CN103589053A - Long glass fiber reinforced polypropylene material, and preparation method and application thereof - Google Patents
Long glass fiber reinforced polypropylene material, and preparation method and application thereof Download PDFInfo
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- CN103589053A CN103589053A CN201210288577.8A CN201210288577A CN103589053A CN 103589053 A CN103589053 A CN 103589053A CN 201210288577 A CN201210288577 A CN 201210288577A CN 103589053 A CN103589053 A CN 103589053A
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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
- B29C48/50—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]
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- 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
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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
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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
- B29C48/50—Details of extruders
- B29C48/505—Screws
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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
- B29C48/92—Measuring, controlling or regulating
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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
- 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
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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
- 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
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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 the technical field of high-molecular materials, and discloses a long glass fiber reinforced polypropylene material, and a preparation method and an application thereof. The material is prepared by using the following components, by weight, 80-85 parts of polypropylene, 2.0-3.0 parts of maleic anhydride grafted polypropylene, 13-17 parts of a glass fiber, 0.5-1.5 parts of a coupling agent, 0.75-1.25 parts of a composite antioxidant, 0.5-0.8 parts of a lubricant and 0.1-0.3 parts of a metal deactivator. The invention also discloses a preparation method of the long glass fiber reinforced polypropylene material, and a use of the long glass fiber reinforced polypropylene material in a drum washing machine outer cylinder. The long glass fiber reinforced polypropylene material prepared in the invention has the advantages of excellent poach resistance, high thermal-oxidizing resistance, and good mechanical properties, and can be used in washing machine drum materials.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of long glass fiber-reinforced polypropylene materials, preparation method and application thereof.
Background technology
Compare with rotary drum washing machine, roller washing machine has obvious advantage: 1) wash degree is high.Roller washing machine can be heated to water, makes washing powder bring into play splendid soil removability; 2) wear of clothes is little.Clothing directly contacts with inner core tongue, forms to rub, to beat, as hand washing---the washing effect of Here it is roller washing machine.It has been avoided because impeller high speed rotating current are to the vigorous agitation of clothing, winding, the phenomenon of therefore not tiing knots, and wear of clothes is little, can not be out of shape, and can wash the high-grade clothings such as wool.There will not be woollen sweater at washing back neck, to pack into the situation of shoulder; 3) save water power.Roller washing machine is to reach washing effect by rotary drum, and without relying on a large amount of current to carry out washing work, so it only needs water dilution washing composition, can soak into clothing just passable, therefore reduce water consumption greatly.Conventional laundry apparatus is to rely on to rotate current washing clothes, so water consumption is larger; 4) save washing powder.Because water consumption is few, and roller washing machine can add temperature laundering, and the effect of washing powder can be given full play to, so roller washing machine only needs a small amount of washing powder just can reach desirable wash concentration.
The rotating speed of roller washing machine when dewatering is middling speed 800 ~ 1000r/min left and right, under this speed conditions, the cylinder material of washing machine adopts mineral filled polypropylene or short fiber Reinforced Polypropylene material more, more than but rotating speed reaches 1200r/min, the intensity of short fiber Reinforced Polypropylene material is just difficult to meet the job requirement of cylinder, because long fiber reinforced polypropylene has higher rigidity and toughness, therefore in high rotating speed roller washing machine, adopt long fiber reinforced polypropylene materials abroad more, but the external polyacrylic price of long fiber reinforced is higher, limited the application on roller washing machine at home of this material.
Chinese patent CN91101408 has proposed a kind of modified polypropene making internal drum of washer, and this patent is by secondary granulation after the polyethylene of different performance, polypropylene, SBS blend, and technique is simple, but is difficult to meet the requirement of high rotating speed roller washing machine to the strength of materials.
