CN103421239A - Preparation method of recycled polypropylene/leather powder compound - Google Patents
Preparation method of recycled polypropylene/leather powder compound Download PDFInfo
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- CN103421239A CN103421239A CN2013102022994A CN201310202299A CN103421239A CN 103421239 A CN103421239 A CN 103421239A CN 2013102022994 A CN2013102022994 A CN 2013102022994A CN 201310202299 A CN201310202299 A CN 201310202299A CN 103421239 A CN103421239 A CN 103421239A
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Abstract
The invention discloses a preparation method of a recycled polypropylene/leather powder compound, and belongs to the field of natural high-molecular modified polymer materials. The compound is composed of leather powder, recycled polypropylene, a compatibilizer and an initiator, wherein the amounts of the added compatibilizer and the initiator are respectively 5%-20% and 0.8%-1.8% of the weight of the recycled polypropylene; the weight ratio of the leather powder to the recycled polypropylene is (1:20) to (1:1); the raw materials are simultaneously added into a high-speed mixer to be subjected to blending, then the uniformly mixed materials are added into an internal mixer to be subjected to internal mixing, and then the discharging of the materials is performed instantly so as to obtain the recycled polypropylene/hide powder compound. The preparation of the recycled polypropylene/hide powder compound provided by the invention can be realized in the internal mixer by one step, so that the problem that the compatibility of the hide powder and the recycled polypropylene is difficult to realize is solved; the preparation technology is simple and easy to operate; the recycled polypropylene/leather powder compound is suitable for large-scale industrial production, and can realize resource utilization of waste materials.
Description
Technical field
The invention belongs to natural macromolecule modification polymer materials field, particularly relate to a kind of preparation method who reclaims polypropylene/skin flour complexes.
Background technology
Polypropylene is cheap has good processing, physics and chemistry performance simultaneously, be widely used in the every field of national economy, but the following annual waste and old polypropylene produced is also more and more, how to reclaim and to utilize these waste and old polypropylenes to become increasingly serious environment and social concern.The comprehensive utilization of waste and old polypropylene at present comprises regeneration, pyrolysis recycling and burning, and regeneration is divided into again simple regeneration utilization and modification regeneration utilization.The simple regeneration utilization is that the plastics of recovery are reprocessed to moulding after classification, cleaning, fragmentation, granulation.The technique of this class regeneration is simpler, and the regeneration product properties is not good enough, generally can only do plastics that class is lower such as plastic beer case, plastics fence etc.The modification regeneration utilization is after reworked material is passed through to physics or chemical process modification, the reprocessing moulding, such as preparation reclaim polypropylene/wood powder composite material (Nie Hengkai. reclaim the polypropylene/wood powder composite material performance study. the engineering plastics application, 2010, 38 (5): 25-27), preparation recovery polypropylene/useless book paper fibre composite (Zhang Xiaolin. reclaim the research of polypropylene/useless book paper fiber composite structure and mechanical property. Chinese Plastics, 2012, 26 (4): 102-105), reprocessed plastic(s) after modification, mechanical property improves or improves, can be used for making the plastics that class is higher, application prospect is larger.And pyrolysis recycling and burning utilization are reclaimed in polypropylene process and can be had greater environmental impacts by the generation toxic and harmful, application is restricted.China is process hides big country in addition, annual produces a large amount of leather castoffs, and leather castoff is mainly raw hide deburring corner material, the grey skin graft compositions such as bits and blue skin shaving, deburring of peeling.Approximately contain the collagen protein more than 80% in Leather Solid Waste, the non-protein ingredient that also contains in addition a small amount of Keratin sulfate and sphaeroprotein and trace, wherein leather castoff the most directly being utilized is grinding and processing cutification powder, prepare corresponding skin powder/plastic composite materials or skin powder/rubber composite as main additive, this technique can realize the high-value-use to leather castoff, can not produce secondary pollution, such as Shao Shuanxi etc. utilize increasing reaction to prepare the polyethylene of consistency/skin powder blend (Shao Shuanxi. a kind of preparation method .ZL201010542094.7 of compatible hide powder/polyethylene mixture), Japanese Patent (the flat 3-162500A of TOHKEMY) discloses the leather powder that has added particle diameter to be not more than 250 microns in polyvinyl resin and has prepared leather powder/polyethylene blend as filler, the method is physical blending, the skin powder is directly to add blend, the mechanical property of prepared blend is poor, the interpolation of skin powder is mainly for having improved the water absorbing properties of intermingling material.Up to the present, directly with the polypropene blended research of recovery, have no bibliographical information about leather castoff or skin powder, the components such as softening agent, stopping composition, stiffening agent, stablizer have also been comprised mainly due to reclaiming polypropylene, the consistency that reclaims polypropylene and skin powder is poor, therefore for the mixture of the recovery polypropylene for preparing good mechanical properties/skin powder, the present invention introduces novel expanding material water-soluble chitosan graft polypropylene or water-soluble chitosan grafted polyethylene, improves polypropylene and the poor problem of skin powder consistency of reclaiming.Reclaim the mixture of polypropylene/skin powder by preparation and can realize the recycling to waste.
