CN106380697A - High-modulus and low-density polypropylene and preparation method thereof - Google Patents

High-modulus and low-density polypropylene and preparation method thereof Download PDF

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Publication number
CN106380697A
CN106380697A CN201610801193.XA CN201610801193A CN106380697A CN 106380697 A CN106380697 A CN 106380697A CN 201610801193 A CN201610801193 A CN 201610801193A CN 106380697 A CN106380697 A CN 106380697A
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Prior art keywords
polypropylene
moduluss
low density
glass fiber
density polypropylene
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Chinese (zh)
Inventor
卢军
祖勇
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DALIAN JUXING TECHNOLOGY Co Ltd
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DALIAN JUXING TECHNOLOGY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high-modulus and low-density polypropylene and a preparation method thereof. The high-modulus and low-density polypropylene is prepared from, by weight, 81-100 parts of polypropylene and 0.5-15 parts of long glass fiber reinforced polypropylene. Polypropylene and the long glass fiber reinforced polypropylene are uniformly mixed according to a certain ratio to obtain the high-modulus and low-density polypropylene. Dispersion of glass fibers with a certain length in a polypropylene system of the long glass fiber reinforced polypropylene reserves the length of the glass fibers as possible, and the glass fibers have a skeleton effect on polypropylene, so the mechanical performances of polypropylene are obviously improved; and the content of introduced glass fibers does not exceed 6%, so the density of the polypropylene material is not affected.

