CN102250420A - Warpage-resistant reinforced polypropylene composite material and preparation method thereof - Google Patents
Warpage-resistant reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- CN102250420A CN102250420A CN2011102409921A CN201110240992A CN102250420A CN 102250420 A CN102250420 A CN 102250420A CN 2011102409921 A CN2011102409921 A CN 2011102409921A CN 201110240992 A CN201110240992 A CN 201110240992A CN 102250420 A CN102250420 A CN 102250420A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The invention relates to a warpage-resistant reinforced polypropylene composite material and a preparation method thereof. The warpage-resistant reinforced polypropylene composite material comprises the following components in percentage by weight: 53 to 89 percent of polypropylene (PP), 5 to 30 percent of low-orientation glass fiber, 5 to 15 percent of compatilizer, 0.1 to 1.0 percent of heat stabilizer DSTP, 0.1 to 1.0 percent of antioxidant 3114, and 0.1 to 0.5 percent of antioxidant 619, wherein the low-orientation glass fiber is common glass fiber of which the cross section is elliptical. The preparation process for the polypropylene composite material is simple, and low in cost; and the warpage-resistant characteristic of the material is ensured, other basic properties, such as mechanical properties and thermo-oxidative stability are excellent.
Description
Technical field
The present invention relates to polypropylene composite material, relate in particular to a kind of anti-warpage reinforced polypropylene compound material; The invention still further relates to this preparation methods.
Background technology
Polypropylene (be called for short PP) has that density is little, chemical proofing good, the mechanical property advantages of higher, but have that molding shrinkage is big, shortcoming such as low temperature brittleness, heat-drawn wire are low.And glass fibre (be called for short glass, adding GF) then can reduce the molding shrinkage of PP, improves its heat-drawn wire, can improve its mechanical property simultaneously, such as: the tensile strength of raising material, flexural strength, modulus in flexure etc.
Yet, because the cross section of we normally used GF is circular, length-to-diameter ratio is big, make the orientation degree of GF in material than higher, therefore glass fiber reinforced polypropylene composite material has typical anisotropic characteristics, as, the glass enhanced polypropylene matrix material with 30%, horizontal shrinking percentage is 0.9, and shrinking percentage is 0.4 longitudinally.Because this anisotropy of material, thereby caused material generation buckling deformation.For the research of injected articles warpage, adopting maximum methods at present is to carry out the CAE model analysis by computer, though and this method can be saved human and material resources, shortcoming is that numerical simulation itself has a lot of inevitably errors.It is by optimizing injection technological parameter, change products thickness and improve methods such as cast gate and improve warpage that certain methods is arranged, but there is significant limitation in these methods to the use of material.The investigator who has solves warpage issues by adding other undersized fiber, and U.S. Pat 4990554 has been reported and used diameter to be the 0.1-0.8 inorganic fibrous fillers, improved the anti-warpage performance of material, but reinforced effects has been poorer than common glass.
In addition, patent CN00115313.7 discloses a kind of glass-fibre reinforced warp-resistant polypropylene with low shrinkage ratio, use the simple glass fiber to do toughener, and add the noncrystalline resin of styrenic with the shrinking percentage that reduces material and shrinking percentage poor in length and breadth, also need coupling agent in this prescription, linking agent, molecular weight regulator is (as dicumyl peroxide, the butanone of dibenzoyl peroxide class or ethyl acetate solution), obviously, this invention is the orientation degree that reduces glass indirectly, so that prescription is too numerous and diverse, the not enough environmental protection of product manufacturing, instabilities such as conditioning agent, can from material, overflow.
Therefore seek a kind of glass fibre of low orientation, tensile strength, flexural strength, modulus in flexure that not only can Reinforced Polypropylene, and can solve the buckling deformation problem that it brings.
Summary of the invention
For addressing the above problem, the invention provides that a kind of preparation technology is simple, cost is low, when guaranteeing the anti-warping characteristic of material, anti-warpage reinforced polypropylene compound material of other fundamental propertys such as mechanical property, thermo-oxidative stability excellence and preparation method thereof.
The technical solution used in the present invention is:
A kind of anti-warpage reinforced polypropylene compound material comprise following component, and the weight proportion of each component is:
Polypropylene PP 53-89%;
Low orientation glass 5-30%;
Compatilizer 5-15%;
Thermo-stabilizer DSTP 0.1-1.0%;
Antioxidant 3114 0.1-1.0%;
Oxidation inhibitor 619 0.1-0.5%;
Wherein, low orientation glass fibre is that cross section is oval simple glass fiber.
