CN107513203A - A kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale - Google Patents
A kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale Download PDFInfo
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- CN107513203A CN107513203A CN201710875267.9A CN201710875267A CN107513203A CN 107513203 A CN107513203 A CN 107513203A CN 201710875267 A CN201710875267 A CN 201710875267A CN 107513203 A CN107513203 A CN 107513203A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
A kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale, belongs to plastic composite technical field, comprises the following steps：Prepare Grafted Nano-scale silica, alkali lignin pretreatment, mixed material is made in addition auxiliary agent, composite filler particles are made in addition calcium carbonate, material is kneaded.The addition of nano silicon improves the mechanical property of material.The surface of nano silicon is modified, and improves the interfacial adhesion level of nano silicon and rubber mass, improves the combination property of rubber composite.
Description
Technical field
The invention belongs to plastic composite technical field, and in particular to a kind of silica-filled modeling of Grafted Nano-scale
Expect the preparation method of composite.
Background technology
Polyvinyl resin due to it is cheap, performance is good, as the continuous development of technology, polyethylene are excellent with its
Mechanical performance and chemical stability, it is widely used in each sides such as industry, agricultural, medicine, health and daily living article
Face, have become the kind that yield is maximum in plastic resin.In most cases, polyvinyl resin is not single use
, but want mixed filler.Filler, also known as filler, he is for improving the performance of vinyon product, reducing product
Cost, have very significant effect.Due to filler wide material sources, cheap, so being processed in vinyon
In have a wide range of applications.But solving filler and polyvinyl resin compatibility at present, improving the side such as composite materials property
Face need further to improve.
The content of the invention
In order to solve problems of the prior art, doing invention, to provide a kind of Grafted Nano-scale silica-filled
The preparation method of plastic composite, it is intended that the compatibility of raising filler and polyvinyl resin, filler are in polyvinyl resin
The degree that is evenly distributed and raising composite materials property.
In order to solve problems of the prior art, the present invention uses following technical scheme：
A kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale, comprises the following steps：
Step 1：The nano silicon of 3 parts by weight is dissolved in ultrasonic disperse in the ethanol of volumetric concentration 95% of 7 parts by weight
15min, suspension is made, the γ of 1 parts by weight-methacryloxypropyl trimethoxy silicon is added to the volume of 3 parts by weight
2h is hydrolyzed in the ethanol of concentration 95%, obtained solution, suspension is well mixed to obtain mixed liquor with solution, is adjusted and mixed with triethylamine
Liquid PH to 10,6h being stirred at 25 DEG C, being warming up to 50 DEG C, isothermal reaction 1h, cooling, centrifugation alcohol washes 3 times, distillation washing 2 times, freezing
It is dried to obtain Grafted Nano-scale silica；
Step 2：Weigh alkali lignin 150g to be positioned in container, continuously dried in 80 DEG C, 80bar vacuum drying chamber
Dry 24h, stirs a sample every 12h, is sealed after taking-up standby；
Step 3：Air-flow crushing processing is carried out to the sample, air-flow crushing, control are carried out using BPQ-50 airslide disintegrating mills
Sample preparation product charging rate is 300g/h, and it is 0.6MPa, exit pressure 0.6MPa to crush air inlet pressure；
Step 4：Alkali lignin after crushing is positioned in 80 DEG C of thermostatic drying chamber processing is dried, dry 24h
Afterwards, it is standby to take out sealing；
Step 5：The alkali lignin for weighing dried 20g is laid on surface plate, with rubber head dropper by 7.5g neighbour's benzene two
Formic acid dioctyl ester disperses to be added on alkali lignin dropwise, and adds 3g silane couplers and 3g calcium stearates, after stirring,
Taken out after mixing 1min using mixed at high speed crusher in crushing, 24h is dried in 80 DEG C of thermostatic drying chambers and is taken out, obtains mixture
Material；
Step 6：Mixed material 10g and calcium carbonate 10g is weighed, 200ml water is added, is stirred using magnetic stirring apparatus,
Suspension system is become, suspension is spray-dried, sets vapo(u)rizing temperature as 180 DEG C, outlet temperature is 90 DEG C, spraying
Speed is 6ml/min, obtain composite filler particles, in 80 DEG C of thermostatic drying chambers dry 24h after take out it is standby；
Step 7：Weigh high density polyethylene materials particle 300g to be positioned in container, done in the vacuum of 80 DEG C, 80bar
Continuous drying 24h in dry case, a sample is stirred every 12h, is sealed after taking-up standby；
Step 8：The high density polyethylene materials particle of 80 dry parts by weight is weighed, rubber mixing machine is preheated, when double roller temperature
When reaching 170 DEG C high density polyethylene materials are carried out with refining glue, after 2min, adds the composite filler particles and 10 of 10 parts by weight
The Grafted Nano-scale silica of parts by weight is kneaded, and after being kneaded 10min, obtains composite.
