CN103435913A - Reinforcing and toughening POSS (Polyhedral Oligomeric Silsesquioxane) master batch for polypropylene and preparation method of master batch - Google Patents
Reinforcing and toughening POSS (Polyhedral Oligomeric Silsesquioxane) master batch for polypropylene and preparation method of master batch Download PDFInfo
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Abstract
The invention discloses reinforcing and toughening POSS (Polyhedral Oligomeric Silsesquioxane) master batch for polypropylene and a preparation method of the master batch, wherein the reinforcing and toughening POSS master batch comprises the following raw materials in parts by mass: 100 parts of PP (Polypropylene) resin, 1-5 parts of surface treating agents, 1-5 parts of PP wax and 20-40 parts of POSS. According to the master batch and the preparation method thereof disclosed by the invention, the POSS master batch and the matrix PP resin are injection-molded after being molten and blended. Moreover, the dispersity of the high-content POSS nanometer particles in the PP matrix is improved and the interface adhesion is reinforced by the POSS master batch disclosed by the invention, so that an obvious reinforcing and toughening effect is achieved for the PP resin.
Description
One, technical field
The present invention relates to a kind of polypropylene with strengthening toughness reinforcing POSS masterbatch and preparation method thereof.
Two, background technology
Polypropylene (PP) is a kind of thermoplastic polymer, and its mechanical property is high, and acid-and base-resisting and chemical drugs moral character are outstanding, and its production cost is lower than other thermoplastic polymer, is one of resins for universal use of current consumption maximum in the world.But also there is very fatal shortcoming in PP, as large as poor toughness, molding shrinkage, easily aging etc.For improving the toughness of PP, usually add thermoplastic elastic body, but the raising of toughness is to sacrifice the intensity of PP preciousness and rigidity is cost.And adopt the inorganic nano rigid particles to carry out modification to PP, can realize strengthening with toughness reinforcing simultaneously.
Add inorganic nano particle modified PP, can improve multinomial mechanical property and the thermomechanical property of material, such as rigidity, Vicat softening point, creep resistance etc.Inorganic nano-particle mainly depends on the performance of shape, size, particle cluster aggressiveness size, particle surface feature and the polymkeric substance collective of inorganic nano-particle on the impact of PP mechanical property.Inorganic nano-particle strengthens Toughened PP must meet two conditions: (1) particle is uniformly dispersed, and avoids forming the large particle cluster aggressiveness that can cause crackle; (2) particle must with polymeric matrix generation unsticking, thereby make around particle expedite viscous deformation can occur.
Multiaspect oligomeric silsesquioxane (polyhedral oligomericsilsesquioxane is called for short POSS) is that U.S. Hybrid Plastics company is towards global development, novel molecular decentralized nanometer strengthener that develop for the polymer regeneration product.POSS is the silicoorganic compound that a class has the cage modle molecular structure, and general molecular formula is (RSiO
1.5)
n, there is the polyhedron inorganic framework core of Si-O nanostructure, be with organic group outward and surround.Inorganic kernel provides good thermotolerance for material, and peripheral organic group can increase the consistency with polymkeric substance collective, be preparation inorganic/properties-correcting agent that the organic polymer nano-hybrid material is good.
Three, summary of the invention
The present invention aims to provide a kind of polypropylene with strengthening toughness reinforcing POSS masterbatch and preparation method thereof, with POSS molecule dispersed bad, easy reunion, the interface in PP that the solves high-content bad technical problem that bonds, thereby reaches the purpose that strengthens Toughened PP.
Technical solution problem of the present invention adopts following technical scheme:
Polypropylene of the present invention, with strengthening toughness reinforcing POSS masterbatch, is called for short the POSS masterbatch, and its raw material is configured to by mass fraction:
100 parts of PP resins,
Surface treatment agent 1-5 part,
PP wax 1-5 part,
POSS 20-40 part.
The melting index of described PP resin is 4-6g/10min.
Described PP resin is selected from F401, K8303 or T30S.
Described surface treatment agent is selected from one or more in stearic acid, silane coupling agent, aluminate coupling agent, titanate coupling agent.The preferred KH-550 of silane coupling agent wherein, the preferred DL-411 of aluminate coupling agent, the preferred TMC201 of titanate coupling agent.
Described surface treatment agent preferred silane coupling agent KH-550.
Described PP wax is PP6105A, and Guangzhou Chuan Jinxin Chemical Industry Science Co., Ltd produces.
Described POSS is selected from prestox eight silicious sesquioxanes (prestox POSS), eight isobutyl-eight silicious sesquioxanes (eight isobutyl-POSS) or eight iso-octyl eight silicious sesquioxanes (eight iso-octyl POSS).
Described POSS is eight isobutyl-eight silicious sesquioxanes preferably.
The preparation method who strengthens toughness reinforcing POSS masterbatch for polypropylene of the present invention, operation according to the following steps:
1) after being mixed, PP resin, surface treatment agent, PP wax and POSS obtain compound;
2) described compound is added extruding pelletization in twin screw extruder obtain the POSS masterbatch, the temperature of twin screw extruder is controlled at 175-220 ℃, screw speed 60-110 rev/min.
