CN103589053B - A kind of long glass fiber-reinforced polypropylene materials, preparation method and applications - Google Patents

A kind of long glass fiber-reinforced polypropylene materials, preparation method and applications Download PDF

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CN103589053B
CN103589053B CN201210288577.8A CN201210288577A CN103589053B CN 103589053 B CN103589053 B CN 103589053B CN 201210288577 A CN201210288577 A CN 201210288577A CN 103589053 B CN103589053 B CN 103589053B
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glass fiber
parts
reinforced polypropylene
polypropylene
long glass
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CN103589053A (en
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杨桂生
蒋超杰
孙利明
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Hefei Genius New Materials Co Ltd
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Hefei Genius New Materials 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
    • C08L23/12—Polypropene
    • 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
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • 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
    • 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
    • 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
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92609—Dimensions
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
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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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention belongs to technical field of polymer materials, a kind of long glass fiber-reinforced polypropylene materials, preparation method and applications are disclosed.The material is made up of the component including following weight portion：80 ~ 85 parts of polypropylene, 2.0 ~ 3.0 parts of maleic anhydride inoculated polypropylene, 13 ~ 17 parts of glass fibre, 0.5 ~ 1.5 part of coupling agent, 0.75 ~ 1.25 part of composite antioxidant, 0.5 ~ 0.8 part of lubricant, 0.1 ~ 0.3 part of matal deactivator.Preparation method and above-mentioned long glass fiber-reinforced polypropylene materials the invention also discloses above-mentioned long glass fiber-reinforced polypropylene materials are used as the purposes of outer drum for drum washing machine.Fiber glass reinforced polypropylene material obtained by the present invention, with good mechanical property, is suitably applied washing machine drum material while excellent water boiling resistance, thermal oxidation resistance performance high is ensured.

Description

A kind of long glass fiber-reinforced polypropylene materials, preparation method and applications
Technical field
The invention belongs to technical field of polymer materials, be related to a kind of long glass fiber-reinforced polypropylene materials, preparation method and Its application.
Background technology
Compared with rotary drum washing machine, roller washing machine has clear advantage：1）Wash degree is high.Roller washing machine can be right Water is heated, and washing powder is played splendid dirt-removing power；2）Wear of clothes is small.Clothing is directly contacted with inner cylinder tongue, Formation is rubbed, beaten, such as hand washing --- here it is the clean result of roller washing machine.It is avoided because impeller rotates at a high speed water Vigorous agitation, the winding to clothing, therefore phenomenon of not tiing knots are flowed, wear of clothes is small, will not deform, and can wash wool contour Shelves clothing.Be not in that neckline packs into the situation of shoulder to woollen sweater after washing；3）Save water power.Roller washing machine is by turning Dynamic roller reaches clean result, and without carry out washing work by substantial amounts of current, so it only needs water to dilute wash Agent, can be impregnated with clothing just can be with, therefore can greatly save water consumption.Conventional laundry apparatus are by rotation current washing clothing Thing, therefore water consumption is than larger；4）Save washing powder.Because water consumption is few, and roller washing machine can heat washing, laundry Effect of powder can be given full play to, therefore roller washing machine only needs a small amount of washing powder just to reach preferable wash concentration.
Rotating speed of the roller washing machine in dehydration is middling speed in 800 ~ 1000r/min or so, under this speed conditions, is washed Mineral filled polypropylene or short fiber reinforced polypropylene material are used the roller material of clothing machine more, but rotating speed reaches 1200r/ More than min, the intensity of short fiber reinforced polypropylene material is difficult to meet the job requirement of roller, due to long fiber reinforced polypropylene tool There is rigidity and toughness higher, therefore foreign countries are more using long fiber reinforced polypropylene material in rotating speed roller washing machine high, but The external polyacrylic price of long fiber reinforced is higher, limits application of the material at home on roller washing machine.
Chinese patent CN91101408 proposes a kind of modified polypropene making internal drum of washer, and the patent is by different performance Secondary granulation, process is simple, it can be difficult to it is strong to material to meet rotating speed roller washing machine high after polyethylene, polypropylene, SBS blendings The requirement of degree.
