CN102229750B - Modified polypropylene composite material and preparation technology thereof - Google Patents
Modified polypropylene composite material and preparation technology thereof Download PDFInfo
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- CN102229750B CN102229750B CN 201110175766 CN201110175766A CN102229750B CN 102229750 B CN102229750 B CN 102229750B CN 201110175766 CN201110175766 CN 201110175766 CN 201110175766 A CN201110175766 A CN 201110175766A CN 102229750 B CN102229750 B CN 102229750B
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Abstract
The invention relates to a modified polypropylene composite material and a preparation technology thereof. The composite material is prepared from the following main raw materials: 5 to 20 wt% of calcium sulfate, 20 to 35 wt% of thermoplastic starch, 30 to 50 wt% of plant fiber, and 20 to 40 wt% of polypropylene with processing auxiliary agents comprising a compatilizer silane coupling agent KH550, a compatilizer titanate coupling agent, a plasticizer glycerin, a lubricant eleaostearic acid and an anti-oxidant 1010. The invention also relates to the preparation technology of the modified polypropylene composite material. The modified polypropylene composite material which has the advantages of good mechanical properties, fine degradability and low preparation cost is especially adapted to manufacture package containers such as circulating boxes, pallets, snack boxes and the like.
Description
Technical field
The present invention relates to a kind of PP composite material and preparation technology thereof, especially relate to a kind of modified polypropylene composite material and preparation technology thereof.
Background technology
The source of plastics mainly is a natural oil, and the storage capacity of these energy has certain limit, and plastics very difficult degraded fast under natural condition, has caused very big pressure for environment and resource.The filling degradable material is the heat subject of studying in recent ten years in plastic substrate; For example interpolation vegetable fibre or starch are processed the material that can partly degrade in plastic substrate; Shenyang fertile and matrix material scientific & trading Co., Ltd. Development and Production goes out the substitute of a kind of new green environment protection material, plastics---mould wooden composite pallet; " plastics industry " 2002 the 5th phases the 45th page of development paper of having delivered a kind of degradable plant fibre enhancing starch plastic foaming plastic tableware; But these two kinds of mechanics of materials intensity are all very low, are difficult to be applied to other field.
Summary of the invention
The technical problem that the present invention will solve is, overcomes the deficiency of prior art, provides a kind of mechanical property good, and degradation property is good, the modified polypropylene composite material of low cost of manufacture and preparation technology thereof.
The present invention solve the technical problem the technical scheme that is adopted:
The present invention's modified polypropylene composite material is processed by the main raw material of following weight percent: calcium sulfate 5-20wt%, thermoplastic starch 20-35wt%, vegetable fibre 30-50wt%, Vestolen PP 7052 (PP) 20-40wt%.
Preferred weight percent is: calcium sulfate 10wt%, thermoplastic starch 25wt%, vegetable fibre 45wt%, Vestolen PP 7052 (PP) 20wt%.
Processing aid is: compatilizer silane coupling agent KH550, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010;
Compatilizer silane coupling agent KH550 consumption is the 4-10% (preferred 5%) of calcium sulfate quality, and compatilizer titanate coupling agent consumption is the 1-6% (preferred 5%) of vegetable fibre quality;
Softening agent glycerine consumption is the 15-50% (preferred 40%) of thermoplastic starch quality;
The consumption of lubricant stearic acid is the 2-6% (preferred 4%) of calcium sulfate, thermoplastic starch and vegetable fibre total mass;
Antioxidant 1010 (four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester), consumption is the 0.5-4% (preferred 4%) of calcium sulfate, thermoplastic starch and vegetable fibre total mass;
The size distribution of said calcium sulfate is at 50nm-500nm (preferred 100nm);
Said vegetable fibre can be the wood powder fiber, and the length-to-diameter ratio of fiber can be 5-20 (preferred 10).
The preparation technology of the present invention's modified polypropylene composite material may further comprise the steps:
(1) place absolute ethyl alcohol under 75-85 ℃ of (preferred 80 ℃) condition, to react 4-6 hour (preferred 5 hours) compatilizer silane coupling agent KH550 and calcium sulfate, filter, oven dry gets modification calcium sulfate, and is subsequent use;
(2) use mass concentration to soak 1-8 hour (preferred 6 hours) on vegetable fibre as the sodium hydroxide solution of 2-9% (preferred 6%), then with the clear water washing to neutral, in 70-80 ℃ of (preferred 80 ℃) baking oven, dry to water ratio 4%, subsequent use;
(3) thermoplastic starch, Vestolen PP 7052, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010, step (1) gained modification calcium sulfate and step (2) gained vegetable fibre are added 7-10 minute (preferred 10 minutes) of mixing in the high-speed mixer;
(4) place forcing machine to extrude in step (3) gained mixture, granulation.