The polypropylene material that glass strengthens is as a kind of general engineering plastic, it has the performance of high strength, high rigidity, firm shock strength, low density, low warpage creep properties, anti-dynamic fatigue property excellence, because of its cost performance high, be widely used in the structure component such as automobile, household electrical appliances, the materials such as substituted metal, short glass fiber Reinforced Nylon.When but polypropylene is applied to some high standard parts, its water boiling resistance performance and heatproof oxidation performance can just can not meet the demands.Such as the washing machine occurring on present market has high-temperature wash, sterilization and drying function, this makes not only have good mechanical property and intensity for the production of the polypropylene material of washing machine drum, also require to have good water boiling resistance performance and high heatproof oxidation performance energy, therefore all polypropylene articles all must add oxidation inhibitor.Common antioxidant system, as very effective to common non-filling or Reinforced Polypropylene material in antioxidant 1010, irgasfos 168, oxidation inhibitor DSTP collaboration system, but to filling or the effect of Reinforced Polypropylene material is not just very desirable.It is particularly outstanding that fiber glass reinforced polypropylene material seems in this problem.This is because some components that one side glass fibre is contained and some treatment agent components of using when glass is carried out to surface treatment can be accelerated the aging of polypropylene material conventionally; On the other hand in the preparation process of glass fiber reinforced polypropylene material, that people need to add is conventionally a certain amount of, can impel glass and acrylic resin to form the toughener of good interface good bonding effect, as the polypropylene of some organic acid or acid anhydride-grafted functionalization, the compatilizer of these function graftings has very large Conflict effect to the common antioxidant system adding, and has weakened the resist oxygen aging effect of oxidation inhibitor in polypropylene material; In addition, common antioxidant system has certain water-soluble, and in poach process, oxidation inhibitor can constantly be separated out, and oxidation inhibitor remaining in material is fewer and feweri, thereby the antioxidant capacity of material is constantly declined.
Although domestic polypropylene modification manufacturer is many, but due to material prescription and complete processing imperfection also, so the modified polypropylene material that domestic manufacturer produces can be gone up or have a certain distance with foreign material at mechanical property, water boiling resistance performance and heatproof oxidation performance.
Summary of the invention
The problem existing in order to overcome existing fiber glass reinforced polypropylene material, the object of this invention is to provide the long glass fiber-reinforced polypropylene materials that a kind of cost is lower, have excellent mechanical property and water boiling resistance and high resistance thermal oxidation, be exclusively used in high rotating speed outer drum for drum washing machine.
Another object of the present invention is to provide a kind of preparation method of above-mentioned long glass fiber-reinforced polypropylene materials.
The 3rd object of the present invention is to provide a kind of above-mentioned long glass fiber-reinforced polypropylene materials as the purposes of outer drum for drum washing machine.
Technical scheme of the present invention is as follows:
The invention provides a kind of long glass fiber-reinforced polypropylene materials, this material is made by the component that comprises following weight part:
80 ~ 85 parts of polypropylene,
2.0 ~ 3.0 parts of maleic anhydride inoculated polypropylenes,
13 ~ 17 parts, 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 metal passivator.
Described polypropylene is one or more in high crystallization homo-polypropylene or block copolymerization polypropylene, and polyacrylic melt flow rate (MFR) (230 ℃ * 2.16Kg) is 25 ~ 65g/10min, preferably 25 ~ 45g/10min; Wherein: the comonomer of block copolymerization polypropylene is that ethylene-vinyl content is 5 ~ 8mol%, and the degree of crystallinity of high crystallization homo-polypropylene is more than or equal to 75%, and degree of isotacticity is more than or equal to 95%.
The density of described maleic anhydride inoculated polypropylene is 0.89 ~ 0.91g/cm
3, fusing point is 160 ~ 180 ℃, and melt flow rate (MFR) (230 ℃ * 2.16Kg) is 30 ~ 120g/10min, is preferably 60 ~ 100g/10min, and the percentage of grafting of maleic anhydride is 0.5 ~ 1.5%.
Described glass fibre is alkali-free glass fiber, and Fibre diameter is 10 ~ 17 microns, and linear density is 1200 ~ 2400tex.
Described coupling agent is γ-aminopropyl-triethoxyl silane (KH-550).
