CN1597756A - Composite of polyolefine/Ca Co3 and preparation process thereof - Google Patents
Composite of polyolefine/Ca Co3 and preparation process thereof Download PDFInfo
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- CN1597756A CN1597756A CN 03156982 CN03156982A CN1597756A CN 1597756 A CN1597756 A CN 1597756A CN 03156982 CN03156982 CN 03156982 CN 03156982 A CN03156982 A CN 03156982A CN 1597756 A CN1597756 A CN 1597756A
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Abstract
The invention relates to a polyolefin/CaCO3 composite and its preparing method, taking powder polytene or polypropylene synthesized directly by synthetic tower as the principal resin to mix with activated CaCO3, functional assistant and processing aid, then extruding their mixture to granulate. For different properties of powder polyolefin, CaCO3 contents, CaCO3 surface activating methods and functional assistants, it can prepare a series of polyolefin/CaCO3 composites with different properties and uses. As the current polyolefin/CaCO3 composite, it has simple process and low cost, and on the condition of the same CaCO3 content, its synthetic mechanical property can be increased by 10-15% and its cost can be reduced by 20-30%.
Description
Technical field
The present invention relates to a kind of polyolefine/CaCO
3Matrix material and preparation method thereof is with directly from synthetic tower the come out polyolefine powder of undressed processing and the active CaCO of special methods processing specifically
3After the mixing, under the effect of functional agent and processing aid, polyolefine/CaCO that single stage method is produced
3Matrix material.According to the matrix resin of used different sorts, different performance, the active CaCO that different methods is handled
3With use different functional agents, can produce and have different performance, be fit to multi-purpose serial polyolefine/CaCO
3Matrix material is the polyolefine/CaCO that produces that a kind of technology is simple, cost is low, composite property is good
3Composite process.
Background technology
When petrochemical industry department produced polypropylene and low pressure polyethylene, what come out from synthetic tower all was meal, needs to add some functional agent (PP need add oxidation inhibitor) before dispatching from the factory and carries out granulation, supplies with the user with the form of pellet.Plastic industry for the use properties or the processability that improve goods or reduce cost, usually needs that material resin is carried out modification and handles when producing most goods, and it is with resin and CaCO that the most frequently used way is handled in modification at present
3The compound matrix material of making.Polyolefin resin is pellet and CaCO
3Be powder, the two compound polyolefine powder and CaCO of being far from
3The powder compound is effective.Adopt way of the present invention can save petrochemical industry department granulating working procedure on the one hand, save the energy, can improve the over-all properties of matrix material on the other hand, because any polyolefin resin is through melt extruding granulation, because the shearing action of screw rod will make the mechanical property of resin reduce, wherein polypropylene reduces by 15% at most, and polyethylene reduces about 10%, so adopt the inventive method to prepare polyolefine/CaCO
3Matrix material, technology is simple, cost is low, composite property is good, is preparation polyolefine/CaCO
3Matrix material opens up a new way, and to the development of plastic industry, will make significant contribution to the quality improvement of plastics.
Summary of the invention
The present invention relates to a kind of polyolefine/CaCO
3Matrix material, comprise polyolefine powder and once or the lime carbonate handled of secondary coating method, by the weight of the two, wherein polyolefine powder accounts for 40-88wt%, lime carbonate accounts for 12-60wt%, also contain in addition based on the functional agent of the 0-6wt% of polyolefine powder and lime carbonate gross weight with based on the processing aid of the 2-8wt% of polyolefine powder and lime carbonate gross weight.Wherein a coating method comprises the coupling agent treatment lime carbonate of using based on the 0.5-3wt% of weight of calcium carbonate, secondary coating method comprises the lime carbonate reactive compounds that contains epoxy group(ing) or hydroxyl with a coating method processing, especially the fatty acid ester that contains epoxy group(ing) or hydroxyl is handled, it is to carry out in the Centrifugal vibration mill that a coating method is handled, each time processing that secondary coating method is handled can be carried out in homogenizer or Centrifugal vibration mill, preferably carry out in the Centrifugal vibration mill, wherein polyolefine powder is preferably the powder without processing treatment that directly is synthesized by synthetic tower.
Another object of the present invention provides preparation polyolefine/CaCO
3The method of matrix material comprises polyolefine powder and coating or the active CaCO of secondary coating
3, directly send the twin screw extruder extruding pelletization after processing aid and optional functional agent mix in height stirs machine or mixer.Different performance be can prepare and different purposes degradables or nondegradable PP/CaCO are fit to
3Matrix material and PE/CaCO
3Matrix material.Wherein PP is a polypropylene, and PE is a polyethylene.