Above-mentioned thermo-stabilizer DSTP chemical name is the thio-2 acid octadecyl ester; The antioxidant 3114 chemical name is 1,3,5-three (3,5-di-t-butyl, 4-hydroxybenzyl) s-triazine; Oxidation inhibitor 619 chemical names are diphosphorous acid tetramethylolmethane distearyl alcohol ester.
Further, described compatilizer is that graft polypropylene is grafting PP.
Further, described polypropylene is to have different mobile homo-polypropylenes or/and co-polypropylene.Wherein, the molar content of the ethene in the comonomer of co-polypropylene is in the scope of 4-10mol%.
In addition, described polyacrylic melt flow rate (MFR) (230 ℃ * 2.16kg) be 5-50g/10min, preferred 5-30g/10min.
A kind of preparation method of anti-warpage reinforced polypropylene compound material may further comprise the steps:
(1) takes by weighing raw material by aforementioned weight proportion: polypropylene, low orientation glass fibre, compatilizer, thermo-stabilizer DSTP, antioxidant 3114 and oxidation inhibitor 619;
(2) the described raw material of step (1) was done in super mixer mixed 3-5 minute;
(3) the mixed raw material of step (2) is placed twin screw extruder, through melt extruding granulation, glass fibre adds at the glass mouth, make the pellet of anti-warpage reinforced polypropylene compound material, its process control condition is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2min, and pressure is 12-18MPa.
Beneficial effect of the present invention is:
Technical scheme of the present invention is in the prescription of Reinforced Polypropylene material a kind of glass fibre of low orientation to be replaced conventional glass fibre, this glass fibre characteristics are that cross section is oval, the orientation of the glass of Jiang Diing greatly, thereby improved the anti-warpage performance of material, and the glass fibre of this low orientation has the effect of enhancing, reduction shrinking percentage equally to material; Polypropylene composite material preparation technology of the present invention is simple, cost is low, when guaranteeing the anti-warping characteristic of material, and other fundamental propertys such as mechanical property, thermo-oxidative stability excellence.
Embodiment
Below in conjunction with the contrast experiment, technical solution of the present invention is described in further detail:
Selection:
Described polypropylene is to have the different mobile homo-polypropylenes and the mixture (can certainly adopt homo-polypropylene or co-polypropylene separately) of co-polypropylene, wherein, the molar content of ethene is in the scope of 4-10mol% in the co-polypropylene monomer, and described polyacrylic melt flow rate (MFR) (230 ℃ * 2.16kg) be 5-50g/10min, more commonly used is 5-30g/10min;
Described low orientation glass fibre is that cross section is oval common glass, and its trade mark is 988, and diameter is 6-17um;
In addition, described compatilizer is that graft polypropylene is grafting PP; Described antioxidant 3114 is that a certain company produces, trade names are ST-3114; Described thermal oxidation stabilizer 619 is for a certain company produces, trade names are Weston 619F; Described thermal oxidation stabilizer DSTP is that a certain company produces, trade names are Negonox DSTP.
Wherein, the weight proportion of each above-mentioned component is respectively: polypropylene PP 53-90%; Low orientation glass 5-30%; Compatilizer 5-15%; Thermo-stabilizer DSTP 0.1-1.0%; Antioxidant 3114 0.1-1.0%; Oxidation inhibitor 6190.1-0.5%.