POSS masterbatch of the present invention is mixed with the mass ratio of matrix PP resin by 10-40:100, and melt blending injection moulding obtain the enhancing Toughened PP according to a conventional method.Strengthen tensile strength, notched Izod impact strength and the Vicat softening point of Toughened PP according to GB/T1040.1-2006, GB/T21189-2007, GB/T1633-2000 canonical measure.
The present invention has improved the dispersiveness of POSS nanoparticle in matrix PP resin of high-content, has strengthened the interface bonding, thereby the PP resin has been played to obvious enhancing toughening effect.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, POSS masterbatch of the present invention has improved the consistency of POSS and matrix PP resin greatly, and then improved the dispersiveness of POSS in matrix PP resin, avoid forming and can cause the large particle cluster aggressiveness of crackle, thereby matrix PP resin has been played to obvious enhancing toughening effect.
2, the nanometer cage modle of POSS masterbatch of the present invention can be given the good resistance toheat of PP.
3, the preparation method of POSS masterbatch of the present invention is simple, workable, suitability for industrialized production.
Four, accompanying drawing explanation
Fig. 1 directly adds POSS in matrix PP resin and prepares matrix material (mass ratio of POSS and matrix PP is 10:100), and carry out the EDS ultimate analysis by scanning electronic microscope, observe the distribution of Si element, obtain the dispersion state figure of POSS in matrix PP resin.
Fig. 2 adds POSS masterbatch of the present invention in matrix PP resin to and prepares matrix material (wherein the mass ratio of the POSS in the POSS masterbatch and matrix PP is 10:100), and carry out the EDS ultimate analysis by scanning electronic microscope, observe the distribution of Si element, obtain the dispersion state figure of POSS in matrix PP resin.
From the contrast of Fig. 1, Fig. 2, can find out, it is more even that POSS masterbatch of the present invention disperses in matrix PP resin.
Five, embodiment
Embodiment 1:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), eight isobutyl-POSS of the stearic acid of 4 parts, the PP6105A of 4 parts and 40 parts add in high-speed mixer to mix and obtain compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 20:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 1#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 2:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), eight isobutyl-POSS of the silane resin acceptor kh-550 (NanJing Shuguang Chemical Group Co., Ltd.'s production) of 4 parts, the PP6105A of 4 parts and 40 parts add in high-speed mixer to mix and obtain compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 20:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 2#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 3:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), titanate coupling agent TMC201(NanJing Shuguang Chemical Group Co., Ltd. of 4 parts produces), eight isobutyl-POSS of the PP6105A of 4 parts and 40 parts add in high-speed mixer to mix and obtain compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 20:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 3#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 4:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), the peaceful coupling agent of the aluminate coupling agent DL-411(Nanjing product company limited of 4 parts produces), eight isobutyl-POSS of the PP6105A of 4 parts and 40 parts add in high-speed mixer to mix and obtain compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 20:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 4#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 5:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), the prestox POSS of the silane resin acceptor kh-550 (NanJing Shuguang Chemical Group Co., Ltd.'s production) of 4 parts, the PP6105A of 4 parts and 40 parts adds in high-speed mixer to mix and obtains compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 20:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 5#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 6:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), eight iso-octyl POSS of the silane resin acceptor kh-550 (NanJing Shuguang Chemical Group Co., Ltd.'s production) of 4 parts, the PP6105A of 4 parts and 40 parts add in high-speed mixer to mix and obtain compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 20:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 6#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 7:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), eight isobutyl-POSS of the silane resin acceptor kh-550 (NanJing Shuguang Chemical Group Co., Ltd.'s production) of 4 parts, the PP6105A of 4 parts and 40 parts add in high-speed mixer to mix and obtain compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 10:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 7#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 8:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), eight isobutyl-POSS of the silane resin acceptor kh-550 (NanJing Shuguang Chemical Group Co., Ltd.'s production) of 4 parts, the PP6105A of 4 parts and 40 parts add in high-speed mixer to mix and obtain compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 30:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 8#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 9:
1, the preparation of POSS masterbatch
PP resin K8303(Beijing yanshan petrochemical company limiteds of 100 parts are produced), eight isobutyl-POSS of the silane resin acceptor kh-550 (NanJing Shuguang Chemical Group Co., Ltd.'s production) of 4 parts, the PP6105A of 4 parts and 40 parts add in high-speed mixer to mix and obtain compound; Add extruding pelletization in twin screw extruder to obtain the POSS masterbatch described compound, 190 ℃ of the barrel zone temperatures of twin screw extruder, 100 rev/mins of screw speeds.
2, strengthen the preparation of Toughened PP
By the POSS masterbatch of step 1 preparation and matrix PP resin according to the ratio melt blending of mass ratio 40:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 9#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Embodiment 10: Comparative Examples-POSS directly adds matrix PP resin to
By eight isobutyl-POSS and matrix PP resin according to the ratio melt blending of mass ratio 10:100 after injection moulding, 240 ℃ of melt temperatures, injection pressure 1500bar, obtain 10#PP, its mechanical property, degree of crystallinity, resistance toheat test result are in Table 1.