Description

A kind of high-moduluss low density polypropylene and preparation method thereof
Technical field
The present invention relates to chemical material technical field, more particularly, to a kind of polypropylene and preparation method thereof.
Background technology
Polypropylene density is low, and mechanical performance is more excellent, has good stress crack resistant, endurance surrender and chemicals-resistant Performance, and have low price, the advantages of easy processing molding.But polypropylene has the shortcomings that the modulus of elasticity in static bending is relatively low, This shortcoming also limits its application in the industry.Therefore in order that polypropylene obtain good application in the industry must be to it It is modified.In order to increase the modulus of modified polypropene, select interpolation nanoclay, Pulvis Talci etc. inorganic generally in polypropylene Mineral dust, but the increase of inorganic mineral powder can make its density raise again；Or by adding nucleator, using nucleator Nucleation and crystallization ability is it is also possible to improve polyacrylic modulus.
The patent of Application No. 200910194556.8 discloses a kind of low-density, high rigidity, the polypropylene of high tenacity are received Nano composite material and preparation method thereof, obtains the raising of polypropylene bending moduluses and density by adding a small amount of nanoclay Increase less.The patent of Application No. 201110443064.5 discloses a kind of high transparency, high-moduluss impact modified polypropylene material Material and preparation method thereof, by adding nucleator to be two (3,4- dimethyl two benzal) Sorbitol (DMDBS), using nucleator Nucleation and crystallization ability, improve PP matrix modulus.
Said method all exists to keep polypropylene density to be basically unchanged, and little the asking of material modulus increase rate Topic, and in order to nanoclay or nucleator can be uniformly scattered in polypropylene, be required for melting through plastic extruder Melt extruding pelletization, increased energy resource consumption and material secondary is heated the risk of performance degradation.
Content of the invention
Obtain high-moduluss and do not increase contradiction between density to solve polypropylene, the present invention provides a kind of preparation method Simply, cost is relatively low, effect obvious high-moduluss low density polypropylene and preparation method thereof.
The present invention be employed technical scheme comprise that for achieving the above object：A kind of high-moduluss low density polypropylene, by following The component carrying out proportioning by weight is made：
81 ~ 100 parts of polypropylene
0.5 ~ 15 part of long glass fiber-reinforced polypropylene
Preferably, described polypropylene is HOPP or COPP or HOPP and COPP arbitrary proportion Mixture.
Preferably, in described high-moduluss low density polypropylene, total glass fiber content is the 0.2% ~ 6% of system total amount.
Preferably, herein described high-moduluss low density polypropylene also includes processing aid, and described processing aid is lubrication One or more of agent, antioxidant, light stabilizer, coloring agent.
Described lubricant is one of stearate, polyolefin-wax, ethylene bis stearamide, pentaerythritol stearate Or it is multiple.
Described antioxidant is one or more of phenolic antioxidant, phosphite ester kind antioxidant, sulphur ester antioxidant.
Described light stabilizer is hindered amine light stabilizer, triazines as light stabilizer, in benzotriazole light stabilizer one Plant or multiple.
Described coloring agent is one or more of inorganic pigment, organic pigment.
The preferred calcium stearate of stearate.
Polyolefin-wax preferably polyethylene wax.
The preferred antioxidant 1010 of phenolic antioxidant.
The preferred irgasfos 168 of phosphite ester kind antioxidant.
Sulphur ester antioxidant preferred antioxidant DSTP
Light stabilizer preferred U.S. cyanogen spy's V703, V680 light stabilizer
Present invention also provides the preparation method of above-mentioned high-moduluss low density polypropylene, specifically include following steps：
（1）Long glass fiber-reinforced polypropylene is obtained using known technology；
（2）Processing aid master batch is obtained using known technology：Polypropylene, lubricant, antioxidant, light stabilizer, coloring agent are mixed Close and melt extrude pelletize uniformly through plastic extruding pelletization machine, obtain processing aid master batch；
（3）By polypropylene, long glass fiber-reinforced polypropylene and processing aid master batch by a certain percentage mix homogeneously to make high-moduluss low Density polypropylene.
Beneficial effect：The present invention is distributed in Pp System using the glass of certain length in long glass fiber-reinforced polypropylene Formed dimensional network structure, due to remaining the length of glass as far as possible, glass play skeleton function in polypropylene hence it is evident that Improve polyacrylic mechanical property.Glass fiber content due to introducing is less than 6%, not appreciably affects polypropylene material density.
Specific embodiment
A kind of high-moduluss low density polypropylene, is made up of the following component carrying out proportioning by weight：
81 ~ 100 parts of polypropylene
0.5 ~ 15 part of long glass fiber-reinforced polypropylene
Preferably, described polypropylene is HOPP or COPP or HOPP and COPP arbitrary proportion Mixture.
Preferably, in described high-moduluss low density polypropylene, total glass fiber content is the 0.2% ~ 6% of system total amount.
Preferably, herein described high-moduluss low density polypropylene also includes processing aid, and described processing aid is lubrication One or more of agent, antioxidant, light stabilizer, coloring agent.
Described lubricant is one of stearate, polyolefin-wax, ethylene bis stearamide, pentaerythritol stearate Or it is multiple.
Described antioxidant is one or more of phenolic antioxidant, phosphite ester kind antioxidant, sulphur ester antioxidant.
Described light stabilizer is hindered amine light stabilizer, triazines as light stabilizer, in benzotriazole light stabilizer One or more.
Described coloring agent is one or more of inorganic pigment, organic pigment.
The preferred calcium stearate of stearate, polyolefin-wax preferably polyethylene wax, the preferred antioxidant 1010 of phenolic antioxidant, sub- The preferred irgasfos 168 of phosphoric acid ester antioxidant, sulphur ester antioxidant preferred antioxidant DSTP, light stabilizer preferred U.S. cyanogen is special V703 light stabilizer, V680 light stabilizer.
The preparation method of above-mentioned high-moduluss low density polypropylene, specifically includes following steps：
（1）Long glass fiber-reinforced polypropylene is obtained using known technology；
（2）Processing aid master batch is obtained using known technology：Polypropylene, lubricant, antioxidant, light stabilizer mix homogeneously are led to Cross plastic extruding pelletization machine and melt extrude pelletize, obtain processing aid master batch；
（3）By polypropylene, long glass fiber-reinforced polypropylene and processing aid master batch by a certain percentage mix homogeneously to make high-moduluss low Density polypropylene.
Long glass fiber-reinforced polypropylene can be combined using a kind of long glass fiber-reinforced polypropylene of application number 201210288635.7 Material, preparation method and applications；Application number CN201410033762.1 Long Glass Fiber Reinforced PP Composite and its preparation Method；Etc. known technology obtain.