Used as a kind of general engineering plastic, it has high intensity, high rigidity, just impact strong to the polypropylene material of fiberglass reinforced The excellent performance of degree, low-density, low warpage creep properties, anti-dynamic fatigue property, because its cost performance is high, be widely used in automobile, The materials such as the structural elements such as household electrical appliances, substituted metal, short glass fiber enhancing nylon.But polypropylene is applied to some high standard quasi-components When, its water boiling resistance performance and heatproof oxidation performance can cannot meet requirement.The washing machine for such as occurring currently on the market has height Temperature laundering, sterilization and drying function, this causes not only there is good mechanics for the polypropylene material for producing washing machine drum Performance and intensity, it is also desirable to have good water boiling resistance performance and heatproof oxidation performance energy high, therefore all of polypropylene articles Antioxidant must all be added.Common antioxidant system, such as antioxidant 1010, irgasfos 168, antioxidant DSTP collaboration systems are to general Logical non-filling or RPP material is highly effective, but is not just to manage very much to filling or the effect of RPP material Think.Fiber glass reinforced polypropylene material seems especially prominent in this problem.Because, contained by one side glass fibre Some components and some the inorganic agent components used when being surface-treated to glass would generally accelerate polypropylene material It is aging；On the other hand in the preparation process of glass fiber reinforced polypropylene material, people generally need add it is a certain amount of, Can promote glass that the reinforcing agent of good interface good bonding effect, such as some organic acids or acid anhydrides are formed with acrylic resin Graft-functionalized polypropylene, the compatilizer of these function graftings has very big conflict to make the common antioxidant system for adding With, reduce antioxidant in polypropylene material resist oxygen aging effect；In addition, common antioxidant system have it is certain water-soluble Property, antioxidant can be separated out constantly during water is boiled, and the antioxidant of remaining is fewer and feweri in material, so that the antioxygen of material Ability constantly declines.
Although the comparing of domestic polypropylene modification manufacturer is more, due to material prescription and processing technology also imperfection, Therefore the modified polypropylene material of domestic manufacturer's production can be gone up or with state in mechanical property, water boiling resistance performance and heatproof oxidation performance Outer material has a certain distance.
The content of the invention
For the problem for overcoming existing fiber glass reinforced polypropylene material to exist, it is an object of the invention to provide a kind of cost compared with Long glass fiber-reinforced polypropylene materials low, with excellent mechanical property and water boiling resistance and thermal oxidation resistance performance high, are exclusively used in Rotating speed outer drum for drum washing machine high.
It is a further object to provide a kind of preparation method of above-mentioned long glass fiber-reinforced polypropylene materials.
Third object of the present invention is to provide a kind of above-mentioned long glass fiber-reinforced polypropylene materials as outside roller washing machine The purposes of bucket.
Technical scheme is as follows：
The invention provides a kind of long glass fiber-reinforced polypropylene materials, the material is by the component system including following weight portion Into：
80 ~ 85 parts of polypropylene,
2.0 ~ 3.0 parts of maleic anhydride inoculated polypropylene,
13 ~ 17 parts of glass fibre,
0.5 ~ 1.5 part of coupling agent,
0.75 ~ 1.25 part of composite antioxidant,
0.5 ~ 0.8 part of lubricant,
0.1 ~ 0.3 part of matal deactivator.
Described polypropylene is one or more in highly crystalline HOPP or block copolymerization polypropylene, poly- third The melt flow rate (MFR) of alkene（230℃×2.16Kg）It is 25 ~ 65g/10min, preferably 25 ~ 45g/10min；Wherein：Block copolymerization Polyacrylic comonomer is that ethylene-vinyl content is 5 ~ 8mol%, and the crystallinity of highly crystalline HOPP is more than or equal to 75%, isotacticity is more than or equal to 95%.
The density of described maleic anhydride inoculated polypropylene is 0.89 ~ 0.91g/cm3, fusing point is 160 ~ 180 DEG C, melt flow Dynamic speed（230℃×2.16Kg）It is 30 ~ 120g/10min, preferably 60 ~ 100g/10min, the grafting rate of maleic anhydride is 0.5~1.5%。
Described glass fibre is alkali-free glass fiber, and fibre diameter is 10 ~ 17 microns, and line density is 1200 ~ 2400tex.
Described coupling agent is γ-aminopropyl-triethoxysilane（KH-550）.