The present invention's modified polypropylene composite material, mechanical property is good, and degradation property is good, and low cost of manufacture is particularly suitable for being used for making packaging vessels such as Turnover Box, pallet mess-tin.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explain.
Embodiment 1
The modified polypropylene composite material of present embodiment is processed by the main raw material of following weight percent: calcium sulfate 10wt%, thermoplastic starch 20wt%, wood powder fiber 30wt%, Vestolen PP 7052 (PP) 40wt%.
Processing aid is: compatilizer silane coupling agent KH550, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010;
Compatilizer silane coupling agent KH550 consumption is 6% of a calcium sulfate quality, and compatilizer titanate coupling agent consumption is 4% of a wood powder fiber quality;
Softening agent glycerine consumption is 20% of a thermoplastic starch quality;
The consumption of lubricant stearic acid is the 2wt% of calcium sulfate, thermoplastic starch and wood powder total fiber mass;
Antioxidant 1010 (four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester), consumption is 1% of calcium sulfate, thermoplastic starch and a wood powder total fiber mass;
The particle diameter of said calcium sulfate is 50nm;
The length-to-diameter ratio of said wood powder fiber is 5.
The preparation method:
(1) place absolute ethyl alcohol under 80 ℃ of conditions, to react 5 hours compatilizer silane coupling agent KH550 and calcium sulfate, filter, oven dry gets modification calcium sulfate, and is subsequent use;
(2) the wood powder fiber being used mass concentration is that 4% sodium hydroxide solution soaked 6 hours, then with the clear water washing to neutral, in 80 ℃ of baking ovens, dry to water ratio 3%, subsequent use;
(3) with mixing 7 minutes in thermoplastic starch, Vestolen PP 7052, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010, step (1) gained modification calcium sulfate and step (2) the gained wood powder fiber adding high-speed mixer;
(4) place forcing machine to extrude in step (3) gained mixture, granulation.
Present embodiment product performance detection method; Tensile strength is tested according to GB/T 1040.1-2006 prescriptive procedure; Elongation at break is tested according to GB/T 1040.1-2006 prescriptive procedure; Flexural strength is according to the test of GB/T 9341-2008 prescriptive procedure, and cantilever beam impact strength is according to the test of GB/T 1843-2008 prescriptive procedure, and degradability is according to ASTM D5071 and the test of GB 18006.1 prescriptive procedures.
Present embodiment product detected result: tensile strength is 14.2Mpa; Elongation at break is 53%; Flexural strength is 14.9MPa; Cantilever beam impact strength is 7.9kJ/m
2The weight-average molecular weight rate of descent is 83%.
Embodiment 2
The modified polypropylene composite material of present embodiment is processed by the main raw material of following weight percent: calcium sulfate 10wt%, thermoplastic starch 25wt%, wood powder fiber 45wt%, Vestolen PP 7052 (PP) 20wt%.
Processing aid is: compatilizer silane coupling agent KH550, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010;
Compatilizer silane coupling agent KH550 consumption is 5% of a calcium sulfate quality, and compatilizer titanate coupling agent consumption is 5% of a wood powder fiber quality;
Softening agent glycerine consumption is 40% of a thermoplastic starch quality;
The consumption of lubricant stearic acid is the 4wt% of calcium sulfate, thermoplastic starch and wood powder total fiber mass;
Antioxidant 1010 (four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester), consumption is 4% of calcium sulfate, thermoplastic starch and a wood powder total fiber mass;
The particle diameter of said calcium sulfate is 100nm;
The length-to-diameter ratio of said wood powder fiber is 10.
The preparation method:
(1) place absolute ethyl alcohol under 80 ℃ of conditions, to react 5 hours compatilizer silane coupling agent KH550 and calcium sulfate, filter, oven dry gets modification calcium sulfate, and is subsequent use;
(2) the wood powder fiber being used mass concentration is that 6% sodium hydroxide solution soaked 6 hours, then with the clear water washing to neutral, in 80 ℃ of baking ovens, dry to water ratio 3%, subsequent use;
(3) with mixing 10 minutes in thermoplastic starch, Vestolen PP 7052, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010, step (1) gained modification calcium sulfate and step (2) the gained wood powder fiber adding high-speed mixer;
(4) place forcing machine to extrude in step (3) gained mixture, granulation.
Present embodiment product performance detection method; Tensile strength is tested according to GB/T 1040.1-2006 prescriptive procedure; Elongation at break is tested according to GB/T 1040.1-2006 prescriptive procedure; Flexural strength is according to the test of GB/T 9341-2008 prescriptive procedure, and cantilever beam impact strength is according to the test of GB/T 1843-2008 prescriptive procedure, and degradability is according to ASTM D5071 and the test of GB 18006.1 prescriptive procedures.