Table 1
As can be seen from Table 1, while by embodiment 1,2,3,4 is known, using silane resin acceptor kh-550 as surface treatment agent, strengthen toughness reinforcing effect best; Best to performance boost by the known eight isobutyl-POSS of embodiment 2,5,6; First increase rear reduction by the known performance that increases along with POSS masterbatch content of embodiment 2,7,8,9, the performance of embodiment 2 is best; From embodiment 9,10, POSS masterbatch of the present invention is good than direct interpolation POSS to the lifting of matrix PP performance.
Claims (9)
1. a polypropylene, with strengthening toughness reinforcing POSS masterbatch, is characterized in that its raw material is configured to by mass fraction:
100 parts of PP resins,
Surface treatment agent 1-5 part,
PP wax 1-5 part,
POSS 20-40 part.
2. polypropylene according to claim 1, with strengthening toughness reinforcing POSS masterbatch, is characterized in that:
The melting index of described PP resin is 4-6g/10min.
3. polypropylene according to claim 1 and 2, with strengthening toughness reinforcing POSS masterbatch, is characterized in that:
Described PP resin is selected from F401, K8303 or T30S.
4. polypropylene according to claim 1, with strengthening toughness reinforcing POSS masterbatch, is characterized in that:
Described surface treatment agent is selected from one or more in stearic acid, silane coupling agent, aluminate coupling agent, titanate coupling agent.
5. according to the toughness reinforcing POSS masterbatch of enhancing for the described polypropylene of claim 1 or 4, it is characterized in that:
Described surface treatment agent is silane resin acceptor kh-550.
6. polypropylene according to claim 1, with strengthening toughness reinforcing POSS masterbatch, is characterized in that:
Described PP wax is PP6105A.
7. polypropylene according to claim 1, with strengthening toughness reinforcing POSS masterbatch, is characterized in that:
Described POSS is selected from prestox eight silicious sesquioxanes, eight isobutyl-eight silicious sesquioxanes or eight iso-octyl eight silicious sesquioxanes.
8. according to the toughness reinforcing POSS masterbatch of enhancing for the described polypropylene of claim 1 or 7, it is characterized in that:
Described POSS is eight isobutyl-eight silicious sesquioxanes.
9. a preparation method who strengthens toughness reinforcing POSS masterbatch for polypropylene claimed in claim 1 is characterized in that operating according to the following steps:
1) after being mixed, PP resin, surface treatment agent, PP wax and POSS obtain compound;
2) described compound is added extruding pelletization in twin screw extruder obtain the POSS masterbatch, the temperature of twin screw extruder is controlled at 175-220 ℃, screw speed 60-110 rev/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104212065A (en) * | 2014-09-24 | 2014-12-17 | 广东天安新材料股份有限公司 | Polypropylene foam material and preparation method thereof |
| CN104672607A (en) * | 2014-12-30 | 2015-06-03 | 苏州度辰新材料有限公司 | Biaxially oriented polypropylene high-modulus film master batch and production process thereof |
| CN106519455A (en) * | 2016-10-13 | 2017-03-22 | 汕头市贝斯特科技有限公司 | Low-friction coefficient anti-bonding master batch special for metallized base film and preparation method thereof |
| CN108059758A (en) * | 2018-01-11 | 2018-05-22 | 缪金斌 | A kind of modified material of sunbonnet the brim of a hat sheet material |
| CN109679216A (en) * | 2018-12-28 | 2019-04-26 | 重庆普利特新材料有限公司 | A kind of high rigid-tough balance, resistance to stress whiten, halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN112812426A (en) * | 2020-12-30 | 2021-05-18 | 河南驼人医疗器械研究院有限公司 | Radiation-resistant polypropylene composition and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212065A (en) * | 2014-09-24 | 2014-12-17 | 广东天安新材料股份有限公司 | Polypropylene foam material and preparation method thereof |
| CN104672607A (en) * | 2014-12-30 | 2015-06-03 | 苏州度辰新材料有限公司 | Biaxially oriented polypropylene high-modulus film master batch and production process thereof |
| CN106519455A (en) * | 2016-10-13 | 2017-03-22 | 汕头市贝斯特科技有限公司 | Low-friction coefficient anti-bonding master batch special for metallized base film and preparation method thereof |
| CN106519455B (en) * | 2016-10-13 | 2018-11-27 | 汕头市贝斯特科技有限公司 | A kind of dedicated low-friction coefficient bonding-prevention master batch of metallization basement membrane and its preparation |
| CN108059758A (en) * | 2018-01-11 | 2018-05-22 | 缪金斌 | A kind of modified material of sunbonnet the brim of a hat sheet material |
| CN109679216A (en) * | 2018-12-28 | 2019-04-26 | 重庆普利特新材料有限公司 | A kind of high rigid-tough balance, resistance to stress whiten, halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN112812426A (en) * | 2020-12-30 | 2021-05-18 | 河南驼人医疗器械研究院有限公司 | Radiation-resistant polypropylene composition and preparation method and application thereof |
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Application publication date: 20131211 |