CN104130562A - Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof - Google Patents
Nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and preparation method thereof Download PDFInfo
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- CN104130562A CN104130562A CN201410361753.5A CN201410361753A CN104130562A CN 104130562 A CN104130562 A CN 104130562A CN 201410361753 A CN201410361753 A CN 201410361753A CN 104130562 A CN104130562 A CN 104130562A
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- butyric ester
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Abstract
The invention discloses a nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic and a preparation method thereof. The nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic comprises, by weight, 50-85% of polyhydroxybutyrate, 5-30% of a nano-bentonite composite flame-retardant, 0.1-5% of a processing assistant, 5-25% of degradable toughened resin, 0.1-5% of a coupling agent and 0.1-5% of a grafting agent. The preparation method comprises the following steps of drying the polyhydroxybutyrate, degradable toughened resin and nano-bentonite composite flame-retardant, adding the coupling agent into the above materials, carrying out activation by a high-rate mixer, mixing the mixture with the processing assistant and the grafting agent to obtain a uniform mixture, carrying out fusion extrusion by a double screw extruder and carrying out cooling, air-drying and grain-sized dicing. The nano-bentonite composite flame-retardant polyhydroxybutyrate bioplastic satisfies flame retardation standard of UL94V-0 level and retains mechanical properties and processing performances.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of nano-bentonite composite flame-proof poly butyric ester biological plastics and preparation method thereof.
Background technology
Day by day lack at petroleum resources, under the current form that environmental protection pressure increases day by day, the various rosin productss that are raw material with oil have greatly the trend that biological plastics replaced that is base material with natural biomass such as starch.The biological plastics of various countries' research and development at present mainly concentrates on these kinds: poly(lactic acid) (PLA), polyhydroxyalkanoate (PHA), polyglycolic acid (PGA).Biomass starting material is mainly derived from corn, potato, sugarcane, cereal, timber, wet goods.Poly butyric ester (polyhydroxybutyrate, PHB) be a kind of polyhydroxyalkanoate, first from cell, separate in nineteen twenty-seven, this material non-toxic and biodegradable, main application is to produce hot injecting products at present, manufactures as valve protection cap, pen, toy, food box etc.; Also be used as suture material in body and be applied to medical industry.Conventional plastic degraded needs 100 years, and the product of producing with poly butyric ester be as long as just can decompose for 12 months, and what discharge only has water and carbonic acid gas.
But consider for aspects such as product safety, but take more country's formulation laws and regulations requirement plastics and there is flame retardant resistance, especially environmental-protection flame-retardant function.Unstable when poly butyric ester is heated, its fusing point is close to decomposition temperature (175 degrees Celsius).This drawbacks limit its application in each field.At present the resinoid fire retardant of petrochemical industry mainly contains halogen system (chloride, brominated etc.), phosphorus system (phosphide, phosphoric acid ester etc.), nitrogen system (Dyhard RU 100, guanidinesalt etc.), silicon system (silicone resin, silicon rubber etc.), inorganic salt fire retardant (magnesium hydroxide, aluminium hydroxide etc.) and composite fire retardant etc., but fire retardant adds in poly butyric ester and tends to have a strong impact on poly butyric ester bulk material physical and mechanical property, it is obviously reduced.Therefore, from combustion environmental-friendly and various fire retardant, the equal angles that affects of plastic material physical and mechanical property is considered, still there is no at present a kind of, Effect on Mechanical Properties circlet environment friendly flame-retardant method high to poly butyric ester flame retarding efficiency.
Summary of the invention
The object of this invention is to provide a kind of nano-bentonite composite flame-proof poly butyric ester biological plastics, this matrix material has that fire-retardant rank is high, environmental protection, can keep the feature of poly butyric ester bulk material physical and mechanical property.
Another object of the present invention is to provide the preparation method of this nano-bentonite composite flame-proof poly butyric ester biological plastics.
In order to achieve the above object, by the following technical solutions of the present invention:
A kind of nano-bentonite composite flame-proof poly butyric ester biological plastics, this matrix material is made (gross weight meets 100%) by the component of following weight percentage:
Poly butyric ester 50～85%
Nano-bentonite compound flame retardant 5～30%
Processing aid 0.1～5%
Degradable toughened resin 5～25%
Coupling agent 0.1～5%
Grafting agent 0.1～5%.