Present embodiment product detected result: tensile strength is 15.7Mpa; Elongation at break is 41%; Flexural strength is 15.9MPa; Cantilever beam impact strength is 6.9kJ/m
2The weight-average molecular weight rate of descent is 90%.
Embodiment 3
The modified polypropylene composite material of present embodiment is processed by the main raw material of following weight percent: calcium sulfate 5wt%, thermoplastic starch 35wt%, wood powder fiber 40wt%, Vestolen PP 7052 (PP) 20wt%.
Processing aid is: compatilizer silane coupling agent KH550, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010;
Compatilizer silane coupling agent KH550 consumption is 5% of a calcium sulfate quality, and compatilizer titanate coupling agent consumption is 2% of a wood powder fiber quality;
Softening agent glycerine consumption is 50% of a thermoplastic starch quality;
The consumption of lubricant stearic acid is the 4wt% of calcium sulfate, thermoplastic starch and wood powder total fiber mass;
Antioxidant 1010 (four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester), consumption is 4% of calcium sulfate, thermoplastic starch and a wood powder total fiber mass;
The particle diameter of said calcium sulfate is 500nm;
The length-to-diameter ratio of said wood powder fiber is 10.
The preparation method:
(1) place absolute ethyl alcohol under 80 ℃ of conditions, to react 5 hours compatilizer silane coupling agent KH550 and calcium sulfate, filter, oven dry gets modification calcium sulfate, and is subsequent use;
(2) the wood powder fiber being used mass concentration is that 6% sodium hydroxide solution soaked 6 hours, then with the clear water washing to neutral, in 80 ℃ of baking ovens, dry to water ratio 3%, subsequent use;
(3) with mixing 10 minutes in thermoplastic starch, Vestolen PP 7052, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010, step (1) gained modification calcium sulfate and step (2) the gained wood powder fiber adding high-speed mixer;
(4) place forcing machine to extrude in step (3) gained mixture, granulation.
Present embodiment product performance detection method; Tensile strength is tested according to GB/T 1040.1-2006 prescriptive procedure; Elongation at break is tested according to GB/T 1040.1-2006 prescriptive procedure; Flexural strength is according to the test of GB/T 9341-2008 prescriptive procedure, and cantilever beam impact strength is according to the test of GB/T 1843-2008 prescriptive procedure, and degradability is according to ASTM D5071 and the test of GB 18006.1 prescriptive procedures.
Present embodiment product detected result: tensile strength is 14.8Mpa; Elongation at break is 39%; Flexural strength is 15.2MPa; Cantilever beam impact strength is 6.7kJ/m
2The weight-average molecular weight rate of descent is 93%.
Claims (10)
1. a modified polypropylene composite material is characterized in that, is processed by the main raw material of following weight percent: calcium sulfate 5-20wt%, thermoplastic starch 20-35wt%, vegetable fibre 30-50wt%, Vestolen PP 7052 20-40wt%;
Processing aid is: compatilizer silane coupling agent KH550, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010;
Compatilizer silane coupling agent KH550 consumption is the 4-10% of calcium sulfate quality, and compatilizer titanate coupling agent consumption is the 1-6% of vegetable fibre quality;
Softening agent glycerine consumption is the 15-50% of thermoplastic starch quality;
The consumption of lubricant stearic acid is the 2-6% of calcium sulfate, thermoplastic starch and vegetable fibre total mass;
The antioxidant 1010 consumption is the 0.5-4% of calcium sulfate, thermoplastic starch and vegetable fibre total mass;
The size distribution of said calcium sulfate is at 50nm-500nm;
The length-to-diameter ratio of said vegetable fibre is 5-20.
2. modified polypropylene composite material according to claim 1 is characterized in that, is processed by the main raw material of following weight percent: calcium sulfate 10wt%, thermoplastic starch 25wt%, vegetable fibre 45wt%, Vestolen PP 7052 20wt%.
3. modified polypropylene composite material according to claim 1 and 2 is characterized in that, said compatilizer silane coupling agent KH550 consumption is 5% of a calcium sulfate quality, and compatilizer titanate coupling agent consumption is 5% of a vegetable fibre quality.
4. modified polypropylene composite material according to claim 1 and 2 is characterized in that, said softening agent glycerine consumption is 40% of a thermoplastic starch quality.
5. modified polypropylene composite material according to claim 1 and 2 is characterized in that, the consumption of said lubricant stearic acid is 4% of calcium sulfate, thermoplastic starch and a vegetable fibre total mass.
6. modified polypropylene composite material according to claim 1 and 2 is characterized in that, said antioxidant 1010 consumption is 4% of calcium sulfate, thermoplastic starch and a vegetable fibre total mass.