Described composite antioxidant includes 1,3,5 that mass percent is 15 ~ 25%, three (3,5- di-t-butyls, 4-hydroxyl Benzyl) s-triazine（Antioxidant 3114）, mass percent for 15 ~ 25% 4,4'- thiobis (the 6- tert-butyl group -3- methylphenols) （Antioxidant 300）, mass percent for 35 ~ 45% antioxidant DSTP（Thio-2 acid two (18) ester）And mass percent It is 15 ~ 25% three ［ 2.4- di-tert-butyl-phenyls ］ phosphite esters（Irgasfos 168）.
Described lubricant is erucyl amide.
Described matal deactivator is hydrazide derivatives, preferably Irganox MD1024.
The pelletizing length of described long glass fiber-reinforced polypropylene materials is 11 ~ 13mm, and particle diameter is 4.5mm.
Present invention also offers a kind of preparation method of above-mentioned long glass fiber-reinforced polypropylene materials, the method includes following step Suddenly：
80 ~ 85 parts of polypropylene, 2 ~ 3 parts of maleic anhydride inoculated polypropylenes, 0.5 ~ 1.5 part of coupling agent, 0.75 ~ 1.25 part are resisted Oxygen agent, 0.5 ~ 0.8 part of lubricant and 0.1 ~ 0.5 part of matal deactivator are added sequentially in high mixer, and mixing time is 3 ~ 5 points , then be added to for mixed material standby in the hopper of extruder by clock；13 ~ 17 parts of glass fibres are drawn in impregnation mold （CN1488674, publication date：2004.04.14）, glass fibre disperses impregnating resin in the presence of jockey pulley, by selection The size of mouth mold of shaping, while adjusting the engine speed and rate of feeding of extruder, fiber content is controlled to 13 ~ 17 parts, adjustment The cutter rotating velocity of pelleter, prepares long glass fiber-reinforced polypropylene materials.
Described extruder is double screw extruder, and screw diameter is 65mm, and the draw ratio of screw rod is 40：1, mixed melting Temperature is set as：160 ~ 170 DEG C of first paragraph, 170 ~ 180 DEG C of second segment, the 3rd section 180 ~ 190 DEG C, the 4th section 190 ~ 200 DEG C, the Five sections 200 ~ 210 DEG C, 200 ~ 210 DEG C of melt temperature, 215 ~ 225 DEG C of head temperature.
Described impregnation mold temperature is 220 ~ 230 DEG C.
Present invention also offers the purposes that a kind of above-mentioned long glass fiber-reinforced polypropylene materials are used as outer drum for drum washing machine.
The present invention compared with the existing technology, has the following advantages that and beneficial effect：
1st, present invention uses efficient antioxidant systems, obtained composite have excellent water boiling resistance performance and Thermal oxidation resistance performance high.
2nd, the fiber glass reinforced polypropylene material obtained by the present invention is ensureing excellent water boiling resistance, thermal oxidation resistance performance high While, with good mechanical property, it is suitably applied washing machine drum material.
3rd, the preparation process is simple of glass fiber reinforced polypropylene composite material proposed by the present invention, low cost.
4th, the performance of resulting materials of the present invention alreadys exceed at present the performance of existing fiber glass reinforced polypropylene material both at home and abroad, There is lower material cost simultaneously.
Specific embodiment
The present invention is further illustrated with reference to embodiments.
Polyacrylic melt flow rate (MFR) used below（230℃×2.16Kg）It is 25 ~ 65g/10min；Block copolymerization Polyacrylic comonomer is that ethylene-vinyl content is 5 ~ 8mol%, and the crystallinity of highly crystalline HOPP is more than or equal to 75%, isotacticity is more than or equal to 95%.
The density of maleic anhydride inoculated polypropylene used below is 0.89 ~ 0.91g/cm3, fusing point is 160 ~ 180 DEG C, is melted Body flow rate（230℃×2.16Kg）It is 30 ~ 120g/10min, the grafting rate of maleic anhydride is 0.5 ~ 1.5%.
Glass fibre used below be alkali-free glass fiber, fibre diameter be 10 ~ 17 microns, line density be 1200 ~ 2400tex。
Performance evaluation mode and implementation standard：
Experimental condition：Pure water impregnates, water temperature：90 DEG C, water boils the time：800h、1600h、2400h、3200h；
Water to be boiled be respectively put into after the above time and carry out thermo-oxidative ageing in baking oven：Aging temperature：150 DEG C, until batten occurs Untill efflorescence.