Summary of the invention
For the better problem of utilizing that reclaims polypropylene and leather castoff that solves, the object of the present invention is to provide a kind of to reclaiming the method for polypropylene and leather castoff high-value-use, thereby the mixture of the good recovery polypropylene of processability/skin powder.
Another object of the present invention is to provide a kind of preparation technology simply and easy handling, thereby the preparation method of the mixture of the recovery of applicable large-scale industrial production polypropylene/skin powder.
In order to achieve the above object, recovery polypropylene provided by the invention/skin flour complexes by the skin powder, reclaim polypropylene, expanding material and initiator and form; Wherein the addition of expanding material and initiator is respectively and reclaims 5%～20% and 0.8%～1.8% of polypropylene weight; Skin powder and the polyacrylic weight ratio of recovery are 1: 20～1: 1.
It is directly to carry out after drying the superfine grinding gained by the grey skin graft of the cattle and sheep leather waste produced of peeling after bits and blue skin shaving, deburring that described skin powder is stated, and the particle diameter of skin powder is controlled between 20～100 orders.
Described recovery polypropylene is mainly from a large amount of polypropylene bottle Turnover Boxes that use on market, and is required to meet and reclaims polypropylene tensile strength >=10Mpa, elongation at break >=10%, polyacrylic weight content >=50%.
Described expanding material is selected from one or both of water-soluble chitosan graft polypropylene, water-soluble chitosan grafted polyethylene.
Described initiator is selected from one or both of benzoyl peroxide, dicumyl peroxide.
The recovery polypropylene provided by the invention/preparation method of skin flour complexes carries out according to the following step order:
(1) add the deionized water of 300mL in 1 liter of autoclave, the water-soluble chitosan of the modification of 30g, the propylene of 100g or ethene, add the oil soluble polyvinyl alcohol of 1g Vltra tears and 1g as dispersion agent, 0.5g two-(2-second hexyl)-peroxy dicarbonate as initiator, at 70 ℃ of lower stirring reaction 5h, filter and obtain water-soluble chitosan graft polypropylene powder or water-soluble chitosan grafted polyethylene powder.
(2) will join together with initiator in high-speed mixer and carry out blend according to the skin powder after above-mentioned ratio weighing, recovery polypropylene, expanding material, or first initiator is joined can be by the volatile organic solvent of its dissolving, then be added to the high speed blender together with recovery polypropylene, skin powder and additive and mixed, until organic solvent volatilizees fully;
(3) material of above-mentioned mixing is joined in small-sized internal mixer, and banburying 20～45min can obtain the mixture of recovery polypropylene/skin powder under the rotating speed of the banburying temperature of 170～190 ℃ and 10～30r/min.
Described volatile organic solvent is acetone, dehydrated alcohol or their mixture.
The mixture desired raw material of recovery polypropylene provided by the invention/skin powder is simple, wherein the skin powder is directly to pulverize preparation by leather castoff, and leather castoff is generally directly to be provided free by leather-making enterprises, thereby can the decrease manufacturing cost, contain the collagen protein more than 80% in the skin powder in addition, interaction by expanding material and initiator, improve the skin powder and reclaim polyacrylic compatibility problem, the mixture of prepared recovery polypropylene/skin powder has higher tensile strength and certain elongation at break.
Embodiment:
Following examples are to further instruction of the present invention, but do not limit the scope of the invention.
Embodiment 1
Accurately take and reclaim polypropylene 100 weight parts, skin powder 10 weight parts, water-soluble chitosan graft polypropylene 10 weight parts, dicumyl peroxide (DCP) 1.2 weight parts, then above-mentioned raw materials is joined in high-speed mixer simultaneously and carries out blend, afterwards the material mixed is joined to the Banbury mixer banburying, first 170 ℃ of lower banburyings 5 minutes, rotating speed 10r/min, moment of torsion 48～56Nm, then be warmed up to 190 ℃ of banburyings 15 minutes again, rotating speed 30r/min, moment of torsion 38～44Nm, discharging while hot, can obtain the mixture of recovery polypropylene/skin powder, its mechanical property is respectively tensile strength 28.8Mpa, elongation at break 35.5%.The melting peak temperature that Differential scanning calorimetry obtains intermingling material is 162.8 ℃.