Wherein matrix resin be preferably by synthetic tower directly be synthesized without the powdered polypropylene of processing treatment and low pressure polyethylene etc.The melt flow rate (MFR) of polypropylene powder is that (230 ℃, 2.16kg), apparent density is 0.38-0.43g/cm to 0.5-50g/10min
3, isotactic index 〉=96%.The melt flow rate (MFR) of low pressure polyethylene powder is that (190 ℃, 2.16kg), apparent density is 0.4-0.55g/cm to 0.1-40g/10min
3Polyolefine content is 40-88wt%, by polyolefine+lime carbonate=100wt%.
CaCO wherein
3Component is preferably 800 orders-2250 order (19um-7um) heavy CaCO
3Or 325 order-1250 order (47um-12um) lightweight CaCO
3Heavy CaCO
3With lightweight CaCO
3In CaCO
3Content 〉=98wt%, hydrochloric acid is fusant≤0.10wt% not, the content≤0.10wt% of iron.CaCO in the matrix material
3Content is 12-60wt%, by polyolefine+lime carbonate=100wt%.
CaCO wherein
3Surface activating process divides two kinds of single coating activation treatment and double-contracting film activation treatment.The coating agent that single coating method is used is a kind of or two or more compound in the coupling agents such as stearic acid, stearate, aluminic acid ester, titanic acid ester, acid phosphorous acid ester, and its consumption is CaCO
3The 0.5-3wt% of weight.A coating method activation treatment is to carry out in the Centrifugal vibration mill, and each time of secondary coating method activatory processing is at stirrer (preferred homogenizer, preferred 100-5000 rev/min) or Centrifugal vibration mill, carries out in the preferred vibration mill.Utilize magnetic ball or the strong centrifugal shearing force of Stainless Steel Ball in the vibration mill, CaCO
3Particle surface can produce big activation energy, makes the coating agent be coated on CaCO equably
3Particle surface.The double-contracting embrane method be on the basis of single coating, adopt can with the activator of coating agent generation chemical reaction in single coating, stir in the machine CaCO at Centrifugal vibration mill or height
3Carrying out the secondary coating handles.Activator is the material that has certain reactive behavior and polyolefin resin is had strong avidity again, they for example are selected from a kind of or two or more compound in butyl epoxy stearate, Stearinsaeure epoxy glyceride, epoxy soybean oil, mono laurate glycol ether ester, the epoxidized methyl acetorieinoleate, and its consumption is CaCO
3The 0.5-5wt% of weight.
Wherein functional agent is oxidation inhibitor, photostabilizer and photosensitizers.Oxidation inhibitor, photostabilizer are mainly used in PP/CaCO
3In the matrix material, prevent the PP oxygenolysis, they are any one or two kinds or multiple compound in Hinered phenols, hindered amines, phosphorous acid esters, benzoates and the benzophenone, consumption is the 0-6wt% of PP weight, as not adding or add less antioxidant and photostabilizer, the matrix material of preparation has degradation function.Photosensitizers is mainly used in the PE/CaCO that preparation has degradation function
3Matrix material, they for example are: a kind of or two kinds or multiple compound in transition metal complex, organo-peroxide, N-halogenated polyimide and the condensed-nuclei aromatics derivative, consumption is the 0.5-2wt% of PE weight.Processing aid wherein for example is lubricant and dispersion agent, and they are a kind of or two or more mixtures in Microcrystalline Wax, Poly Propylene Wax, polyethylene wax, whiteruss and the Magnesium Stearate.Consumption is the 2-8wt% of polyolefine+lime carbonate gross weight, preferred 2-5wt%.
Polyolefine/CaCO wherein
3Matrix material pellet preparation method is: with coating or the active CaCO of secondary coating
3, polyolefine powder, functional agent and processing aid cooperate by a certain percentage, stir at mixer or height and send the twin screw extruder extruding pelletization promptly to get polyolefine/CaCO after mixing under the normal temperature in the machine
3The matrix material pellet.According to used resin kind, performance, CaCO
3Coating number of times and content, functional agent are different, can prepare the PP/CaCO that is fit to different purposes
3, PE/CaCO
3A series of matrix materials.