Tensile property test is carried out according to ASTM D638, draw speed 5mm/min, gauge length 40mm, batten size：Total length 175mm, parallel portion：10mm×4mm；Crooked test is carried out according to ASTM D790, rate of bending 5mm/min, span 100mm, Batten size：127mm×12.7mm×6.4mm；Impact property test is carried out according to ASTM D256, batten size：80mm× 10mm×4mm（Molding breach）.
Embodiment 1
By 83 parts of highly crystalline HOPP, 2.0 parts of maleic anhydride inoculated polypropylene, coupling agent KH-5501.0 parts, antioxygen 31140.2 parts of agent, 0.2 part of antioxidant 300,0.4 part of antioxidant DSTP, 0.2 part of irgasfos 168, lubricant erucyl amide 0.5 Part, the Irganox MD1024 of 0.2 part of matal deactivator Ciba are added sequentially in high mixer, mix 3-5min；
Said mixture is added in double screw extruder carries out fusion plastification, and is injected into impregnation mold；
15 parts of continuous glass fibre is drawn in impregnation mold, dipping is disperseed in the polypropylene miser of melting Afterwards, pulled out by the sizing mouth mold of 4.5mm, cross water cooling, the moisture on drying material strip surface is then cut into length for 11 ~ 13mm Particle, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of rotating speed outer drum for drum washing machine high；
Described extruder is double screw extruder, and screw diameter 65mm, the draw ratio of screw rod is 40：1, mixed melting temperature Degree is set as：160 ~ 170 DEG C of first paragraph, 170 ~ 180 DEG C of second segment, the 3rd section 180 ~ 190 DEG C, the 4th section of 190 ~ 200 DEG C, the 5th 200 ~ 210 DEG C of section, 200 ~ 210 DEG C of melt temperature, 215 ~ 225 DEG C of head temperature；
Described impregnation mold temperature is 220 ~ 230 DEG C；
A kind of above-mentioned long glass fiber-reinforced polypropylene materials are used as the purposes of outer drum for drum washing machine.
To the material of the present invention and existing roller material PP-LGF15 that are obtained according to embodiment 1（KingFa）Carry out Initial stage basic physical properties confirm ,+150 DEG C of thermo-oxidative ageings of 90 DEG C of warm water immersions, and this hair is confirmed by the evaluation comparison of tests below The performance of bright material.The features of the present invention, therefore emphasis can not be reached to the present invention and state through the same type of material in comparator Outer equivalent material carries out experiment comparing, and test method, result of the test are with reference to following data：
1. compared with the initial stage basic physical properties of external equivalent material by embodiment 1, the result of table 1 shows：Embodiment 1 is obtained Material initial performance be better than PP-LGF15（KingFa）Material.
Table 1
Test event Test condition Embodiment 1 PP-LGF15
1 Density（g/cm3） RT 1.0 1.0
2 Ash content（%） RT 15.2 16
3 Tensile strength（MPa） RT 79 75
4 Bending strength（MPa） RT 102 97
5 Bending modulus（MPa） RT 3477 3430
6 Izod notch shocks（kJ/m2） RT 18 13
7 HDT（1.82MPa, DEG C） RT 157 156
2. warm water experiment：Experimental condition：90℃
First time period：800h；Second time period：1600h；3rd time period：2400h；4th time period：3200h
3. thermal oxide experiment：Experimental condition：150℃
The experiment batten for being up to 800h, 1600h, 2400h, 3200h respectively is put into convection oven, oven temperature setting It it is 150 DEG C, termination test when efflorescence occurs in batten is tested after carrying out status adjustment 16h under the conditions of RT.
By new formula test product and PP-LGF15（KingFa）Warm water immersion+thermo-oxidative ageing examination of the material in different time Performance test after testing, as a result shows：The performance in each stage of the trial target of new formula is superior to PP-LGF15（KingFa） Material.
（1）Each stage, PP-LGF15 after 800h warm water immersions+thermal oxide experiment（KingFa）、SELSTRAN+PP- The stretching of GF15 (Ticona) materials and new formula test product, bending, impact strength contrast are as shown in table 2, are existed according to analysis Under 800h warm water+thermal oxide, the stretching of new formula, bending, impact strength are superior to PP-LGF15（KingFa）Material, performance is surveyed Examination comparing result is shown in Table 2.