Preferably, this matrix material is made (gross weight meets 100%) by the component of following weight percentage:
Poly butyric ester 50～70%
Nano-bentonite compound flame retardant 15～25%
Processing aid 0.1～1%
Degradable toughened resin 10～25%
Coupling agent 1～2%
Grafting agent 1～2%.
The be weight percentage inorganic combustion inhibitor of 50～80% nano level wilkinite and 20～50% of described nano-bentonite compound flame retardant is mixed and made into (taking the weight of nano-bentonite compound flame retardant as 100%), and the bentonitic particle diameter of nano level is preferably 1～100nm.
Described poly butyric ester molecular resin amount is preferably 1 × 10
5～3 × 10
5.Inorganic combustion inhibitor can be at least one in magnesium hydroxide, aluminium hydroxide, boride, calcified material, wherein, and boride preferred boric acid sodium, calcified material preferably calcium hydroxide.
Described degradable toughened resin is at least one in poly (propylene carbonate) (PPC), poly-second lactone (PCL), poly butylene succinate (PBS).
Described processing aid is at least one in oxidation inhibitor, lubricant, UV light absorber, white oil, methyl-silicone oil, and wherein oxidation inhibitor can be BASF B225, and UV light absorber can be BASF UV-326, and lubricant can be polyethylene wax.
Described coupling agent is at least one in titanic acid ester, Aluminate and silane coupling agent.
Described grafting agent is at least one in maleic anhydride graft compatilizer and methyl methacrylate.
The preparation method of above-mentioned nano-bentonite composite flame-proof poly butyric ester biological plastics, comprise the steps: first poly butyric ester, degradable toughened resin, nano-bentonite compound flame retardant to be dried, then add coupling agent stir-activating, mix with processing aid, grafting agent again, melt extrude rear cooling air-drying pelletizing finally by twin screw extruder.
In the preparation method of above-mentioned nano-bentonite composite flame-proof poly butyric ester biological plastics, the temperature of twin screw extruder preferably arranges as follows: feeding section 160～170
oc, compression section 160～170
oc, metering zone 170～180
oc, die head section 180～190
oc; Main-machine screw rotating speed is 160～230rpm, and conveying screw rod rotating speed is 20～50rpm, and charging basket rate of feeding is 10～20rpm.
The present invention first by poly butyric ester, degradable toughened resin, nano-bentonite compound flame retardant 80～90
odry 2～3 hours of C, the moisture absorbing from air to remove material, prevents that it from exerting an influence to product performance.
Beneficial effect of the present invention: 1. wilkinite is a kind of silicate minerals that is rich in magnalium, and chemical general formula is Nax (H
2o)
4{ (Al
2.xMgx) [Si
4o
10] (OH)
2, its crystalline structure is sheet as thin as a wafer, and the negative charge on surface can attract various positively charged ions, and can be by other cationic exchange, and wilkinite compound flame retardant of the present invention is not halogen-containing, environmental protection, and cost is lower, and preparation technology is simple; 2. select degradable toughened resin and fire retardant and use and can reduce or eliminate the disadvantageous effect of inorganic combustion inhibitor to poly butyric ester physical and mechanical properties; 3. select coupling agent and grafting agent to increase respectively consistency and the conjugation of wilkinite compound flame retardant and degradable toughened resin and poly butyric ester bulk material, further reduced the impact of fire retardant on poly butyric ester resin physical and mechanical properties.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Formula: 5000g molecular weight is 1.0x10
5the poly-second lactone of poly butyric ester, 1000g, 800g nano level wilkinite (particle diameter 1～100nm), 800g magnesium hydroxide, 50g titanic acid ester and 50g Aluminate, 50g methyl-silicone oil, 50g maleic anhydride graft compatilizer.
Preparation method:
Step 1: be 1.0 × 10 by 5000g molecular weight
5the poly-second lactone of poly butyric ester, 1000g, 800g nano level wilkinite, 800g magnesium hydroxide 85
odry 2 hours of C;
Step 2: by dried material and 50g titanic acid ester and 50g Aluminate in homogenizer with 90
oc, 1400rpm stir-activating 10 minutes;
Step 3: the compound obtaining in step 1 and two is mixed in low-speed mixer with 50g methyl-silicone oil, 50g maleic anhydride graft compatilizer;
Step 4: by all components obtaining in step 3 cooling air-drying pelletizing after twin screw extruder melt extrudes.The temperature of twin screw extruder arranges as follows: feeding section 160～170
oc, compression section 160～170oC, metering zone 170～180
oc, adapter 170～180
oc, die head section 180～190
oc; Main-machine screw rotating speed is 200rpm, and conveying screw rod rotating speed is 30rpm, and charging basket rate of feeding is 15rpm.