The present invention prepares polyolefine/CaCO forefathers
3On the experiential basis of matrix material, under inorganic particulate strengthening and toughening theory and inorganic particulate surface active guide of theory, to preparation polyolefine/CaCO
3Composite process is fundamentally improved.Matrix resin makes powder into by the pellet in past, and cost is low, and easy and CaCO
3Powder mixes by arbitrary proportion, avoids resin to bring the reduction of mechanical property because of granulation.The CaCO that the present invention is used
3Be general heavy CaCO
3With lightweight CaCO
3CaCO
3Surface activating process is an innovation part of the present invention, is that any patent and document are unexistent.Adopt the Centrifugal vibration mill to CaCO
3The surface activates coating.Utilize Centrifugal vibration mill functions peculiar to make CaCO
3Magnetic ball or Stainless Steel Ball height are cut and are cut under the centrifugal action in mill, and the surface is activated, and the coating agent is coated on CaCO equably with the form of molecular film
3Particle surface, clad ratio can reach more than 90%, and this is present any processing CaCO
3Activation method can't be realized.Adopt coating method can make the polyolefine/CaCO of excellent property
3Matrix material.The secondary coating is mainly used in the shock proof polyolefine/CaCO of preparation good toughness
3Matrix material is at same CaCO
3(CaCO under the situation of content
3Content 40-50wt%), shock strength secondary coating can improve 50% than a coating.This be because the used activator of secondary coating at CaCO
3Can form one between particle and the molecular resin chain and have certain elasticity zone of transition, can cushion or disperse the internal stress that is produced because of the external force effect.Adopting double-contracting membrane technique and the used activator of secondary coating is present CaCO
3Surface activating process is unexistent.
Coating and secondary coating preferably at the Centrifugal vibration mill-5 ℃ to 30 ℃ or higher temperature, for example 30-60 ℃, carry out under the preferred normal temperature, a coating is 3-10min, about preferred 5min, about secondary coating 5-10min, for example can select 600-1200 rev/min rotating speed, the Centrifugal vibration mill for example can be buied from the Beijing Youhepanbao Technology and Development Co., Ltd.
The used functional agent of the present invention has two classes: a class is employed at the unstable easy oxygenolysis of acrylic resin.They are: any one in Hinered phenols, hindered amines, phosphorous acid esters, benzoates and the benzophenone, its consumption is the 0-6wt% of PP weight, as uses no or little, and can prepare the PP/CaCO with degradation function
3Matrix material; Another kind of is to be used for preparing the PE/CaCO with degradation function
3The employed photosensitizers of matrix material.They are: a kind of or two kinds of compounds in transition metal complex, organo-peroxide, N-halogenated polyimide and the condensed-nuclei aromatics derivative, consumption is the 0.5-2wt% of PE weight.
The used processing aid of the present invention is general lubricant and dispersion agent, and they are a kind of in Microcrystalline Wax, Poly Propylene Wax, polyethylene wax, whiteruss and the Magnesium Stearate or mixture more than two kinds and two kinds.Consumption is the 2-8wt% of matrix material gross weight, preferred 2-5wt%.
Polyolefine/CaCO of the present invention
3The preparation of matrix material pellet is to adopt plastics-production general-purpose equipment twin screw extruder, height to stir machine or mixer.Coating of the PP, PE powder that adopts different performance and different amounts or secondary coating activity CaCO
3, add or do not add a certain amount of functional agent, add a certain amount of processing aid again, directly send the twin screw extruder extruding pelletization after in height stirs machine or mixer, mixing, different performance be can prepare and different purposes degradables or nondegradable PP/CaCO are fit to
3Matrix material and PE/CaCO
3Matrix material.The comprehensive mechanical property of matrix material and present used preparation PP/CaCO
3, PE/CaCO
3Composite process is compared, at CaCO
3Under the content same case, can improve 10-15%, cost can reduce 20-30%.
Embodiment
Further specify the present invention by the following examples.It is pointed out that these embodiment only are the preferred example of finding, do not constitute any restriction of the scope of the invention in enforcement of the present invention.