Preferably, the average grain diameter for alkali lignin being obtained after the processing of described step three alkali air-flow crushing is 3 μm ± 0.1 μm.
Preferably, the rubber mixing machine described in step 8 is the open refining glue molding machines of X (S) K.
Preferably, the particle diameter of the nano silicon described in step 1 is 7nm ± 1nm.
The beneficial effects of the present invention are:
1) addition of nano silicon improves the mechanical property of material.Nano silicon because its particle diameter is small, than
Surface area is big, and surface has unsaturated residual bond, has the surface-active of height, particularly superficial layer is with the presence of-OH, numerous particles
Side chain is connected to form with hydrogen bond each other, three-dimensional chain structure is interacted to form with hydrogen bond again between side chain, and then formed secondary
Particle, so that aggregate, has had a strong impact on the various properties of obtained nano composite material.The surface of nano silicon changes
Property, the amount of surface silanol groups is eliminated or reduced, product is changed into hydrophobic from hydrophilic, makes nano-silicon dioxide particle in polymer matrix
The good interfacial adhesion level disperseed, improve nano silicon and rubber mass is obtained in body, is improved rubber combined
The combination property of material, nano silicon have a good application prospect.
2) grain diameter that the present invention handles to obtain by air-flow crushing is smaller, and average grain diameter is 3 μm ± 0.1 μm, alkali wood
Quality grain diameter is smaller, and the tensile strength of composite is bigger.It is favorably improved the mechanical property of composite
3) present invention is by adding plastic additive：Dioctyl phthalate, silane coupler and calcium stearate improve
Interface compatibility between alkali lignin and polyvinyl resin, improve the lubrication between alkali lignin molecule and polyethylene molecular chain
Effect, improve the comprehensive mechanical property of composite.
4) organic modifier of the lignin as calcium carbonate, the compatibility of calcium carbonate and base polyethylene can be improved；And
Calcium carbonate can prevent the reunion of lignin in mixing process, promote lignin in the base scattered.In a word, lignin and
The effect of synergistic reinforcement is shown when calcium carbonate is as filler, and lignin can improve the power of calcium carbonate in the composite
Performance is learned, there is modification to calcium carbonate.
Embodiment
Below by the description to embodiment, the present invention is further detailed explanation, to help people in the art
Member has more complete, accurate and deep understanding to inventive concept of the invention, technical scheme.