Embodiment 2
Accurately take polyethylene 100 weight parts, skin powder 20 weight parts, water-soluble chitosan graft polypropylene 10 weight parts, water-soluble chitosan grafted polyethylene 10 weight parts, benzoyl peroxide 1.2 weight parts, at first benzoyl peroxide is joined in appropriate acetone and make its dissolving, then with the skin powder, reclaim polypropylene, polypropylene grafted maleic anhydride joins high-speed mixer and carries out blend together with EAA, after acetone volatilizees fully, the mixture material is joined to the Banbury mixer banburying, first 170 ℃ of lower banburyings 5 minutes, rotating speed 10r/min, moment of torsion 44～49Nm, then be warmed up to 190 ℃ of banburyings 15 minutes again, rotating speed 30r/min, moment of torsion 32～36Nm, discharging while hot, can obtain the mixture of recovery polypropylene/skin powder, its mechanical property is respectively tensile strength 25.4Mpa, elongation at break 28.7%.The melting peak temperature that Differential scanning calorimetry obtains intermingling material is 160.9 ℃.
Embodiment 3
Accurately take polyethylene 100 weight parts, skin powder 50 weight parts, water-soluble chitosan graft polypropylene 20 weight parts, dicumyl peroxide (DCP) 1.2 weight parts, at first dicumyl peroxide is joined in appropriate ethanol and make its dissolving, then above-mentioned raw materials is joined in high-speed mixer simultaneously and carries out blend, afterwards the material mixed is joined to the Banbury mixer banburying, first 170 ℃ of lower banburyings 10 minutes, rotating speed 10r/min, moment of torsion 36～40Nm, then be warmed up to 190 ℃ of banburyings 30 minutes again, rotating speed 30r/min, moment of torsion 26～32Nm, discharging while hot, can obtain the mixture of recovery polypropylene/skin powder, its mechanical property is respectively tensile strength 19.5Mpa, elongation at break 18.2%.The melting peak temperature that Differential scanning calorimetry obtains intermingling material is 159.2 ℃.
Embodiment 4
Accurately take polyethylene 100 weight parts, skin powder 100 weight parts, water-soluble chitosan grafted polyethylene 10 weight parts, water-soluble chitosan graft polypropylene 10 weight parts, dicumyl peroxide (DCP) 1.8 weight parts, then above-mentioned raw materials is joined in high-speed mixer simultaneously and carries out blend, afterwards the material mixed is joined to the Banbury mixer banburying, first 170 ℃ of lower banburyings 15 minutes, rotating speed 10r/min, moment of torsion 30～35Nm, then be warmed up to 190 ℃ of banburyings 15 minutes again, rotating speed 30r/min, moment of torsion 26～30Nm, discharging while hot, can obtain the mixture of recovery polypropylene/skin powder, its mechanical property is respectively tensile strength 16.7Mpa, elongation at break 12.5%.The melting peak temperature that Differential scanning calorimetry obtains intermingling material is 158.3 ℃.
Embodiment 5
Accurately take polyethylene 100 weight parts, skin powder 80 weight parts, water-soluble chitosan grafted polyethylene 15 weight parts, dicumyl peroxide (DCP) 1.4 weight parts, then above-mentioned raw materials is joined in high-speed mixer simultaneously and carries out blend, afterwards the material mixed is joined to the Banbury mixer banburying, first 170 ℃ of lower banburyings 10 minutes, rotating speed 10r/min, moment of torsion 33～38Nm, then be warmed up to 190 ℃ of banburyings 20 minutes again, rotating speed 30r/min, moment of torsion 28～33Nm, discharging while hot, can obtain the mixture of recovery polypropylene/skin powder, its mechanical property is respectively tensile strength 18.2Mpa, elongation at break 16.4%.The melting peak temperature that Differential scanning calorimetry obtains intermingling material is 158.8 ℃.
Embodiment 6
Accurately take polyethylene 100 weight parts, skin powder 5 weight parts, water-soluble chitosan graft polypropylene 5 weight parts, dicumyl peroxide (DCP) 0.8 weight part, then above-mentioned raw materials is joined in high-speed mixer simultaneously and carries out blend, afterwards the material mixed is joined to the Banbury mixer banburying, first 170 ℃ of lower banburyings 15 minutes, rotating speed 10r/min, moment of torsion 53～60Nm, then be warmed up to 190 ℃ of banburyings 20 minutes again, rotating speed 30r/min, moment of torsion 44～48Nm, discharging while hot, can obtain the mixture of recovery polypropylene/skin powder, its mechanical property is respectively tensile strength 27.5Mpa, elongation at break 36.2%.The melting peak temperature that Differential scanning calorimetry obtains intermingling material is 162.5 ℃.
