in table 1.
Example 4
100 parts of PHA resins, 200 parts of talcum powder, 200 parts of kaolin, 0.18 part of antioxidant 1010,0.12 part of irgasfos 168 make inorganic interpolation masterbatch, dried for standby through the twin screw extruder mixing granulation.
With PHA resin, PBAT resin at 70 ℃ of abundant dry 3h; Get 100 parts of PHA resins, 14 parts of PBAT resins, 50 parts of inorganic interpolation masterbatch, 0.02 part SD100 type static inhibitor, 0.01MK400 the abundant mix and blend of type static inhibitor, extrude through single screw extrusion machine, curtain coating, stretch, cooling, 182 ℃ of extrusion temperatures, 188 ℃, 192 ℃, 195 ℃, first draws longitudinal stretching district temperature 70 C, draw ratio 3.0,95 ℃ of setting temperatures, 69 ℃ of the second longitudinal stretching district temperature, draw ratio 2.5,110 ℃ of setting temperatures, 68 ℃ of the first cross directional stretch district temperature, draw ratio 4.5,95 ℃ of setting temperatures carry out rolling with film and cut, namely get biological degradation PHA air-permeable envelope, its performance is as shown in table 1.
Example 5
100 parts of PHA resins, 200 parts of calcium carbonate, 200 parts of talcum powder, 0.18 part of antioxidant 1010,0.12 part of irgasfos 168 make inorganic interpolation masterbatch, dried for standby through the twin screw extruder mixing granulation.
With PHA resin, PBAT resin at 70 ℃ of abundant dry 3h; Get 100 parts of PHA resins, 15 parts of PBAT resins, 55.6 part inorganic interpolation masterbatch, 0.02 part SD100 type static inhibitor, 0.01MK400 the abundant mix and blend of type static inhibitor, extrude through single screw extrusion machine, curtain coating, stretch, cooling, 182 ℃ of extrusion temperatures, 188 ℃, 192 ℃, 195 ℃, first draws longitudinal stretching district temperature 70 C, draw ratio 2.5,115 ℃ of setting temperatures, the second longitudinal stretching district temperature 70 C, draw ratio 2.2,105 ℃ of setting temperatures, the first cross directional stretch district temperature 70 C, draw ratio 4.5,106 ℃ of setting temperatures carry out rolling with film and cut, namely get biological degradation PHA air-permeable envelope, its performance is as shown in table 1.
Example 6
100 parts of PHA resins, 200 parts of calcium carbonate, 200 parts of talcum powder, 0.18 part of antioxidant 1010,0.12 part of irgasfos 168 make inorganic interpolation masterbatch, dried for standby through the twin screw extruder mixing granulation.
With PHA resin, PBAT resin at 70 ℃ of abundant dry 3h; Get 100 parts of PHA resins, 15 parts of PBAT resins, 55.6 part inorganic interpolation masterbatch, 0.02 part SD100 type static inhibitor, 0.01MK400 the abundant mix and blend of type static inhibitor, extrude through single screw extrusion machine, curtain coating, stretch, cooling, 182 ℃ of extrusion temperatures, 188 ℃, 192 ℃, 195 ℃, first draws 75 ℃ of longitudinal stretching district temperature, draw ratio 2.5,95 ℃ of setting temperatures, the second longitudinal stretching district temperature 70 C, draw ratio 2.2,110 ℃ of setting temperatures, the first cross directional stretch district temperature 70 C, draw ratio 3.8,110 ℃ of setting temperatures carry out rolling with film and cut, namely get biological degradation PHA air-permeable envelope, its performance is as shown in table 1.
The physicals of table 1 embodiment sample
Tensile strength in the embodiment of the invention, elongation at break are measured according to GB/T 1040-1992, and draw speed is 50mm/min, and test result is got 5 times on average; Dimension card heat resisting temperature is measured according to GB/T1633, and counterweight weight is 10N, and temperature rise rate is 120 ℃/h; Water vapor transmission rate (WVTR) selects Permatran-W 100K vapor permeation analytical system to measure.
Claims (6)
1. biological degradation PHA air-permeable envelope is characterized in that it comprises the component of following parts by weight:
100 parts of PHA resins
PBAT resin 10-15 part
Inorganic interpolation masterbatch 25-55.6 part
Static inhibitor 0.01-0.03 part.
2. biological degradation PHA air-permeable envelope according to claim 1 is characterized in that: described PHA resin be melting index at 4-15g/10min, fusing point is between 90 ℃-135 ℃, degree of crystallinity is lower than 20% polyhydroxyalkanoate.