This experiment is divided into 7 samples, and concrete corresponding embodiment is as follows:
Sample 1
Get polypropylene 79% by weight, grafting PP 10%, thermo-stabilizer DSTP 0.5%, antioxidant 3114 0.3%, oxidation inhibitor 619 0.2% is done in super mixer and was mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, common glass 10% adds at the glass mouth, make polypropylene composite material, its process control condition is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
The comparative example of sample 2(sample 1)
Get polypropylene 79% by weight, grafting PP 10%, thermo-stabilizer DSTP 0.5%, antioxidant 3114 0.3%, oxidation inhibitor 619 0.2% is done in super mixer and was mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, low orientation glass 10% adds at the glass mouth, make polypropylene composite material, its process control condition is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Sample 3
Get polypropylene 69% by weight, grafting PP 10%, thermo-stabilizer DSTP 0.5%, antioxidant 3114 0.3%, oxidation inhibitor 619 0.2% is done in super mixer and was mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, common glass 20% adds at the glass mouth, make polypropylene composite material, its process control condition is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
The comparative example of sample 4(sample 3)
Get polypropylene 69% by weight, grafting PP 10%, thermo-stabilizer DSTP 0.5%, antioxidant 3114 0.3%, oxidation inhibitor 619 0.2% is done in super mixer and was mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, low orientation glass 20% adds at the glass mouth, make polypropylene composite material, its process control condition is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Sample 5
Get polypropylene 54% by weight, grafting PP 15%, thermo-stabilizer DSTP 0.5%, antioxidant 3114 0.3%, oxidation inhibitor 619 0.2% is done in super mixer and was mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, common glass 30% adds at the glass mouth, make polypropylene composite material, its process control condition is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
The comparative example of sample 6(sample 5)
Get polypropylene 54% by weight, grafting PP 15%, thermo-stabilizer DSTP 0.5%, antioxidant 3114 0.3%, oxidation inhibitor 619 0.2% is done in super mixer and was mixed 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, low orientation glass 30% adds at the glass mouth, make polypropylene composite material, its process control condition is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Control sample 7(does not add glass fibre and compatilizer in prescription)
Get polypropylene 99%, thermo-stabilizer DSTP 0.5%, antioxidant 3114 0.3%, oxidation inhibitor 619 0.2% by weight and in super mixer, do to mix 3-5 minute, afterwards, again in twin screw extruder through melt extruding, granulation, its technology is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2 minute, and pressure is 12-18MPa.
Performance evaluation mode and implementation standard:
With the particulate material of finishing granulation as stated above in 90～100 ℃ convection oven dry 2～3 hours in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injection moulding machine.
The tensile property test is undertaken by ISO 527-2, and specimen size is 150*10*4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO 179, and specimen size is 80*6*4mm, and notch depth is 1/3rd of a sample thickness; Heat-drawn wire is undertaken by ISO 75, and specimen size is 120*10*3.0mm, and load is 1.8MPa; The thermal-oxidative aging property of material is undertaken by ISO4577, and specimen size is 50*10*10mm, and probe temperature is 150 ℃; The anti-warpage of material is according to range estimation, and specimen size is 150*100*3.2, and test sample guarantees totally complete before test.
Comprehensive mechanical performance is passed through the tensile strength of test gained, elongation at break, and modulus in flexure, the numerical value of thermal denaturation temperature and shock strength is passed judgment on; The thermal-oxidative aging property of material is passed judgment on according to the heat oxygen aging resistance time length of measuring by standard: the time is long more, and the heatproof air aging performance of material is good more; The anti-warpage performance of material, with the mode of range estimation, material is smooth more, and anti-warpage effect is good more.
Sample 1-7 prescription and material property table:
By above table as can be seen, along with the adding of glass, the intensity and the rigidity of material all increase considerably, and the cross section is that the anti-warpage effect of glass of oval low orientation is obviously effective than common glass, and do not influence the aging resistance of material.So this cross section is the good anti-warpage filler of a kind of performance for oval low orientation glass.
Claims (6)
1. an anti-warpage reinforced polypropylene compound material is characterized in that, comprise following component, and the weight proportion of each component is:
Polypropylene 53-89%;
Low orientation glass fibre 5-30%;
Compatilizer 5-15%;
Thermo-stabilizer DSTP 0.1-1.0%;
Antioxidant 3114 0.1-1.0%;
Oxidation inhibitor 619 0.1-0.5%;
Wherein, low orientation glass fibre is that cross section is oval simple glass fiber.
2. anti-warpage reinforced polypropylene compound material according to claim 1 is characterized in that described compatilizer is a graft polypropylene.
3. anti-warpage reinforced polypropylene compound material according to claim 1 is characterized in that, described polypropylene is that homo-polypropylene is or/and co-polypropylene.
4. anti-warpage reinforced polypropylene compound material according to claim 3 is characterized in that the molar content of the ethene in the comonomer of described co-polypropylene is 4-10%.
5. anti-warpage reinforced polypropylene compound material according to claim 1 is characterized in that, described polyacrylic melt flow rate (MFR) is 5-50g/10min under the condition of 230 ℃ * 2.16kg, preferred 5-30g/10min.