Claims (2)
1. a preparation method who reclaims polypropylene/skin flour complexes, it is characterized in that: the preparation method comprises the following steps: take and reclaim polypropylene 100 weight parts, skin powder 5～100 weight parts, expanding material 5～20 weight parts, initiator 0.8～1.8 weight part, above-mentioned raw materials is joined in high-speed mixer simultaneously and carries out blend, afterwards the material mixed is joined to the Banbury mixer banburying, first 170 ℃ of lower banburyings 5～15 minutes, rotating speed 10r/min, moment of torsion 24～62Nm, then be warmed up to 190 ℃ of banburyings 15～30 minutes again, rotating speed 30r/min, moment of torsion 24～52Nm, discharging while hot, can obtain recovery polypropylene/skin flour complexes,
Wherein, described recovery polypropylene tensile strength >=10Mpa, elongation at break >=10%, polyacrylic weight content >=50%;
Wherein, described skin powder is directly to carry out after drying the superfine grinding gained by the grey skin graft of the cattle and sheep leather waste produced of peeling after bits and blue skin shaving, deburring, and the particle diameter of skin powder is controlled between 20～100 orders;
Wherein, described initiator is selected from one or both of benzoyl peroxide, dicumyl peroxide.
2. a kind of preparation method who reclaims polypropylene/skin flour complexes according to claim 1, it is characterized in that: described expanding material is selected from one or both of water-soluble chitosan graft polypropylene, water-soluble chitosan grafted polyethylene; Water-soluble chitosan graft polypropylene, water-soluble chitosan grafted polyethylene adopt following method preparation: the deionized water that adds 300mL in 1 liter of autoclave, the water-soluble chitosan of the modification of 30g, the propylene of 100g or ethene, add the oil soluble polyvinyl alcohol of 1g Vltra tears and 1g as dispersion agent, 0.5g two-(2-second hexyl)-peroxy dicarbonate as initiator, at 70 ℃ of lower stirring reaction 5h, filter and obtain water-soluble chitosan graft polypropylene powder or water-soluble chitosan grafted polyethylene powder.
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| CN201310202299.4A CN103421239B (en) | 2013-05-15 | 2013-05-15 | A kind of preparation method reclaiming polypropylene/leather powder compound |
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| CN201310202299.4A CN103421239B (en) | 2013-05-15 | 2013-05-15 | A kind of preparation method reclaiming polypropylene/leather powder compound |
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| CN103421239B CN103421239B (en) | 2015-10-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440807A (en) * | 2018-05-25 | 2018-08-24 | 中国皮革制鞋研究院有限公司 | Material for sole of shoe and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03162500A (en) * | 1989-11-21 | 1991-07-12 | Idemitsu Petrochem Co Ltd | Leather powder-containing resin composition, leather-like molding and production thereof |
| EP0456264A2 (en) * | 1990-05-11 | 1991-11-13 | Idemitsu Petrochemical Co. Ltd. | Powdered leather and method of producing the same |
| CN102002180A (en) * | 2010-11-03 | 2011-04-06 | 宁波工程学院 | Method for preparing compatible hide powder/polyethylene mixture |
| CN102471808A (en) * | 2009-08-18 | 2012-05-23 | 巴德尔有限责任两合公司 | Method for producing leather pellets and compound granules and use thereof |
-
2013
- 2013-05-15 CN CN201310202299.4A patent/CN103421239B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03162500A (en) * | 1989-11-21 | 1991-07-12 | Idemitsu Petrochem Co Ltd | Leather powder-containing resin composition, leather-like molding and production thereof |
| EP0456264A2 (en) * | 1990-05-11 | 1991-11-13 | Idemitsu Petrochemical Co. Ltd. | Powdered leather and method of producing the same |
| CN102471808A (en) * | 2009-08-18 | 2012-05-23 | 巴德尔有限责任两合公司 | Method for producing leather pellets and compound granules and use thereof |
| CN102002180A (en) * | 2010-11-03 | 2011-04-06 | 宁波工程学院 | Method for preparing compatible hide powder/polyethylene mixture |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440807A (en) * | 2018-05-25 | 2018-08-24 | 中国皮革制鞋研究院有限公司 | Material for sole of shoe and preparation method thereof |
| CN108440807B (en) * | 2018-05-25 | 2020-11-03 | 中国皮革制鞋研究院有限公司 | Sole material and preparation method thereof |
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| CN103421239B (en) | 2015-10-21 |
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