Embodiment 1
A kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale, comprises the following steps：
Step 1：The nano silicon of 3 parts by weight is dissolved in ultrasonic disperse in the ethanol of volumetric concentration 95% of 7 parts by weight
15min, suspension is made, the γ of 1 parts by weight-methacryloxypropyl trimethoxy silicon is added to the volume of 3 parts by weight
2h is hydrolyzed in the ethanol of concentration 95%, obtained solution, suspension is well mixed to obtain mixed liquor with solution, is adjusted and mixed with triethylamine
Liquid PH to 10,6h being stirred at 25 DEG C, being warming up to 50 DEG C, isothermal reaction 1h, cooling, centrifugation alcohol washes 3 times, distillation washing 2 times, freezing
It is dried to obtain Grafted Nano-scale silica；
Step 2：Weigh alkali lignin 150g to be positioned in container, continuously dried in 80 DEG C, 80bar vacuum drying chamber
Dry 24h, stirs a sample every 12h, is sealed after taking-up standby；
Step 3：Air-flow crushing processing is carried out to the sample, air-flow crushing, control are carried out using BPQ-50 airslide disintegrating mills
Sample preparation product charging rate is 300g/h, and it is 0.6MPa, exit pressure 0.6MPa to crush air inlet pressure；
Step 4：Alkali lignin after crushing is positioned in 80 DEG C of thermostatic drying chamber processing is dried, dry 24h
Afterwards, it is standby to take out sealing；
Step 5：The alkali lignin for weighing dried 20g is laid on surface plate, with rubber head dropper by 7.5g neighbour's benzene two
Formic acid dioctyl ester disperses to be added on alkali lignin dropwise, and adds 3g silane couplers and 3g calcium stearates, after stirring,
Taken out after mixing 1min using mixed at high speed crusher in crushing, 24h is dried in 80 DEG C of thermostatic drying chambers and is taken out, obtains mixture
Material；
Step 6：Mixed material 10g and calcium carbonate 10g is weighed, 200ml water is added, is stirred using magnetic stirring apparatus,
Suspension system is become, suspension is spray-dried, sets vapo(u)rizing temperature as 180 DEG C, outlet temperature is 90 DEG C, spraying
Speed is 6ml/min, obtain composite filler particles, in 80 DEG C of thermostatic drying chambers dry 24h after take out it is standby；
Step 7：Weigh high density polyethylene materials particle 300g to be positioned in container, done in the vacuum of 80 DEG C, 80bar
Continuous drying 24h in dry case, a sample is stirred every 12h, is sealed after taking-up standby；
Step 8：The high density polyethylene materials particle of 80 dry parts by weight is weighed, rubber mixing machine is preheated, when double roller temperature
When reaching 170 DEG C high density polyethylene materials are carried out with refining glue, after 2min, adds the composite filler particles and 10 of 10 parts by weight
The Grafted Nano-scale silica of parts by weight is kneaded, and after being kneaded 10min, obtains composite.
The average grain diameter that alkali lignin is obtained after described step three alkali air-flow crushing processing is 3 μm ± 0.1 μm.
Rubber mixing machine described in step 8 is the open refining glue molding machines of X (S) K.
The particle diameter of nano silicon described in step 1 is 7nm ± 1nm.
Claims (4)
1. a kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale, it is characterised in that including following
Step：
Step 1：The nano silicon of 3 parts by weight is dissolved in ultrasonic disperse in the ethanol of volumetric concentration 95% of 7 parts by weight
15min, suspension is made, the γ of 1 parts by weight-methacryloxypropyl trimethoxy silicon is added to the volume of 3 parts by weight
2h is hydrolyzed in the ethanol of concentration 95%, obtained solution, suspension is well mixed to obtain mixed liquor with solution, is adjusted and mixed with triethylamine
Liquid PH to 10,6h being stirred at 25 DEG C, being warming up to 50 DEG C, isothermal reaction 1h, cooling, centrifugation alcohol washes 3 times, distillation washing 2 times, freezing
It is dried to obtain Grafted Nano-scale silica；
Step 2：Weigh alkali lignin 150g to be positioned in container, the continuous drying in 80 DEG C, 80bar vacuum drying chamber
24h, a sample is stirred every 12h, is sealed after taking-up standby；
Step 3：Air-flow crushing processing is carried out to the sample, air-flow crushing is carried out using BPQ-50 airslide disintegrating mills, controls sample