3. biological degradation PHA air-permeable envelope according to claim 1, it is characterized in that: described inorganic interpolation masterbatch comprises the component of following parts by weight:
100 parts of PHA resins
Mineral filler 300-400 part
0.18 part of antioxidant 1010
0.12 part of irgasfos 168.
4. biological degradation PHA air-permeable envelope according to claim 3, it is characterized in that: described mineral filler is one or more in calcium carbonate, talcum powder or the kaolin.
5. biological degradation PHA air-permeable envelope according to claim 1, it is characterized in that: described static inhibitor is one or more in permanent anti-static agent SD100 type, MK400 type and the AS500 type.
6. the preparation method of the described biological degradation PHA of claim 1 ~ 5 air-permeable envelope is characterized in that it may further comprise the steps:
1) the inorganic interpolation masterbatch of preparation:
100 parts of PHA resins, the mineral filler of 300-400 part, 0.18 part of antioxidant 1010,0.12 part of irgasfos 168 through the twin screw extruder mixing granulation, are made inorganic interpolation masterbatch, dried for standby;
2) biological degradation PHA air-permeable envelope:
With PHA resin, the oven dry of PBAT resin; 100 parts of PHA resins, 10-15 part PBAT resin, the inorganic interpolation masterbatch of 25-55.6 part, 0.01-0.03 part static inhibitor are fully mixed, then extrude, curtain coating, stretching, cooling, rolling, cut through single screw extrusion machine, namely get biological degradation PHA air-permeable envelope; Wherein: extrusion temperature 170-195 ℃, first draws longitudinal stretching district temperature 50-75 ℃, draw ratio 2.5-3.0, setting temperature 90-115 ℃, the second longitudinal stretching district temperature 55-70 ℃, draw ratio 2.2-2.5, setting temperature 90-110 ℃, the first cross directional stretch district temperature 55-70 ℃, draw ratio 3.5-4.5, setting temperature 90-115 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286904A (en) * | 2022-08-16 | 2022-11-04 | 江西广源新材料有限公司 | Biodegradable breathable material, biodegradable breathable master batch, biodegradable breathable film and application thereof |
| CN115401956A (en) * | 2022-09-05 | 2022-11-29 | 山东恒鹏卫生用品有限公司 | Antistatic soft composite film fabric and production process thereof |
| CN115772290A (en) * | 2023-01-29 | 2023-03-10 | 河北海德塑业有限公司 | Antibacterial breathable film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056985A (en) * | 2008-05-06 | 2011-05-11 | 梅塔玻利克斯公司 | Biodegradable polyester blends |
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- 2012-12-18 CN CN201210549767.0A patent/CN103013071B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056985A (en) * | 2008-05-06 | 2011-05-11 | 梅塔玻利克斯公司 | Biodegradable polyester blends |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286904A (en) * | 2022-08-16 | 2022-11-04 | 江西广源新材料有限公司 | Biodegradable breathable material, biodegradable breathable master batch, biodegradable breathable film and application thereof |
| CN115286904B (en) * | 2022-08-16 | 2024-02-02 | 江西广源新材料有限公司 | Biodegradable breathable material, biodegradable breathable master batch, biodegradable breathable film and application thereof |
| CN115401956A (en) * | 2022-09-05 | 2022-11-29 | 山东恒鹏卫生用品有限公司 | Antistatic soft composite film fabric and production process thereof |
| CN115772290A (en) * | 2023-01-29 | 2023-03-10 | 河北海德塑业有限公司 | Antibacterial breathable film |
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Address after: 221416, No. 189 East Bridge Road, Xuzhou City, Jiangsu, Xinyi Applicant after: JIANGSU HUAXIN NEW MATERIAL Co.,Ltd. Address before: 221416, No. 189 East Bridge Road, Xuzhou City, Jiangsu, Xinyi Applicant before: JIANGSU HUAXIN PLASTIC INDUSTRY DEVELOPING Co.,Ltd. |
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Effective date of registration: 20230331 Address after: 221000 West side of the Pearl River Road, Zone B, Xinyi Economic and Technological Development Zone, Xuzhou, Jiangsu Province (No. 19, the Pearl River Road) Patentee after: Jiangsu Huaxin High-tech Materials Co.,Ltd. Address before: 221416 No.189 Daqiao East Road, Xinyi City, Xuzhou City, Jiangsu Province Patentee before: JIANGSU HUAXIN NEW MATERIAL Co.,Ltd. |