Table 2
（2）Each stage, PP-LGF15 after 1600h warm water immersions+thermal oxide experiment（KingFa）Material and new formula examination Test stretching, bending, the impact strength contrast of product as shown in table 3, according to analysis under 1600h warm water+thermal oxide, the drawing of new formula Stretch, bend, impact strength is superior to PP-LGF15（KingFa）Material, performance test comparing result is shown in Table 3.
Table 3
（3）Each stage, PP-LGF15 after 2400h warm water immersions+thermal oxide experiment（KingFa）Material and new formula examination Test stretching, bending, the impact strength contrast of product as shown in table 4, according to analysis under 2400h warm water+thermal oxide, the drawing of new formula Stretch, bend, impact strength is superior to PP-LGF15（KingFa）) material, performance test comparing result is shown in Table 4.
Table 4
（4）Each stage, PP-LGF15 after 3200h warm water immersions+thermal oxide experiment（KingFa）With new formula test product Stretching, bending, impact strength contrast it is as shown in table 5, according to analysis under 3200h warm water+thermal oxide, the stretching of new formula, Bending, impact strength are superior to PP-LGF15（KingFa）, the performance test results are shown in Table 5.
Table 5
Comparative example 1
By 83 parts of polypropylene, 2.0 parts of maleic anhydride inoculated polypropylene, coupling agent KH-5500.5 parts, antioxidant 3114 0.1 Part, 0.1 part of antioxidant 300,0.8 part of antioxidant DSTP, 0.2 part of irgasfos 168,0.5 part of lubricant erucyl amide, metallic blunt 0.2 part of agent is added sequentially in high mixer, mixes 3-5min；
Said mixture is added in double screw extruder carries out fusion plastification, and is injected into impregnation mold；
15 parts of continuous glass fibre is drawn in impregnation mold, dipping is disperseed in the polypropylene miser of melting Afterwards, pulled out by the sizing mouth mold of 4.5mm, cross water cooling, the moisture on drying material strip surface is then cut into length for 11 ~ 13mm Particle, obtain being exclusively used in the long glass fiber-reinforced polypropylene materials of rotating speed outer drum for drum washing machine high；
Described extruder is double screw extruder, and screw diameter 65mm, the draw ratio of screw rod is 40：1, mixed melting temperature Degree is set as：160 ~ 170 DEG C of first paragraph, 170 ~ 180 DEG C of second segment, the 3rd section 1800 ~ 190 DEG C, the 4th section 190 ~ 200 DEG C, the Five sections 200 ~ 210 DEG C, 200 ~ 210 DEG C of melt temperature, 215 ~ 225 DEG C of head temperature；
Described impregnating equipment temperature is 220 ~ 230 DEG C；
The proportioning of antioxidant is adjusted, the material of comparative example 1 is contrasted with embodiment 1, comparing result is as follows：
1. compared with the initial stage basic physical properties of embodiment 1 by comparative example 1, the result of table 6 shows：The material that comparative example 1 is obtained The initial performance of material is approached with the material property of embodiment 1.
Table 6
Test event Test condition Embodiment 1 Comparative example 1
1 Density（g/cm3） RT 1.0 1.0
2 Ash content（%） RT 15.3 15.1
3 Tensile strength（MPa） RT 81 82
4 Bending strength（MPa） RT 101 99
5 Bending modulus（MPa） RT 3462 3455
6 Izod notch shocks（kJ/m2） RT 18 19
7 HDT（1.82MPa, DEG C） RT 158 156
2. warm water experiment：Experimental condition：90℃
First time period：800h；Second time period：1600h；3rd time period：2400h；4th time period：3200h
3. thermal oxide experiment：Experimental condition：150℃
The experiment batten for being up to 800h, 1600h, 2400h, 3200h respectively is put into convection oven, oven temperature setting It it is 150 DEG C, termination test when efflorescence occurs in batten is tested after carrying out status adjustment 16h under the conditions of RT.
（1）Each stage after the experiment of 800h warm water immersions+thermal oxide, the stretching of comparative example 1 and the material of embodiment 1, bending, Impact strength contrast is as shown in table 7, according to analysis under 800h warm water+thermal oxide, the stretching of the material of comparative example 1, bending, impact Intensity is below embodiment 1, and the performance test results are shown in Table 7.