1, CaCO
3Surface activation process
Take by weighing 100kg 800 orders or 1250 order heavy CaCO
3Or lightweight CaCO
3Add the 2.5kg stearic acid, behind the high-speed mixing 5min, continuously join in the Centrifugal vibration mill in mixer, feed rate is controlled at CaCO
3Batch mixing residence time in vibration mill is 5-6min, grinds a mouthful CaCO who discharges from Centrifugal vibration
3Be once the active CaCO of coating
3
With an above-mentioned coating CaCO who makes
3Behind the high-speed mixing 5min, carry out the secondary coating with same the operating in of an above-mentioned coating in the Centrifugal vibration mill and just can obtain double-contracting film activity CaCO in mixer with 2kg butyl epoxy stearate and 1.5kg epoxy soybean oil
3
2, the polyolefine/CaCO of different performance and purposes
3Composite Preparation:
Embodiment 1. Polywoven Bag PP/CaCO
3Matrix material
Taking by weighing the 65kg melt flow rate (MFR) is 2g/10min, the PP powder of isotactic index 〉=96% and 1.5kg antioxidant 264,1.5kg whiteruss, 2kg Poly Propylene Wax and coating of 30kg 800 order lightweight CaCO
3In height stirs machine under the room temperature behind the high-speed stirring 5min, with length-to-diameter ratio 1: 32,75 type twin screw extruder extruding pelletizations.With the woven bag plastic flat fiber that this pellet is drawn into, press SG213-80 GB test result, can reach the one-level technical indicator.
Embodiment 2. injection stage PP/CaCO
3Matrix material
Taking by weighing the 55kg melt flow rate (MFR) is 12g/10min, the PP powder of isotactic index 〉=96% and 2kg oxidation inhibitor 246,1kg Microcrystalline Wax, 2.5kg Poly Propylene Wax and 39.5kg double-contracting film 1250 order heavy CaCO
3In height stirs machine under the room temperature behind the high-speed stirring 5min, with length-to-diameter ratio 1: 32,75 type twin screw extruder extruding pelletizations.The pure PP resin of the notched Izod impact strength of this matrix material and bending strength ratio improves 28% and 24% respectively.
Embodiment 3. food and drink tools degradable PP/CaCO
3Matrix material
Taking by weighing the 45kg melt flow rate (MFR) is 4g/10min, the PP powder of isotactic index 〉=96% and 1kg Microcrystalline Wax, 2kg polyethylene wax and coating of 52kg 800 order heavy CaCO
3In height stirs machine under the room temperature behind the high-speed stirring 5min, with length-to-diameter ratio 1: 36,72 type twin screw extruder extruding pelletizations.Make mess-tin, beverage cup and supermarket pallet with this pellet pulling-on piece, plastic uptake, can satisfy the use properties requirement, with after be discarded under the sun, be degradable in 2-3 month.
Embodiment 4. blown film PE/CaCO
3Degradable composite material
Taking by weighing the 66kg melt flow rate (MFR) is low pressure polyethylene powder and 1kg whiteruss, 2kg polyethylene wax, 1kg dibutyl dithiocaarbamate iron and coating of the 30kg 1250 order heavy CaCO of 6g/10min
3In height stirs machine under the room temperature behind the high-speed stirring 5min, with length-to-diameter ratio 1: 36,72 type twin screw extruder extruding pelletizations.Can make various plastics bags of packaging and refuse bag with this pellet blown film, the plastics bag that makes can meet or exceed GB/T2461-1999 (packaging degrading polyethylene film) technological standard.
Embodiment 5. injection PE/CaCO
3Matrix material
Taking by weighing the 58kg melt flow rate (MFR) is low pressure polyethylene powder and the active heavy CaCO of 1kg Microcrystalline Wax, 2kg polyethylene wax and 39kg double-contracting film 1250 orders of 6g/10min
3In height stirs machine under the room temperature behind the high-speed stirring 5min, with length-to-diameter ratio 1: 32,75 type twin screw extruder extruding pelletizations.Use pallet with these pellet injection loading and unloading, the capability and performance test result can reach country-level technological standard.
Claims (10)
1, a kind of polyolefine/CaCO
3Matrix material, this matrix material contains polyolefine powder and once or the lime carbonate handled of secondary coating method, by the two gross weight, polyolefine powder accounts for 40-88wt%, lime carbonate accounts for 12-60wt%, also contain based on the functional agent of the 0-6wt% of polyolefine powder and lime carbonate gross weight with based on the processing aid of the 2-8wt% of polyolefine powder and lime carbonate gross weight.