Processing aid master batch can adopt a kind of low abnormal smells from the patient of application number CN201410827389.7, the high dispersive auxiliary agent of resistance to scratching Master batch and preparation method thereof, with reference to adopting its preparation method, sets extrusion processing temperature according to polyacrylic melt temperature, will gather Pass through extruder extruding pelletization after the mix homogeneously such as propylene, antioxidant, lubricant, light stabilizer, coloring agent.Shen can also be adopted Please number 200410091120.3 particle antioxygen for machining plastic preparation method, with reference to adopting its preparation method, according to profit The fusion temperature of lubrication prescription sets extrusion processing temperature, will be logical after the mix homogeneously such as antioxidant, lubricant, light stabilizer, coloring agent Cross extruder extruding pelletization.
The making of processing aid master batch：By powdered polypropylene Z30S 75Kg, calcium stearate 5Kg, Tissuemat E 7.5kg, resist Oxygen agent 1010 5kg, irgasfos 168 7.5kg mix homogeneously melt extrudes pelletize by plastic extruding pelletization machine, obtains processing and helps Agent master batch.
Polypropylene and long glass fiber-reinforced polypropylene and processing aid master batch are mixed according to the ratio of embodiment or comparative example Close uniformly, standard testing batten is molded into by injection machine, according to ISO1183 standard testing density, survey according to ISO178 standard Examination bending moduluses.
Long glass fiber-reinforced polypropylene gathers the trade mark LGF PP-40 of the company limited's production that makes the science and technology prosperous using Dalian, and roving glass fiber contains Amount 40%, short glass fiber RPP gathers the trade mark PP10 of the company limited's production that makes the science and technology prosperous, short glass fiber content 30% using Dalian.
The trade mark Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Polypropylene Z30S 86 91 95.5 81
Long glass fiber-reinforced polypropylene LGF PP-40 10 5 0.5 15
Processing aid master batch 4 4 4 4
Actual glass fiber content 4% 2% 0.2% 6%
The trade mark Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8
Polypropylene 7726 86 91 95.5 81
Long glass fiber-reinforced polypropylene LGF PP-40 10 5 0.5 15
Processing aid master batch 4 4 4 4
Actual glass fiber content 4% 2% 0.2% 6%
The trade mark Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12
Polypropylene Z30S 43 45.5 47.75 40.5
Polypropylene 7726 43 45.5 47.75 40.5
Long glass fiber-reinforced polypropylene LGF PP-40 10 5 0.5 15
Processing aid master batch 4 4 4 4
Actual glass fiber content 4% 2% 0.2% 6%
The trade mark Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16
Polypropylene Z30S 90 0 99.5 0
Polypropylene 7726 0 95 0 85
Long glass fiber-reinforced polypropylene LGF PP-40 10 5 0.5 15
Actual glass fiber content 4% 2% 0.2% 6%
The trade mark Embodiment 17 Embodiment 18
Polypropylene Z30S 45 47.5
Polypropylene 7726 45 47.5
Long glass fiber-reinforced polypropylene LGFPP40 10 5
Actual glass fiber content 4% 2%
The trade mark Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Polypropylene Z30S 82.7 89.3 0 0
Polypropylene 7726 0 0 82.7 89.3
Short glass fiber RPP PP10 (glass fiber content 30%) 13.3 6.7 13.3 6.7
Processing aid master batch 4 4 4 4
Actual glass fiber content 4% 2% 4% 2%
The trade mark Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8
Polypropylene Z30S 41.35 44.65 0 100
Polypropylene 7726 41.35 44.65 0 0
Polypropylene 5029 0 0 100 0
Short glass fiber RPP PP10 (glass fiber content 30%) 13.3 6.7 0 0
Processing aid master batch 4 4 0 0
Actual glass fiber content 4% 2% 0 0
Test result
Unit Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Density g/cm3 0.940 0.925 0.915 0.951
Bending moduluses MPa 1850 1683 1459 2029
Unit Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8
Density g/cm3 0.939 0.925 0.913 0.949
Bending moduluses MPa 1578 1461 1285 1850
Unit Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12
Density g/cm3 0.940 0.925 0.914 0.950
Bending moduluses MPa 1730 1580 1438 1947
Unit Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16
Density g/cm3 0.939 0.924 0.914 0.951
Bending moduluses MPa 1830 1430 1470 1830
Unit Embodiment 17 Embodiment 18
Density g/cm3 0.934 0.925
Bending moduluses MPa 1713 1599
Unit Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Density g/cm3 0.940 0.925 0.940 0.925
Bending moduluses MPa 1662 1574 1419 1328
Unit Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8
Density g/cm3 0.939 0.925 0.914 0.912
Bending moduluses MPa 1554 1491 1911 1454
From embodiment 1 and comparative example 8 relatively, HOPP only increases by 4% glass, the bending moduluses of material carry High by 27%, and density only increases by 3%.
From embodiment 2 and comparative example 8 relatively, HOPP only increases by 2% glass, the bending die of material Amount improves 16%, and density only increases by 1.4%.
From embodiment 9 and comparative example 8 relatively, the mixture with HOPP for the COPP only increases by 4% Glass, the bending moduluses of material improve 19%, and density only increases by 3%.
Contrasted it is seen that a small amount of roving glass fiber is to polypropylene mould with comparative example 8 by embodiment 1, embodiment 2, embodiment 9 The castering action of amount is very big.
From embodiment 1 and comparative example 1 relatively, HOPP increases by 4% roving glass fiber and short glass fiber respectively, The bending moduluses of embodiment 1 material improve 11.3% than comparative example 1, and density is the same.It can be seen that roving glass fiber is wanted to the lifting of modulus It is better than short glass fiber.
From embodiment 2 and comparative example 2 relatively, HOPP increases by 2% roving glass fiber and short glass fiber respectively, The bending moduluses of embodiment 2 material improve 7% than comparative example 2, and density is the same.It can be seen that roving glass fiber will be got well to the lifting of modulus In short glass fiber.
From embodiment 14 and embodiment 6 relatively, in COPP same containing 2% roving glass fiber, embodiment 14 Do not use processing aid master batch, the bending moduluses of material and embodiment 6 differ only by 2%, and density is the same.
From embodiment 1 and embodiment 13 relatively, in HOPP same containing 4% roving glass fiber, embodiment 13 Do not use processing aid master batch, the bending moduluses of material and embodiment 1 differ only by 1%, and density is the same.
Comparative example 7 is that the polypropylene of the trade mark 5029 adopting belongs to the high-crystallinity polypropylene that with the addition of nucleator, from enforcement Example 1, embodiment 4 are relatively seen with comparative example 7, curved as high-crystallinity polypropylene by adding a small amount of roving glass fiber also can obtain Bent modulus.
The present invention is described by embodiment, and those skilled in the art know, in the spirit without departing from the present invention In the case of scope, various changes or equivalence replacement can be carried out to these features and embodiment.In addition, the religion in the present invention Lead down, these features and embodiment can be modified with the essence adapting to particular situation and material without departing from the present invention God and scope.Therefore, the present invention is not limited to the particular embodiment disclosed, fallen with claims hereof In the range of embodiment broadly fall into protection scope of the present invention.