Described composite antioxidant comprise mass percent be 15 ~ 25% 1,3,5, three (3,5-di-t-butyl, 4-hydroxybenzyl) s-triazine (antioxidant 3114), mass percent are 15 ~ 25% 4, oxidation inhibitor DSTP(thio-2 acid two (18) ester that 4'-thiobis (the 6-tertiary butyl-3-methylphenol) (antioxidant 300), mass percent are 35 ~ 45%) and mass percent three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters (irgasfos 168) that are 15 ~ 25%.
Described lubricant is erucicamide.
Described metal passivator is hydrazide derivatives, is preferably Irganox MD1024.
The pelletizing length of described long glass fiber-reinforced polypropylene materials is 11 ~ 13mm, and particle diameter is 4.5mm.
The present invention also provides a kind of preparation method of above-mentioned long glass fiber-reinforced polypropylene materials, and the method comprises the following steps:
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 of oxidation inhibitor, 0.5 ~ 0.8 part of lubricant and 0.1 ~ 0.5 part of metal passivator are joined in high mixer successively, mixing time is 3 ~ 5 minutes, then mixed material is added in the hopper of forcing machine standby; 13 ~ 17 parts of glass fibre are drawn to (CN1488674 in impregnation mold; publication date: 2004.04.14); glass fibre disperses solvent impregnated resin under the effect of tensioning roller; by the shape size of mouthful mould of selection; adjust engine speed and the rate of feeding of forcing machine simultaneously; it is 13 ~ 17 parts that fibre content is controlled, and adjusts the cutting knife rotating speed of dicing machine, prepares long glass fiber-reinforced polypropylene materials.
Described forcing machine is twin screw extruder, screw diameter is 65mm, the length-to-diameter ratio of screw rod is 40:1, mixed melting Temperature Setting is: 160 ~ 170 ℃ of first paragraphs, 170 ~ 180 ℃ of second segments, the 3rd section 180 ~ 190 ℃, the 4th section 190 ~ 200 ℃, the 5th section 200 ~ 210 ℃, 200 ~ 210 ℃ of melt temperatures, 215 ~ 225 ℃ of head temperatures.
Described impregnation mold temperature is 220 ~ 230 ℃.
The present invention also provides the purposes of a kind of above-mentioned long glass fiber-reinforced polypropylene materials as outer drum for drum washing machine.
Compared with the existing technology, tool has the following advantages and beneficial effect in the present invention:
1, the present invention has used efficient antioxidant systems, and prepared matrix material has excellent water boiling resistance performance and high resistance thermal oxidation.
2, the prepared fiber glass reinforced polypropylene material of the present invention, when guaranteeing excellent water boiling resistance, high resistance thermal oxidation, has good mechanical property, is applicable to being applied to washing machine drum material.
3, the preparation technology of the glass fiber reinforced polypropylene composite material of the present invention's proposition is simple, cost is low.
4, the performance of resulting materials of the present invention has surpassed the performance of domestic and international existing fiber glass reinforced polypropylene material at present, has lower material cost simultaneously.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Polyacrylic melt flow rate (MFR) used (230 ℃ * 2.16Kg) is 25 ~ 65g/10min below; The comonomer of block copolymerization polypropylene is that ethylene-vinyl content is 5 ~ 8mol%, and the degree of crystallinity of high crystallization homo-polypropylene is more than or equal to 75%, and degree of isotacticity is more than or equal to 95%.
The density of maleic anhydride inoculated polypropylene used is 0.89 ~ 0.91g/cm below
3, fusing point is 160 ~ 180 ℃, and melt flow rate (MFR) (230 ℃ * 2.16Kg) is 30 ~ 120g/10min, and the percentage of grafting of maleic anhydride is 0.5 ~ 1.5%.
Glass fibre used is alkali-free glass fiber below, and Fibre diameter is 10 ~ 17 microns, and linear density is 1200 ~ 2400tex.
Performance evaluation mode and implementation standard:
Test conditions: pure water dipping, water temperature: 90 ℃, poach time: 800h, 1600h, 2400h, 3200h;
Poach is put into respectively baking oven and is carried out thermo-oxidative ageing after the above time: aging temperature: 150 ℃, until there is efflorescence in batten.
