CN1587309A - Process for preparing light degradable nano TiO2 polyethylene composite plastics - Google Patents
Process for preparing light degradable nano TiO2 polyethylene composite plastics Download PDFInfo
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- CN1587309A CN1587309A CN 200410060618 CN200410060618A CN1587309A CN 1587309 A CN1587309 A CN 1587309A CN 200410060618 CN200410060618 CN 200410060618 CN 200410060618 A CN200410060618 A CN 200410060618A CN 1587309 A CN1587309 A CN 1587309A
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Abstract
The present invention relates to the preparation process of light degradable nanometer composite TiO2-polyethylene plastic. The preparation process includes the modification of nanometer TiO2 powder with surface modifier to obtain nanometer modified TiO2 powder; mixing and extruding in double-screw mixing mill nanometer modified TiO2 powder, polyethylene and polyethylene wax to form agglomerate containing TiO2 20-40 wt%, polyethylene 0-20 wt% and polyethylene wax 40-80 wt%; mixing the agglomerate with polyethylene material in double-screw mixing mill to prepare the light degradable nanometer composite TiO2-polyethylene plastic containing TiO2 in 0.5-5 wt%. The present invention has low cost and simple technological process, and the prepared light degradable nanometer composite TiO2-polyethylene plastic may be degraded in the sun to reduce white pollution.
Description
Technical field
The present invention relates to a kind of degradable nano-TiO
2-polyethylene composite plastic particularly relates to a kind of preparation method of efficiency light degradative plastics, belongs to polymkeric substance-field of nanocomposite materials.
Background technology
Polyethylene as a kind of conventional plastics particularly its disposable product purposes is widely arranged.Because polyethylene structure is stable, be difficult to degraded under field conditions (factors).Increasing waste polymer material-white pollution has brought huge pressure for our ecotope, how to handle " white garbage ", is a very urgent problem.The main way that tackles these wastes at present has buried, burns, and reclaims reprocessing or the like, and in fact these ways are not to have brought new environmental problem in treating refuse, allows prestige with its high cost and low excessively return rate exactly and steps back.Such polymer materials is suitably handled, and making it can be that people urgently wish by natural degradation after discarded.
TiO
2Under UV-irradiation, it is right to produce light induced electron-hole, they further with water and oxygen effect, produce hydroxyl free radical and superoxide radical with strong oxidation capacity, its oxidation capacity can kill bacteria and the various organism of degraded.Nano-TiO
2Because its huge specific surface area, small-size effect has than conventional TiO it
2Stronger photocatalytic activity, the present invention utilizes nano-TiO exactly
2This character, be introduced into polystyrene, thereby make it can natural degradation under the effect of sunlight reach the purpose of low-cost degraded waste polystyrene.
Nano-TiO
2It is serious to reunite in low polarizable medium such as organic solvent and plastics, if can not well disperse, with not having the effect of nano material highlight catalytic active, how with TiO
2Evenly introducing polymkeric substance is the key of preparation efficiency light degradation polymer.If not to TiO
2Carry out any processing, directly be introduced into polymkeric substance, cause TiO
2Reunion in polymkeric substance is very serious, greatly reduces TiO
2Photocatalytic degradation efficient, if to TiO
2Carry out surface treatment, it is under the ideal dispersion state, catalytic efficiency will be than surface-treated nano-TiO not
2Improve several times.
We are at first with nano-TiO
2Carry out surface modification, to improve TiO
2The dispersiveness of particle in polymkeric substance, and then itself and polyethylene, Ployethylene Wax is mixing, prepare degradable nano-TiO
2-polyethylene composite plastic.Thereby finished task of the present invention.
Summary of the invention
Problem to be solved by this invention provides a kind of photodegradation nano-TiO
2The preparation method of-polyethylene composite plastic, the photodegradation nano-TiO of this method preparation
2-polyethylene composite plastic can be degraded under the irradiation of sunlight effectively.And manufacturing cost is lower, and technology is simpler, is easy to scale operation.
Technical scheme provided by the invention is a kind of degradable efficiently nano-TiO
2The preparation method of-polyethylene composite plastic is with nano-TiO
2Powder carries out surface modification with surface-modifying agent and obtains modified Nano TiO
2Powder is with modified Nano TiO
2The blend on the twin-screw mixer machine of powder, polyethylene, Ployethylene Wax is extruded and is contained nano-TiO
2Master batch, TiO in the master batch
2Content is 20-40wt%, and polymerized ethylene content is 0-20wt%, and the content of Ployethylene Wax is 40-80wt%, will contain nano-TiO then
2Master batch and the blend of polyethylene raw material, adopt the mixing preparation of twin-screw mixer machine TiO
2Content be the photodegradation nano-TiO of 0.5-5wt%
2The polyethylene composite plastic.