Claims (9)

1. a kind of high-moduluss low density polypropylene it is characterised in that：It is made up of the following component carrying out proportioning by weight：
81 ~ 100 parts of polypropylene
0.5 ~ 15 part of long glass fiber-reinforced polypropylene.
2. high-moduluss low density polypropylene according to claim 1 it is characterised in that：Described polypropylene is HOPP Or the mixture of COPP or HOPP and COPP arbitrary proportion.
3. high-moduluss low density polypropylene according to claim 1 it is characterised in that：Described high-moduluss low density polypropylene In total glass fiber content be the 0.2% ~ 6% of system total amount.
4. high-moduluss low density polypropylene according to claim 1 it is characterised in that：Also include processing aid, described plus Work auxiliary agent is one or more of lubricant, antioxidant, light stabilizer, coloring agent.
5. high-moduluss low density polypropylene according to claim 4 it is characterised in that：Described lubricant be stearate, One or more of polyolefin-wax, ethylene bis stearamide, pentaerythritol stearate.
6. high-moduluss low density polypropylene according to claim 4 it is characterised in that：Described antioxidant is phenols antioxygen One or more of agent, phosphite ester kind antioxidant, sulphur ester antioxidant.
7. high-moduluss low density polypropylene according to claim 4 it is characterised in that：Described light stabilizer is hindered amines One or more of light stabilizer, triazines as light stabilizer, benzotriazole light stabilizer.
8. high-moduluss low density polypropylene according to claim 4 it is characterised in that：Described coloring agent be inorganic pigment, One or more of organic pigment.
9. the high-moduluss low density polypropylene described in the claims preparation method it is characterised in that：Comprise the steps：
Long glass fiber-reinforced polypropylene is obtained using known technology；
Processing aid master batch is obtained using known technology：By polypropylene, lubricant, antioxidant, light stabilizer, coloring agent mixing all Even pelletize is melt extruded by plastic extruding pelletization machine, obtain processing aid master batch；
（3）By polypropylene, long glass fiber-reinforced polypropylene and processing aid master batch by a certain percentage mix homogeneously to make high-moduluss low Density polypropylene.
CN201610801193.XA 2016-09-05 2016-09-05 High-modulus and low-density polypropylene and preparation method thereof Pending CN106380697A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101343392A (en) * 2008-08-27 2009-01-14 蔡增坤 Halogen-free flame-proof reinforced polypropylene composite material and preparation thereof
CN101418100A (en) * 2008-12-11 2009-04-29 上海金发科技发展有限公司 Halogen-free flame retardant long glass fibre reinforcement polypropylene composite material and preparation method thereof
CN102127260A (en) * 2010-01-13 2011-07-20 江苏纤强复合材料有限公司 Tough long glass fiber-reinforced polypropylene composition plate material and preparation method thereof
CN102516667A (en) * 2011-12-19 2012-06-27 江苏金发科技新材料有限公司 Halogen-free flame-retardant long glass fiber reinforced polypropylene material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101343392A (en) * 2008-08-27 2009-01-14 蔡增坤 Halogen-free flame-proof reinforced polypropylene composite material and preparation thereof
CN101418100A (en) * 2008-12-11 2009-04-29 上海金发科技发展有限公司 Halogen-free flame retardant long glass fibre reinforcement polypropylene composite material and preparation method thereof
CN102127260A (en) * 2010-01-13 2011-07-20 江苏纤强复合材料有限公司 Tough long glass fiber-reinforced polypropylene composition plate material and preparation method thereof
CN102516667A (en) * 2011-12-19 2012-06-27 江苏金发科技新材料有限公司 Halogen-free flame-retardant long glass fiber reinforced polypropylene material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
何巧玲等: "长玻璃纤维增强聚丙烯复合材料力学性能的研究", 《2009年中国工程塑料复合材料技术研讨会论文集》 *

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Application publication date: 20170208