Table 7
（2）Each stage after 1600h warm water immersions+thermal oxide experiment, the stretching of comparative example 1 and embodiment 1, bending, punching Hit intensity contrast is as shown in table 8, according to analysis under 1600h warm water+thermal oxide, the stretching of the material of comparative example 1, bending, impact Intensity is below embodiment 1, and the performance test results are shown in Table 8.
Table 8
（3）Each stage after 2400h warm water immersions+thermal oxide experiment, the stretching of comparative example 1 and embodiment 1, bending, punching Hit intensity contrast is as shown in table 10, according to analysis under 2400h warm water+thermal oxide, the stretching of the material of comparative example 1, bending, impact Intensity is below embodiment 1, and the performance test results are shown in Table 9.
Table 9
（4）Stretching, bending, the impact of each phase contrast's example 1 and embodiment 1 after 3200h warm water immersions+thermal oxide experiment As shown in table 11, according to analysis under 3200h warm water+thermal oxide, the stretching of the material of comparative example 1, bending, impact are strong for intensity contrast Degree is below embodiment 1, and the performance test results are shown in Table 10.
Table 10
Be can be seen that using proposed by the present invention water-fast with the Experimental Comparison of external equivalent material by above-described embodiment 1 The fiber glass reinforced polypropylene material with thermal oxidation resistance performance high is boiled, 800h, 1600h, 2400h, 3200h are boiled in experiment initial stage, water Thermo-oxidative ageing can be seen that material of the invention with more preferable resistance to efflorescence from the time experienced and the performance of test afterwards Water is boiled and heatproof air aging performance high.
Be can be seen that by the Experimental Comparison of above-described embodiment 1 and comparative example 1 and resist 3114 in reduction antioxidant system and resist 300 addition, even if increasing the addition of antioxidant DSTP, the antioxidant capacity of material also can substantially weaken, and ageing time is bright It is aobvious to shorten.
Embodiment 2
By 80 parts of block copolymerization polypropylene, 3.0 parts of maleic anhydride inoculated polypropylene, coupling agent KH-5501.5 parts, antioxidant 31140.15 parts, 0.25 part of antioxidant 300,0.3 part of antioxidant DSTP, 0.15 part of irgasfos 168, lubricant erucyl amide 0.8 Part, the Irganox MD1024 of 0.1 part of matal deactivator Ciba are added sequentially in high mixer, mix 3-5min；
Said mixture is added in double screw extruder carries out fusion plastification, and is injected into impregnation mold；
13 parts of continuous glass fibre is drawn in impregnation mold, dipping is disperseed in the polypropylene miser of melting Afterwards, pulled out by the sizing mouth mold of 4.5mm, cross water cooling, the moisture on drying material strip surface is then cut into length for 11 ~ 13mm Particle, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of rotating speed outer drum for drum washing machine high；
Described extruder is double screw extruder, and screw diameter 65mm, the draw ratio of screw rod is 40：1, mixed melting temperature Degree is set as：160 ~ 170 DEG C of first paragraph, 170 ~ 180 DEG C of second segment, the 3rd section 180 ~ 190 DEG C, the 4th section of 190 ~ 200 DEG C, the 5th 200 ~ 210 DEG C of section, 200 ~ 210 DEG C of melt temperature, 215 ~ 225 DEG C of head temperature；
Described impregnation mold temperature is 220 ~ 230 DEG C.
Embodiment 3
By 85 parts of block copolymerization polypropylene, 2.5 parts of maleic anhydride inoculated polypropylene, coupling agent KH-5501.0 parts, antioxidant 31140.25 parts, 0.15 part of antioxidant 300,0.5 part of antioxidant DSTP, 0.25 part of irgasfos 168, lubricant erucyl amide 0.6 Part, the Irganox MD1024 of 0.5 part of matal deactivator Ciba are added sequentially in high mixer, mix 3-5min；
Said mixture is added in double screw extruder carries out fusion plastification, and is injected into impregnation mold；
17 parts of continuous glass fibre is drawn in impregnation mold, dipping is disperseed in the polypropylene miser of melting Afterwards, pulled out by the sizing mouth mold of 4.5mm, cross water cooling, the moisture on drying material strip surface is then cut into length for 11 ~ 13mm Particle, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of rotating speed outer drum for drum washing machine high；
Described extruder is double screw extruder, and screw diameter 65mm, the draw ratio of screw rod is 40：1, mixed melting temperature Degree is set as：160 ~ 170 DEG C of first paragraph, 170 ~ 180 DEG C of second segment, the 3rd section 180 ~ 190 DEG C, the 4th section of 190 ~ 200 DEG C, the 5th 200 ~ 210 DEG C of section, 200 ~ 210 DEG C of melt temperature, 215 ~ 225 DEG C of head temperature；
Described impregnation mold temperature is 220 ~ 230 DEG C.