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 carries 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 high crystallization homo-polypropylene, 2.0 parts of maleic anhydride inoculated polypropylenes, coupling agent KH-5501.0 part, 0.2 part of antioxidant 3114,0.2 part of antioxidant 300,0.4 part of oxidation inhibitor DSTP, 0.2 part of irgasfos 168,0.5 part of lubricant erucicamide, the Irganox MD1024 of 0.2 part of metal passivator Ciba joins in high mixer successively, mixes 3-5min;
Said mixture is joined and in twin screw extruder, carries out fusion plastification, and be injected in impregnation mold;
The continuous glass fibre of 15 parts is drawn in impregnation mold, in the polypropylene miser of melting, disperse after dipping, sizing mouth die drawing by 4.5mm goes out, cross water cooling, dry up the moisture on material strip surface, then be cut into the particle that length is 11 ~ 13mm, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of high rotating speed outer drum for drum washing machine;
Described forcing machine is twin screw extruder, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, mixed melting Temperature Setting is: 160 ~ 170 ℃ of first paragraphs, 170 ~ 180 ℃ of second segments, the 3rd section 180 ~ 190 ℃, the 4th section 190 ~ 200 ℃, the 5th section 200 ~ 210 ℃, 200 ~ 210 ℃ of melt temperatures, 215 ~ 225 ℃ of head temperatures;
Described impregnation mold temperature is 220 ~ 230 ℃;
A kind of above-mentioned long glass fiber-reinforced polypropylene materials is as the purposes of outer drum for drum washing machine.
To the material of the present invention obtaining according to embodiment 1 and existing cylinder material PP-LGF15(KingFa) carry out initial stage basic physical properties confirmation, 90 ℃ of warm water immersion+150 ℃ thermo-oxidative ageings, by the evaluation comparison of following test, confirm the performance of material of the present invention.Same type of material in comparator all can not reach feature of the present invention, so emphasis is tested and compared with external equivalent material the present invention, test method, the following data of test-results reference:
1. the initial stage basic physical properties comparison with external equivalent material by embodiment 1, table 1 result shows: the initial performance of the material that embodiment 1 obtains is better than PP-LGF15(KingFa) material.
Table 1
| Test event | Test condition | Embodiment 1 | PP-LGF15 | |
| 1 | Density (g/cm 3） | RT | 1.0 | 1.0 |
| 2 | Ash content (%) | RT | 15.2 | 16 |
| 3 | Tensile strength (MPa) | RT | 79 | 75 |
| 4 | Flexural strength (MPa) | RT | 102 | 97 |
| 5 | Modulus in flexure (MPa) | RT | 3477 | 3430 |
| 6 | Izod notch shock (kJ/m 2） | RT | 18 | 13 |
| 7 | HDT（1.82MPa，℃） | RT | 157 | 156 |
2. warm water test: test conditions: 90 ℃
Very first time section: 800h; The second time period: 1600h; The 3rd time period: 2400h; The 4th time period: 3200h
3. thermooxidizing test: test conditions: 150 ℃
Respectively the test batten that reaches 800h, 1600h, 2400h, 3200h is put into convection oven, oven temperature is set as 150 ℃, until batten termination test while there is efflorescence carries out testing after status adjustment 16h under RT condition.
By new formula test product and PP-LGF15(KingFa) performance test of material after warm water immersion+thermo-oxidative ageing test of different time, result shows: the performance in each stage of the trial target of new formula is all better than PP-LGF15(KingFa) material.
(1) each stage after 800h warm water immersion+thermooxidizing test, PP-LGF15(KingFa), the stretching of SELSTRAN+PP-GF15 (Ticona) material and new formula test product, bending, shock strength contrast as shown in table 2, according to analyzing under 800h warm water+thermooxidizing, stretching, bending, the shock strength of new formula are all better than PP-LGF15(KingFa) material, performance test comparing result is in Table 2.
Table 2
(2) each stage after 1600h warm water immersion+thermooxidizing test, PP-LGF15(KingFa) stretching of material and new formula test product, bending, shock strength contrast as shown in table 3, according to analyzing under 1600h warm water+thermooxidizing, stretching, bending, the shock strength of new formula are all better than PP-LGF15(KingFa) material, performance test comparing result is in Table 3.