The used nano-TiO of the present invention
2Powder can adopt Detitanium-ore-type or part anatase octahedrite part rutile-type, and particle diameter is 20-200nm.Poly weight-average molecular weight is 80,000-350,000 g/mol, the weight-average molecular weight 1500-5000g/mol of Ployethylene Wax.
Above-mentioned nano-TiO
2The surface modification of powder adopts following step, surface-modifying agent is dissolved in is made into the solution that concentration is 1-3wt% in the organic solvent, mixes with nano-titanium dioxide powder then, is heated to 75-90 ℃, and constant temperature 1-3 hour, the weight of surface-modifying agent was TiO
2The 1-3% of weight.
The used surface-modifying agent of the present invention is a silane coupling agent, titanate coupling agent or clad aluminum titanate coupling agent.Organic solvent is ethanol, acetone or Virahol.
Characteristics of the present invention are the nano-TiO through surface modification and Ployethylene Wax processing
2In polyethylene, have good dispersion, and do not have surface-treated nanoparticle and Ployethylene Wax to handle to compare the contact area that has increased nanoparticle and polymkeric substance, improved the disposal efficiency.Test shows the photodegradation nano-TiO that the similarity condition lower surface is handled
2The disposal efficiency of-polyethylene composite plastic is untreated photodegradation nano-TiO
2The 2-3 of-polyethylene composite plastic the disposal efficiency doubly.
Cost of the present invention is low, and technology is simple, prepared photodegradation nano-TiO
2Effective photodegradation can take place under the situation at solar irradiation through using after discarded in-polyethylene composite plastic, can reduce the influence of white pollution.
Embodiment
Technical process of the present invention is as follows:
1. use silane coupling agent, titanate coupling agent, the clad aluminum titanate coupling agent is to nano-TiO
2Carrying out surperficial oleophylic handles;
2. finish above-mentioned nano-TiO
2After the surface oleophylic is handled, with modified Nano TiO
2The blend on the twin-screw mixer machine of powder, polyethylene, Ployethylene Wax is extruded and is contained nano-TiO
2Master batch, TiO in the master batch
2Content is 20-40wt%, and polymerized ethylene content is 0-20wt%, and the content of Ployethylene Wax is 40-80wt%, will contain TiO then
2Master batch and the blend of polyethylene raw material, adopt the mixing preparation nano-TiO of twin-screw mixer machine
2Content be the TiO of 0.5%-5wt%
2-polyethylene composite plastic.Obtain nano-TiO through the inflation film manufacturing machine blown film
2-polyethylene composite film.
Embodiment 1: with silane coupling agent (the military big organosilicon material company limited trade mark: WD-20) nano-titanium dioxide powder is carried out surface treatment, silane coupling agent may be dissolved in the solution that is made into 2wt% in the acetone, be that the anatase titanium dioxide powder of 25nm mixes with particle diameter then, be heated to 80 ℃, constant temperature 1 hour, the weight of silane coupling agent is TiO
23% of weight.Press TiO
2: polyethylene: Ployethylene Wax is 30: 10: 60 a part by weight, with surface treated TiO
2With polyethylene (weight-average molecular weight 300,000 g/mol, the GPC method is measured) and Ployethylene Wax (weight-average molecular weight 4000g/mol) blend on the twin-screw mixer machine extrude and obtain master batch, then with master batch and polyethylene raw material (weight-average molecular weight 300,000 g/mol, the GPC method is measured) blend, make nano-TiO in the composite plastic
2Content be 2wt%, adopt the mixing nano-TiO that makes of twin-screw mixer machine
2The polyethylene composite plastic prepares degradable nano-TiO through the inflation film manufacturing machine blown film again
2-polyethylene composite film.