Product flame retardant resistance is tested through UL-94V, and flame retardant properties and mechanical properties results are in table 1.
Embodiment 2
Formula: be 3.0 × 10 by 5000g molecular weight
5the poly-second lactone of poly butyric ester, 1000g poly (propylene carbonate), 1000g, 800g nano level wilkinite (particle diameter 1～100nm), 800g aluminium hydroxide, 100g Aluminate, 50g polyethylene wax, 100g methyl methacrylate.
Preparation method:
Step 1: be 3.0 × 10 by 5000g molecular weight
5the poly-second lactone of poly butyric ester, 1000g poly (propylene carbonate), 1000g, 800g nano level wilkinite, 800g aluminium hydroxide are 85
odry 2 hours of C;
Step 2: by dried material and 100g Aluminate in homogenizer with 90
oc, 1400rpm stir-activating 10 minutes;
Step 3: the compound obtaining in step 1 and two is mixed in low-speed mixer with 50g polyethylene wax, 100g methyl methacrylate;
Step 4: by all components obtaining in step 3 cooling air-drying pelletizing after twin screw extruder melt extrudes.The temperature of twin screw extruder arranges as follows: feeding section 160～170
oc, compression section 160～170
oc, metering zone 170～180
oc, adapter 170～180
oc, die head section 180～190
oc; Main-machine screw rotating speed is 200rpm, and conveying screw rod rotating speed is 30rpm, and charging basket rate of feeding is 15rpm.
Product flame retardant resistance is tested through UL-94V, and flame retardant properties and mechanical properties results are in table 1.
Embodiment 3
Formula: 5000g molecular weight is 2.0 × 10
5the poly-second lactone of poly butyric ester, 1000g, 800g nano level wilkinite (particle diameter 1～100nm), 400g calcium hydroxide, 400g Sodium Tetraborate, 50g titanic acid ester and 50g Aluminate, 50g methyl-silicone oil, 50g maleic anhydride graft compatilizer.
Preparation method:
Step 1: be 2.0 × 10 by 5000g molecular weight
5the poly-second lactone of poly butyric ester, 1000g, 800g nano level wilkinite, 400g calcium hydroxide, 400g Sodium Tetraborate 85
odry 2 hours of C;
Step 2: by dried material and 100g titanic acid ester in homogenizer with 90
oc, 1400rpm stir-activating 10 minutes;
Step 3: the compound obtaining in step 1 and two is mixed in low-speed mixer with 60g BASF B225,50g uv-absorbing agent BASF UV-326,50g methyl-silicone oil, 50g maleic anhydride graft compatilizer;
Step 4: by all components obtaining in step 3 cooling air-drying pelletizing after twin screw extruder melt extrudes.The temperature of twin screw extruder arranges as follows: feeding section 160～170
oc, compression section 160～170
oc, metering zone 170～180
oc, adapter 170～180
oc, die head section 180～190
oc; Main-machine screw rotating speed is 230rpm, and conveying screw rod rotating speed is 50rpm, and charging basket rate of feeding is 20rpm.
Product flame retardant resistance is tested through UL-94V, and flame retardant properties and mechanical properties results are in table 1.
What comparative example was measured is the performance of poly butyric ester.
table 1
| Test event | Unit | Testing method | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Flame retardant resistance | mm | UL 94 | UL94V-0 | UL94V-0 | UL94V-0 | UL94HB |
| Melting index | g/ml | ISO 1133 | 10 | 10 | 11 | 11 |
| Tensile strength | MPa | ISO 527 | 37 | 39 | 36 | 37 |
| Notched Izod impact strength | J/m | ISO 179 | 119 | 120 | 130 | 123 |
| Flexural strength | MPa | ISO 178 | 95 | 92 | 87 | 92 |
The specific embodiment of the present invention is described although above-mentioned in conjunction with the embodiments; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendments that performing creative labour can make or distortion still within protection scope of the present invention.
Claims (10)
1. a nano-bentonite composite flame-proof poly butyric ester biological plastics, is characterized in that, this matrix material is made up of the component of following weight percentage:
Poly butyric ester 50～85%
Nano-bentonite compound flame retardant 5～30%
Processing aid 0.1～5%
Degradable toughened resin 5～25%
Coupling agent 0.1～5%
Grafting agent 0.1～5%.