7. modified polypropylene composite material according to claim 1 and 2 is characterized in that, the particle diameter of said calcium sulfate is 100nm.
8. modified polypropylene composite material according to claim 1 and 2 is characterized in that, said vegetable fibre is the wood powder fiber, and the length-to-diameter ratio of said vegetable fibre is 10.
9. the preparation technology of a modified polypropylene composite material according to claim 1 or claim 2 is characterized in that, may further comprise the steps:
(1) place absolute ethyl alcohol under 75-85 ℃ of condition, to react 4-6 hour compatilizer silane coupling agent KH550 and calcium sulfate, filter, oven dry gets modification calcium sulfate, and is subsequent use;
(2) use mass concentration to soak 1-8 hour on vegetable fibre as the sodium hydroxide solution of 2-9%, then with the clear water washing to neutral, in 70-80 ℃ of baking oven, dry to water ratio 4%, subsequent use;
(3) with mixing 7-10 minute in thermoplastic starch, Vestolen PP 7052, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010, step (1) gained modification calcium sulfate and step (2) the gained vegetable fibre adding high-speed mixer;
(4) place forcing machine to extrude in step (3) gained mixture, granulation.
10. the preparation technology of modified polypropylene composite material according to claim 9 is characterized in that, may further comprise the steps:
(1) place absolute ethyl alcohol under 80 ℃ of conditions, to react 5 hours compatilizer silane coupling agent KH550 and calcium sulfate, filter, oven dry gets modification calcium sulfate, and is subsequent use;
(2) vegetable fibre being used mass concentration is that 6% sodium hydroxide solution soaked 6 hours, then with the clear water washing to neutral, in 80 ℃ of baking ovens, dry to water ratio 4%, subsequent use;
(3) with mixing 10 minutes in thermoplastic starch, Vestolen PP 7052, compatilizer titanate coupling agent, softening agent glycerine, lubricant stearic acid, antioxidant 1010, step (1) gained modification calcium sulfate and step (2) the gained vegetable fibre adding high-speed mixer;
(4) place forcing machine to extrude in step (3) gained mixture, granulation.
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| BR112016023164A2 (en) * | 2014-04-10 | 2018-01-16 | Fpinnovations | process for producing a natural fiber / starch thermoplastic composite and natural fiber / starch thermoplastic composite |
| CN104910439A (en) * | 2015-06-16 | 2015-09-16 | 苏州云舒新材料科技有限公司 | High-strength thermoplastic starch composite material and preparation method thereof |
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| CN106633974A (en) * | 2016-11-03 | 2017-05-10 | 金福英 | Wood substituting packing material and preparation method thereof |
| CN106967235A (en) * | 2017-03-16 | 2017-07-21 | 广西睿桂涵农业有限公司 | A kind of degradable plastics and preparation method thereof |
| CN107987548B (en) * | 2017-12-27 | 2021-02-12 | 广州市恒德环保材料有限公司 | High-strength wood-plastic composite material |
| CN108822408A (en) * | 2018-07-11 | 2018-11-16 | 佛山市高明区爪和新材料科技有限公司 | A kind of high temperature resistant anti-pollution takes off the preparation method of epiphragma |
| CN110819130A (en) * | 2019-10-29 | 2020-02-21 | 浙江新亚伦纸业有限公司 | Plant fiber material capable of being degraded quickly and preparation method thereof |
| CN112322061A (en) * | 2020-09-27 | 2021-02-05 | 宿州合鑫食品包装有限公司 | Straw composite material degradable lunch box and preparation process thereof |
| CN114573915B (en) * | 2022-03-08 | 2023-12-01 | 广东新亚光电缆股份有限公司 | Low-energy-consumption pipe production process |
| CN116003913B (en) * | 2023-01-31 | 2023-07-18 | 上海琦识医疗科技有限公司 | Precise medical catheter and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1575226A (en) * | 2001-10-23 | 2005-02-02 | 马库斯·雷滕巴赫尔 | Moulding comprising plastic and reinforced by natural fibre |
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| US8541051B2 (en) * | 2003-08-14 | 2013-09-24 | Halliburton Energy Services, Inc. | On-the fly coating of acid-releasing degradable material onto a particulate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1575226A (en) * | 2001-10-23 | 2005-02-02 | 马库斯·雷滕巴赫尔 | Moulding comprising plastic and reinforced by natural fibre |
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Effective date of registration: 20160728 Address after: An Industrial Park Economic Development Zone, Changde City, Hunan province Linli County 415200 Patentee after: Hunan Fu Xiang new type building material Co., Ltd. Address before: 410005, 12 floor, Haidong mansion, Furong Road, Changsha, Hunan Patentee before: Liu Liwen |