Product charging rate is 300g/h, and it is 0.6MPa, exit pressure 0.6MPa to crush air inlet pressure；
Step 4：Alkali lignin after crushing is positioned in 80 DEG C of thermostatic drying chamber processing is dried, after drying 24h,
It is standby to take out sealing；
Step 5：The alkali lignin for weighing dried 20g is laid on surface plate, with rubber head dropper by 7.5g phthalic acids
Dioctyl ester disperses to be added on alkali lignin dropwise, and adds 3g silane couplers and 3g calcium stearates, after stirring, utilizes
Taken out after mixed at high speed crusher in crushing mixing 1min, 24h is dried in 80 DEG C of thermostatic drying chambers and is taken out, obtains mixed material；
Step 6：Mixed material 10g and calcium carbonate 10g is weighed, 200ml water is added, is stirred, made into using magnetic stirring apparatus
For suspension system, suspension is spray-dried, sets vapo(u)rizing temperature as 180 DEG C, outlet temperature is 90 DEG C, spray velocity
For 6ml/min, obtain composite filler particles, dried in 80 DEG C of thermostatic drying chambers take out after 24h it is standby；
Step 7：Weigh high density polyethylene materials particle 300g to be positioned in container, in 80 DEG C, 80bar vacuum drying chamber
Middle continuous drying 24h, a sample is stirred every 12h, is sealed after taking-up standby；
Step 8：The high density polyethylene materials particle of 80 dry parts by weight is weighed, rubber mixing machine is preheated, when double roller temperature reaches
Refining glue is carried out to high density polyethylene materials at 170 DEG C, after 2min, adds the composite filler particles and 10 weight of 10 parts by weight
The Grafted Nano-scale silica of part is kneaded, and after being kneaded 10min, obtains composite.
A kind of 2. preparation method of the silica-filled plastic composite of Grafted Nano-scale according to claim 1：
The average grain diameter that alkali lignin is obtained after described step three alkali air-flow crushing processing is 3 μm ± 0.1 μm.
3. a kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale according to claim 1,
It is characterized in that：Rubber mixing machine described in step 8 is the open refining glue molding machines of X (S) K.
4. a kind of preparation method of the silica-filled plastic composite of Grafted Nano-scale according to claim 1,
It is characterized in that：The particle diameter of nano silicon described in step 1 is 7nm ± 1nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129752A (en) * | 2018-01-23 | 2018-06-08 | 苏州聚康新材料科技有限公司 | The preparation method of suspension polymerisation nanometer silicon dioxide composite material |
| CN108948797A (en) * | 2018-07-18 | 2018-12-07 | 武汉金牛经济发展有限公司 | A kind of preparation method of modified manometer silicon dioxide |
| CN109260026A (en) * | 2018-10-04 | 2019-01-25 | 南京航空航天大学溧水仿生产业研究院有限公司 | Silica dental filled composite materials and preparation method thereof |
| CN109438843A (en) * | 2018-10-31 | 2019-03-08 | 合肥市丽红塑胶材料有限公司 | A kind of nano-silicon dioxide modified polyacrylic preparation method |
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| CN105482228A (en) * | 2016-01-05 | 2016-04-13 | 广州枫叶管业有限公司 | Polyethylene nano-modified composite and preparing method and application thereof |
| CN106867078A (en) * | 2017-03-06 | 2017-06-20 | 哈尔滨理工大学 | A kind of nano silicon/LDPE Composite and preparation method thereof |
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| CN1944529A (en) * | 2006-10-19 | 2007-04-11 | 上海大学 | Process for preparing biologically degradable SiO2/poly lactic acid nano composite material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129752A (en) * | 2018-01-23 | 2018-06-08 | 苏州聚康新材料科技有限公司 | The preparation method of suspension polymerisation nanometer silicon dioxide composite material |
| CN108948797A (en) * | 2018-07-18 | 2018-12-07 | 武汉金牛经济发展有限公司 | A kind of preparation method of modified manometer silicon dioxide |
| CN109260026A (en) * | 2018-10-04 | 2019-01-25 | 南京航空航天大学溧水仿生产业研究院有限公司 | Silica dental filled composite materials and preparation method thereof |
| CN109438843A (en) * | 2018-10-31 | 2019-03-08 | 合肥市丽红塑胶材料有限公司 | A kind of nano-silicon dioxide modified polyacrylic preparation method |
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Application publication date: 20171226 |