Embodiment 2: (dawn chemical plant, Nanjing NDZ-201) carries out surface treatment to nano-titanium dioxide powder with titanate coupling agent, titanate coupling agent may be dissolved in the ethanol, be made into the solution of 3wt%, be that the anatase titanium dioxide powder of 180nm mixes with particle diameter then, be heated to 90 ℃, constant temperature 1 hour, the weight of titanate coupling agent is TiO
21% of weight.Press TiO
2: polyethylene: Ployethylene Wax is 20: 10: 70 a part by weight, with surface treated TiO
2With polyethylene (weight-average molecular weight 90,000 g/mol, the GPC method is measured) and Ployethylene Wax (weight-average molecular weight 2000g/mol, GPC method mensuration) blend is extruded and is obtained master batch on the twin-screw mixer machine, then with master batch and polyethylene raw material (weight-average molecular weight 90,000 g/mol, the GPC method is measured) blend, make nano-TiO in the composite plastic
2Content be 1wt% (weight percent), adopt the mixing nano-TiO that makes of twin-screw mixer machine
2The polyethylene composite plastic prepares degradable nano-TiO through the inflation film manufacturing machine blown film again
2-polyethylene composite film.
Embodiment 3: (OL-AT1618 of Shanxi Province chemical research institute) carries out surface treatment to nano-titanium dioxide powder with aluminium titanic acid ester composite coupler, the aluminium titanate coupling agent may be dissolved in ethanol or the acetone and other organic solvent, be made into the solution of 1wt%, be that the part anatase octahedrite part rutile titanium dioxide powder powder of 80nm mixes with particle diameter then, be heated to 90 ℃, constant temperature 1 hour, the weight of aluminium titanate coupling agent is TiO
22% of weight.Press TiO
2: Ployethylene Wax is 40: 60 a part by weight, with surface treated TiO
2Extrude and obtain master batch with Ployethylene Wax (weight-average molecular weight 5000g/mol, the GPC method is measured) blend on the twin-screw mixer machine, with master batch and polyethylene raw material (weight-average molecular weight 170,000 g/mol, the GPC method is measured) blend, make nano-TiO in the composite plastic then
2Content be 3wt% (weight percent), adopt the mixing nano-TiO that makes of twin-screw mixer machine
2The polyethylene composite plastic prepares degradable nano-TiO through the inflation film manufacturing machine blown film again
2-polyethylene composite film.
Embodiment 4: photodegradation laboratory sample (the photodegradation nano-TiO of embodiment 1 preparation
2-polyethylene composite film) thickness is 30～40 μ m, and it is cut into the square of 5cm * 5cm.Experimental temperature: room temperature, ultraviolet light irradiation degree (wavelength: 254nm): at 3mw/cm
2, behind 240 hours the ultra violet lamp, the rate of weight loss of composite membrane reaches 41%, at 2mw/cm
2, behind 240 hours the ultra violet lamp, the rate of weight loss of composite membrane reaches 25% at 1mw/cm
2, behind 240 hours the ultra violet lamp, the rate of weight loss of composite membrane reaches 13%.At 2mw/cm
2(wavelength: 254nm) behind 275 hours the solar light irradiation, the rate of weight loss of composite membrane reaches 18%.
Embodiment 5: photodegradation laboratory sample (the photodegradation nano-TiO of embodiment 2 preparations
2-polyethylene composite film) thickness is 30～40 μ m, and it is cut into the square of 5cm * 5cm.Experimental temperature: room temperature, ultraviolet light irradiation degree (wavelength: 254nm): at 3mw/cm
2, behind 240 hours the ultra violet lamp, the rate of weight loss of composite membrane reaches 59%, at 2mw/cm
2, behind 240 hours the ultra violet lamp, the rate of weight loss of composite membrane reaches 40% at 1mw/cm
2, behind 240 hours the ultra violet lamp, the rate of weight loss of composite membrane reaches 25%.At 2mw/cm
2(wavelength: 254nm) behind 275 hours the solar light irradiation, the rate of weight loss of composite membrane reaches 26%.
Embodiment 6: photodegradation laboratory sample (the photodegradation nano-TiO of embodiment 3 preparations
2-polyethylene composite film) thickness is 30～40 μ m, and it is cut into the square of 5cm * 5cm.Experimental temperature: room temperature, ultraviolet light irradiation degree (wavelength: 254nm): at 3mw/cm
2, behind 240 hours the ultra violet lamp, the rate of weight loss of composite membrane reaches 65%, at 2mw/cm
2(wavelength: 254nm) behind 275 hours the solar light irradiation, the rate of weight loss of composite plastic reaches 29%.
With reference to aforesaid method, can obtain similar result with the polyethylene of other weight-average molecular weight and the polyethylene in the Ployethylene Wax alternate embodiment and Ployethylene Wax.