2, according to the polyolefine/CaCO of claim 1
3Matrix material, wherein a coating method comprises the coupling agent treatment lime carbonate of using based on the 0.5-3wt% of weight of calcium carbonate, secondary coating method comprises the reactive compounds that contain epoxy group(ing) or hydroxyl of the lime carbonate that coating method is handled based on the 0.5-5wt% of weight of calcium carbonate, and the fatty acid ester that especially contains epoxy group(ing) or hydroxyl is handled.
3, according to the polyolefine/CaCO of claim 1
3Matrix material, wherein a coating method processing is to carry out in the Centrifugal vibration mill, each time processing that secondary coating method is handled is at homogenizer or Centrifugal vibration mill, especially carries out in the Centrifugal vibration mill.
4, according to the polyolefine/CaCO of claim 1
3Matrix material, wherein the powder without processing treatment of polyolefine powder for directly being synthesized, especially polypropylene or polyethylene by synthetic tower.
5, according to the polyolefine/CaCO of claim 1
3Matrix material, wherein CaCO
3Component is 800 orders-2250 order (19um-7um) heavy CaCO
3Or 325 order-1250 order (47um-12um) lightweight CaCO
3
6, according to the polyolefine/CaCO of claim 1
3Matrix material, wherein coupling agent is selected from a kind of in stearic acid, stearate, aluminic acid ester, titanic acid ester, the acid phosphorous acid ester or compound more than two kinds and two kinds, and its consumption is CaCO
3The 0.5-3wt% of weight.
7, according to the polyolefine/CaCO of claim 1
3Matrix material, the reactive compounds that wherein contains epoxy group(ing) or hydroxyl is selected from a kind of or two or more compound in butyl epoxy stearate, Stearinsaeure epoxy glyceride, epoxy soybean oil, mono laurate glycol ether ester, the epoxidized methyl acetorieinoleate, and its consumption is CaCO
3The 0.5-5wt% of weight.
8, according to the polyolefine/CaCO of claim 1
3Matrix material, wherein functional agent is selected from oxidation inhibitor, photostabilizer and photosensitizers.
9, according to the polyolefine/CaCO of claim 1
3Matrix material, wherein processing aid is selected from a kind of or two or more mixture in Microcrystalline Wax, Poly Propylene Wax, polyethylene wax, whiteruss and the Magnesium Stearate
10, preparation polyolefine/CaCO
3The method of matrix material comprises polyolefine powder and coating or the active CaCO of secondary coating
3, directly send the twin screw extruder extruding pelletization after processing aid and optional functional agent mix in height stirs machine or mixer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156982 CN1260285C (en) | 2003-09-17 | 2003-09-17 | Composite of polyolefine/Ca Co3 and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156982 CN1260285C (en) | 2003-09-17 | 2003-09-17 | Composite of polyolefine/Ca Co3 and preparation process thereof |
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| Publication Number | Publication Date |
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| CN1597756A true CN1597756A (en) | 2005-03-23 |
| CN1260285C CN1260285C (en) | 2006-06-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03156982 Expired - Fee Related CN1260285C (en) | 2003-09-17 | 2003-09-17 | Composite of polyolefine/Ca Co3 and preparation process thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100451056C (en) * | 2006-03-28 | 2009-01-14 | 华南理工大学 | Process for preparing predispersed masterbatch of polyolefin and nano calcium carbonate |
| CN101845172A (en) * | 2010-05-21 | 2010-09-29 | 葛立武 | Polypropylene high-filled toughening masterbatch and preparation method thereof |
| CN113366049A (en) * | 2019-02-11 | 2021-09-07 | 欧米亚国际集团 | Surface treated filler material products providing improved UV stability to polymeric articles |
-
2003
- 2003-09-17 CN CN 03156982 patent/CN1260285C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100451056C (en) * | 2006-03-28 | 2009-01-14 | 华南理工大学 | Process for preparing predispersed masterbatch of polyolefin and nano calcium carbonate |
| CN101845172A (en) * | 2010-05-21 | 2010-09-29 | 葛立武 | Polypropylene high-filled toughening masterbatch and preparation method thereof |
| CN101845172B (en) * | 2010-05-21 | 2013-01-16 | 葛立武 | Polypropylene high-filled toughening masterbatch and preparation method thereof |
| CN113366049A (en) * | 2019-02-11 | 2021-09-07 | 欧米亚国际集团 | Surface treated filler material products providing improved UV stability to polymeric articles |
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| Publication number | Publication date |
|---|---|
| CN1260285C (en) | 2006-06-21 |
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