6. according to the preparation method of the described anti-warpage reinforced polypropylene compound material of each claim of claim 1-5, may further comprise the steps:
(1) takes by weighing raw material by aforesaid weight proportion: polypropylene, low orientation glass fibre, compatilizer, thermo-stabilizer DSTP, antioxidant 3114 and oxidation inhibitor 619;
(2) the described raw material of step (1) was done in super mixer mixed 3-5 minute;
(3) the mixed raw material of step (2) is placed twin screw extruder, through melt extruding granulation, low orientation glass fibre adds at the glass mouth, make the pellet of anti-warpage reinforced polypropylene compound material, its process control condition is: 180～190 ℃ in a district, 200～210 ℃ in two districts, 200～210 ℃ in three districts, 210～215 ℃ in four districts, 210～215 ℃ in five districts, 210～215 ℃ in six districts, 215～225 ℃ in seven districts, 215～225 ℃ in eight districts, 215～225 ℃ in nine districts, 215～225 ℃ in ten districts; The residence time is 1-2min, and pressure is 12-18MPa.
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| CN2011102409921A CN102250420A (en) | 2011-08-22 | 2011-08-22 | Warpage-resistant reinforced polypropylene composite material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102490335A (en) * | 2011-12-21 | 2012-06-13 | 江苏金波新材料科技有限公司 | Preparation method of novel polyethylene-reinforced composite tubing |
| CN102719071A (en) * | 2012-07-02 | 2012-10-10 | 上海锦湖日丽塑料有限公司 | Buckling deformation-resistant glass fiber reinforced polycarbonate resin and preparation method thereof |
| CN110885495A (en) * | 2019-12-13 | 2020-03-17 | 天津金发新材料有限公司 | Low-emission low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN113045852A (en) * | 2021-04-12 | 2021-06-29 | 苏州润佳高分子材料有限公司 | Low-orientation ABS material |
| CN113429684A (en) * | 2021-06-08 | 2021-09-24 | 金发科技股份有限公司 | Low-warpage reinforced polypropylene composition and preparation method and application thereof |
| CN114736452A (en) * | 2022-03-14 | 2022-07-12 | 天津金发新材料有限公司 | Anti-aging and antistatic polypropylene composition and preparation method and application thereof |
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| CN1696187A (en) * | 2005-06-15 | 2005-11-16 | 上海普利特复合材料有限公司 | Fiber glass enhanced polypropylene material with high ageing ressistance of anti heat and oxygen |
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| CN1696187A (en) * | 2005-06-15 | 2005-11-16 | 上海普利特复合材料有限公司 | Fiber glass enhanced polypropylene material with high ageing ressistance of anti heat and oxygen |
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| 《中国建材报》 20110616 李辉 日东纺推出异形截面玻璃纤维 第0003版 1-6 , * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102490335A (en) * | 2011-12-21 | 2012-06-13 | 江苏金波新材料科技有限公司 | Preparation method of novel polyethylene-reinforced composite tubing |
| CN102719071A (en) * | 2012-07-02 | 2012-10-10 | 上海锦湖日丽塑料有限公司 | Buckling deformation-resistant glass fiber reinforced polycarbonate resin and preparation method thereof |
| CN102719071B (en) * | 2012-07-02 | 2014-12-10 | 上海锦湖日丽塑料有限公司 | Buckling deformation-resistant glass fiber reinforced polycarbonate resin and preparation method thereof |
| CN110885495A (en) * | 2019-12-13 | 2020-03-17 | 天津金发新材料有限公司 | Low-emission low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN110885495B (en) * | 2019-12-13 | 2022-06-14 | 天津金发新材料有限公司 | Low-emission low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN113045852A (en) * | 2021-04-12 | 2021-06-29 | 苏州润佳高分子材料有限公司 | Low-orientation ABS material |
| CN113429684A (en) * | 2021-06-08 | 2021-09-24 | 金发科技股份有限公司 | Low-warpage reinforced polypropylene composition and preparation method and application thereof |
| CN114736452A (en) * | 2022-03-14 | 2022-07-12 | 天津金发新材料有限公司 | Anti-aging and antistatic polypropylene composition and preparation method and application thereof |
| CN114736452B (en) * | 2022-03-14 | 2023-05-09 | 天津金发新材料有限公司 | Aging-resistant and antistatic polypropylene composition and preparation method and application thereof |
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Application publication date: 20111123 |