Claims (6)
1. photodegradation nano-TiO
2The preparation method of-polyethylene composite plastic is characterized in that: with nano-TiO
2Powder carries out surface modification with surface-modifying agent and obtains modified Nano TiO
2Powder is with modified Nano TiO
2The blend on the twin-screw mixer machine of powder, polyethylene, Ployethylene Wax is extruded and is contained nano-TiO
2Master batch, TiO in the master batch
2Content is 20-40wt%, and polymerized ethylene content is 0-20wt%, and the content of Ployethylene Wax is 40-80wt%, will contain nano-TiO then
2Master batch and the blend of polyethylene raw material, adopt the mixing preparation of twin-screw mixer machine TiO
2Content be the photodegradation nano-TiO of 0.5-5wt%
2The polyethylene composite plastic.
2. preparation method according to claim 1 is characterized in that: poly weight-average molecular weight is 80,000-350,000 g/mol, the weight-average molecular weight 1500-5000g/mol of Ployethylene Wax.
3. preparation method according to claim 1 and 2 is characterized in that: nano-TiO
2Powder is Detitanium-ore-type or part anatase octahedrite part rutile-type, and particle diameter is 20-200nm.
4. preparation method according to claim 1 and 2 is characterized in that: nano-TiO
2The surface modification of powder adopts following step, surface-modifying agent is dissolved in is made into the solution that concentration is 1-3wt% in the organic solvent, mixes with nano-titanium dioxide powder then, is heated to 75-90 ℃, and constant temperature 1-3 hour, the weight of surface-modifying agent was TiO
2The 1-3% of weight.
5. preparation method according to claim 4 is characterized in that: surface-modifying agent is a silane coupling agent, titanate coupling agent or clad aluminum titanate coupling agent.
6. preparation method according to claim 4 is characterized in that: organic solvent is ethanol, acetone or Virahol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410060618 CN1284823C (en) | 2004-07-23 | 2004-07-23 | Process for preparing light degradable nano TiO2 polyethylene composite plastics |
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|---|---|---|---|
| CN 200410060618 CN1284823C (en) | 2004-07-23 | 2004-07-23 | Process for preparing light degradable nano TiO2 polyethylene composite plastics |
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| CN1587309A true CN1587309A (en) | 2005-03-02 |
| CN1284823C CN1284823C (en) | 2006-11-15 |
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| CN 200410060618 Expired - Fee Related CN1284823C (en) | 2004-07-23 | 2004-07-23 | Process for preparing light degradable nano TiO2 polyethylene composite plastics |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891972A (en) * | 2010-07-16 | 2010-11-24 | 河北惠尔信新材料有限公司 | Method for producing chemical fiber titanium dioxide by surface coating of common titanium dioxide (TiO2) in solvent phase |
| CN101921422A (en) * | 2010-07-30 | 2010-12-22 | 王丽红 | Ecologically degradable plastic garbage bags |
| CN106589542A (en) * | 2016-12-08 | 2017-04-26 | 苏州纳贝通环境科技有限公司 | Environmentally-friendly fireproof buffering package material and preparation method thereof |
| CN107200907A (en) * | 2017-06-20 | 2017-09-26 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of ageing-resistant Polyethylene Nanocomposites |
-
2004
- 2004-07-23 CN CN 200410060618 patent/CN1284823C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891972A (en) * | 2010-07-16 | 2010-11-24 | 河北惠尔信新材料有限公司 | Method for producing chemical fiber titanium dioxide by surface coating of common titanium dioxide (TiO2) in solvent phase |
| CN101891972B (en) * | 2010-07-16 | 2013-04-24 | 河北惠尔信新材料有限公司 | Method for producing chemical fiber titanium dioxide by surface coating of common titanium dioxide (TiO2) in solvent phase |
| CN101921422A (en) * | 2010-07-30 | 2010-12-22 | 王丽红 | Ecologically degradable plastic garbage bags |
| CN101921422B (en) * | 2010-07-30 | 2012-09-19 | 王丽红 | Ecologically degradable plastic garbage bags |
| CN106589542A (en) * | 2016-12-08 | 2017-04-26 | 苏州纳贝通环境科技有限公司 | Environmentally-friendly fireproof buffering package material and preparation method thereof |
| CN107200907A (en) * | 2017-06-20 | 2017-09-26 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of ageing-resistant Polyethylene Nanocomposites |
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| Publication number | Publication date |
|---|---|
| CN1284823C (en) | 2006-11-15 |
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Granted publication date: 20061115 Termination date: 20100723 |