Embodiment 4
By 81 parts of highly crystalline HOPPs, 2.2 parts of maleic anhydride inoculated polypropylenes, 0.5 part of coupling agent KH-550,0.15 Part antioxidant 3114,0.15 part of antioxidant 300,0.3 part of antioxidant DSTP, 0.15 part of irgasfos 168,0.7 part of lubricant erucic acid Acid amides and 0.3 part of matal deactivator Irganox MD1024 are added sequentially in high mixer, and mixing time is 3 ~ 5 minutes, then Mixed material is added to standby in the hopper of extruder；
Said mixture is added in double screw extruder carries out fusion plastification, and is injected into impregnation mold；
14 parts of continuous glass fibre is drawn in impregnation mold, dipping is disperseed in the polypropylene miser of melting Afterwards, pulled out by the sizing mouth mold of 4.5mm, cross water cooling, the moisture on drying material strip surface is then cut into length for 11 ~ 13mm Particle, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of rotating speed outer drum for drum washing machine high；
Extruder is double screw extruder, and screw diameter is 65mm, and the draw ratio of screw rod is 40：1, mixed melting temperature sets It is set to：160 ~ 170 DEG C of first paragraph, 170 ~ 180 DEG C of second segment, the 3rd section 180 ~ 190 DEG C, the 4th section 190 ~ 200 DEG C, the 5th section 200 ~ 210 DEG C, 200 ~ 210 DEG C of melt temperature, 215 ~ 225 DEG C of head temperature.
Impregnation mold temperature is 220 ~ 230 DEG C.
Embodiment 5
By 82 parts of block copolymerization polypropylenes, 2.6 parts of maleic anhydride inoculated polypropylenes, 1.2 parts of coupling agent KH-550,0.25 part Antioxidant 3114,0.25 part of antioxidant 300,0.5 part of antioxidant DSTP, 0.25 part of irgasfos 168,0.6 part of lubricant erucic acid acyl Amine and 0.4 part of matal deactivator Irganox MD1024 are added sequentially in high mixer, and mixing time is 3 ~ 5 minutes, then will Mixed material is added to standby in the hopper of extruder；
Said mixture is added in double screw extruder carries out fusion plastification, and is injected into impregnation mold；
16 parts of continuous glass fibre is drawn in impregnation mold, dipping is disperseed in the polypropylene miser of melting Afterwards, pulled out by the sizing mouth mold of 4.5mm, cross water cooling, the moisture on drying material strip surface is then cut into length for 11 ~ 13mm Particle, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of rotating speed outer drum for drum washing machine high；
Extruder is double screw extruder, and screw diameter is 65mm, and the draw ratio of screw rod is 40：1, mixed melting temperature sets It is set to：160 ~ 170 DEG C of first paragraph, 170 ~ 180 DEG C of second segment, the 3rd section 180 ~ 190 DEG C, the 4th section 190 ~ 200 DEG C, the 5th section 200 ~ 210 DEG C, 200 ~ 210 DEG C of melt temperature, 215 ~ 225 DEG C of head temperature.
Impregnation mold temperature is 220 ~ 230 DEG C.
The above-mentioned description to embodiment is to be understood that and apply this hair for ease of those skilled in the art It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here Example, those skilled in the art's announcement of the invention, not departing from improvement that scope made and modification all should be Within protection scope of the present invention.