2. nano-bentonite composite flame-proof poly butyric ester biological plastics according to claim 1, is characterized in that, described nano-bentonite compound flame retardant be weight percentage 50～80% nano level wilkinite and 20～50% inorganic combustion inhibitor.
3. nano-bentonite composite flame-proof poly butyric ester biological plastics according to claim 1, is characterized in that, described poly butyric ester molecular weight is 1 × 105～3 × 105.
4. nano-bentonite composite flame-proof poly butyric ester biological plastics according to claim 1, is characterized in that, described inorganic combustion inhibitor is at least one in magnesium hydroxide, aluminium hydroxide, boride, calcified material.
5. nano-bentonite composite flame-proof poly butyric ester biological plastics according to claim 1, is characterized in that, described degradable toughened resin is at least one in poly (propylene carbonate), poly-second lactone, poly butylene succinate.
6. nano-bentonite composite flame-proof poly butyric ester biological plastics according to claim 1, is characterized in that, described processing aid is at least one in oxidation inhibitor, lubricant, UV light absorber, white oil, methyl-silicone oil.
7. nano-bentonite composite flame-proof poly butyric ester biological plastics according to claim 1, is characterized in that, described coupling agent is at least one in titanic acid ester, Aluminate and silane coupling agent.
8. nano-bentonite composite flame-proof poly butyric ester biological plastics according to claim 1, is characterized in that, described grafting agent is at least one in maleic anhydride graft compatilizer and methyl methacrylate.
9. according to the preparation method of the nano-bentonite composite flame-proof poly butyric ester biological plastics described in claim 1～8 any one claim, it is characterized in that, the method comprises the steps:
First poly butyric ester, degradable toughened resin, nano-bentonite compound flame retardant are dried, then add coupling agent stir-activating, then mix with processing aid, grafting agent, melt extrude rear cooling air-drying pelletizing finally by twin screw extruder.
10. the preparation method of nano-bentonite composite flame-proof poly butyric ester biological plastics according to claim 9, is characterized in that: the temperature of described twin screw extruder arranges as follows: feeding section 160～170
oc, compression section 160～170
oc, metering zone 170～180
oc, die head section 180～190
oc; Main-machine screw rotating speed is 160～230rpm, and conveying screw rod rotating speed is 20～50rpm, and charging basket rate of feeding is 10～20rpm.
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| CN106700455A (en) * | 2015-11-15 | 2017-05-24 | 合肥杰事杰新材料股份有限公司 | Nano-Al2O3 modified biopolymer material and preparation method thereof |
| CN108440928A (en) * | 2018-05-02 | 2018-08-24 | 安徽九牛塑业科技有限公司 | A kind of high performance modified plastics and preparation method thereof |
| CN110157169A (en) * | 2018-03-19 | 2019-08-23 | 李顺河 | A kind of fire-retardant degradation plastic of environmental protection |
| CN112226057A (en) * | 2020-11-04 | 2021-01-15 | 中国矿业大学 | Natural mineral modified degradable high-molecular flame-retardant composite material and preparation method thereof |
| CN112321900A (en) * | 2020-11-23 | 2021-02-05 | 浙江长安仁恒科技股份有限公司 | Bentonite for flame retardant and preparation method thereof |
| CN112625413A (en) * | 2020-12-17 | 2021-04-09 | 青岛博远高分子材料研究院有限公司 | Modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106700455A (en) * | 2015-11-15 | 2017-05-24 | 合肥杰事杰新材料股份有限公司 | Nano-Al2O3 modified biopolymer material and preparation method thereof |
| CN110157169A (en) * | 2018-03-19 | 2019-08-23 | 李顺河 | A kind of fire-retardant degradation plastic of environmental protection |
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| CN112226057A (en) * | 2020-11-04 | 2021-01-15 | 中国矿业大学 | Natural mineral modified degradable high-molecular flame-retardant composite material and preparation method thereof |
| CN112321900A (en) * | 2020-11-23 | 2021-02-05 | 浙江长安仁恒科技股份有限公司 | Bentonite for flame retardant and preparation method thereof |
| CN112625413A (en) * | 2020-12-17 | 2021-04-09 | 青岛博远高分子材料研究院有限公司 | Modified poly (4-hydroxybutyrate) low-temperature thermoplastic medical splint material |
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Application publication date: 20141105 |