Claims (4)

1. a kind of long glass fiber-reinforced polypropylene materials, it is characterised in that：The material includes the component of following weight portion：
Described polypropylene is one or more of highly crystalline HOPP or block copolymerization polypropylene, polyacrylic melt flow Dynamic speed is 25~45g/10min；Wherein：The comonomer of block copolymerization polypropylene be ethene, contents of ethylene be 5~ 8mol%, the crystallinity of highly crystalline HOPP is more than or equal to 75%, and isotacticity is more than or equal to 95%；
The density of described maleic anhydride inoculated polypropylene is 0.89~0.91g/cm3, fusing point is 160~180 DEG C, melt flows Speed is 60~100g/10min, and the grafting rate of maleic anhydride inoculated polypropylene is 0.5~1.5%；
Described glass fibre is alkali-free glass fibre, and fibre diameter is 10~17 microns, and line density is 1200~2400tex；
Described composite antioxidant includes 1,3,5- tri- (3,5- di-t-butyls, 4- hydroxyl benzyls that mass percent is 15~25% Base) s-triazine, the 4,4'- thiobis (the 6- tert-butyl group -3- methylphenols) that mass percent is 15~25%, mass percent be 35~45% antioxidant DSTP and mass percent is 15~25% three [2,4- di-tert-butyl-phenyls] phosphite esters；
Described coupling agent is γ-aminopropyl-triethoxysilane；
The preparation method of described long glass fiber-reinforced polypropylene materials is comprised the following steps：
By 80~85 parts of polypropylene, 2.0~3.0 parts of maleic anhydride inoculated polypropylenes, 0.5~1.5 part of coupling agent, 0.75~1.25 Part composite antioxidant, 0.5~0.8 part of lubricant and 0.1~0.3 part of matal deactivator are added sequentially in high-speed mixer, are mixed The material time is 3~5 minutes, is then added to mixed material standby in the hopper of extruder；13~17 parts of glass fibres are led In guiding to impregnation mold so that glass fibre disperses impregnating resin in the presence of jockey pulley, by the chi for selecting sizing mouth mold It is very little, while adjusting the engine speed and rate of feeding of extruder so that content of glass fiber is controlled to 13~17 parts, adjustment extrusion The cutter rotating velocity of the pelleter of machine, prepares described long glass fiber-reinforced polypropylene materials；
Described extruder is double screw extruder, and screw diameter is 65mm, and the draw ratio of screw rod is 40：1, mixed melting temperature It is set as：160~170 DEG C of first paragraph, 170~180 DEG C of second segment, the 3rd section 180~190 DEG C, the 4th section 190~200 DEG C, the Five sections 200~210 DEG C, 200~210 DEG C of melt temperature, 215~225 DEG C of head temperature；
Described impregnation mold temperature is 220~230 DEG C；
Described long glass fiber-reinforced polypropylene materials as outer drum for drum washing machine material application.
2. long glass fiber-reinforced polypropylene materials according to claim 1, it is characterised in that：Described lubricant is erucic acid acyl Amine；
Described matal deactivator is hydrazide derivatives；
The pelletizing length of described long glass fiber-reinforced polypropylene materials is 11~13mm, and particle diameter is 4.5mm.
3. long glass fiber-reinforced polypropylene materials according to claim 1, it is characterised in that：Described matal deactivator is Irganox MD1024。
4. a kind of preparation method of long glass fiber-reinforced polypropylene materials as described in any one of claims 1 to 3, its feature exists In：The method is comprised the following steps：
By 80~85 parts of polypropylene, 2.0~3.0 parts of maleic anhydride inoculated polypropylenes, 0.5~1.5 part of coupling agent, 0.75~1.25 Part composite antioxidant, 0.5~0.8 part of lubricant and 0.1~0.3 part of matal deactivator are added sequentially in high-speed mixer, are mixed The material time is 3~5 minutes, is then added to mixed material standby in the hopper of extruder；13~17 parts of glass fibres are led In guiding to impregnation mold so that glass fibre disperses impregnating resin in the presence of jockey pulley, by the chi for selecting sizing mouth mold It is very little, while adjusting the engine speed and rate of feeding of extruder so that content of glass fiber is controlled to 13~17 parts, adjustment extrusion The cutter rotating velocity of the pelleter of machine, prepares described long glass fiber-reinforced polypropylene materials；
Described extruder is double screw extruder, and screw diameter is 65mm, and the draw ratio of screw rod is 40：1, mixed melting temperature It is set as：160~170 DEG C of first paragraph, 170~180 DEG C of second segment, the 3rd section 180~190 DEG C, the 4th section 190~200 DEG C, the Five sections 200~210 DEG C, 200~210 DEG C of melt temperature, 215~225 DEG C of head temperature；
Described impregnation mold temperature is 220~230 DEG C.
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