Table 3
(3) each stage after 2400h warm water immersion+thermooxidizing test, PP-LGF15(KingFa) stretching of material and new formula test product, bending, shock strength contrast as shown in table 4, according to analyzing under 2400h warm water+thermooxidizing, stretching, bending, the shock strength of new formula are all better than PP-LGF15(KingFa)) material, performance test comparing result is in Table 4.
Table 4
(4) each stage after 3200h warm water immersion+thermooxidizing test, PP-LGF15(KingFa) and newly stretching, bending, the shock strength of formula test product contrast as shown in table 5, according to analyzing under 3200h warm water+thermooxidizing, stretching, bending, the shock strength of new formula are all better than PP-LGF15(KingFa), the performance test results is in Table 5.
Table 5
Comparative example 1
By 83 parts of polypropylene, 2.0 parts of maleic anhydride inoculated polypropylenes, coupling agent KH-5500.5 part, 0.1 part of antioxidant 3114,0.1 part of antioxidant 300,0.8 part of oxidation inhibitor DSTP, 0.2 part of irgasfos 168,0.5 part of lubricant erucicamide, 0.2 part of metal passivator joins in high mixer successively, mixes 3-5min;
Said mixture is joined and in twin screw extruder, carries out fusion plastification, and be injected in impregnation mold;
The continuous glass fibre of 15 parts is drawn in impregnation mold, in the polypropylene miser of melting, disperse after dipping, sizing mouth die drawing by 4.5mm goes out, cross water cooling, dry up the moisture on material strip surface, then be cut into the particle that length is 11 ~ 13mm, obtain being exclusively used in the long glass fiber-reinforced polypropylene materials of high rotating speed outer drum for drum washing machine;
Described forcing machine is twin screw extruder, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, mixed melting Temperature Setting is: 160 ~ 170 ℃ of first paragraphs, 170 ~ 180 ℃ of second segments, the 3rd section 1800 ~ 190 ℃, the 4th section 190 ~ 200 ℃, the 5th section 200 ~ 210 ℃, 200 ~ 210 ℃ of melt temperatures, 215 ~ 225 ℃ of head temperatures;
Described impregnating equipment temperature is 220 ~ 230 ℃;
The proportioning of adjusting oxidation inhibitor, contrasts the material of comparative example 1 and embodiment 1, and comparing result is as follows:
1. the initial stage basic physical properties comparison with embodiment 1 by comparative example 1, table 6 result shows: the initial performance of the material that comparative example 1 obtains and embodiment 1 material property approach.
Table 6
| Test event | Test condition | Embodiment 1 | Comparative example 1 | |
| 1 | Density (g/cm 3） | RT | 1.0 | 1.0 |
| 2 | Ash content (%) | RT | 15.3 | 15.1 |
| 3 | Tensile strength (MPa) | RT | 81 | 82 |
| 4 | Flexural strength (MPa) | RT | 101 | 99 |
| 5 | Modulus in flexure (MPa) | RT | 3462 | 3455 |
| 6 | Izod notch shock (kJ/m 2） | RT | 18 | 19 |
| 7 | HDT（1.82MPa，℃） | RT | 158 | 156 |
2. warm water test: test conditions: 90 ℃
Very first time section: 800h; The second time period: 1600h; The 3rd time period: 2400h; The 4th time period: 3200h
3. thermooxidizing test: test conditions: 150 ℃
Respectively the test batten that reaches 800h, 1600h, 2400h, 3200h is put into convection oven, oven temperature is set as 150 ℃, until batten termination test while there is efflorescence carries out testing after status adjustment 16h under RT condition.
(1) each stage after 800h warm water immersion+thermooxidizing test, comparative example 1 is as shown in table 7 with stretching, bending, the shock strength contrast of embodiment 1 material, according to analyzing under 800h warm water+thermooxidizing, the stretching of comparative example 1 material, bending, shock strength are all lower than embodiment 1, and the performance test results is in Table 7.
Table 7
(2) each stage after 1600h warm water immersion+thermooxidizing test, comparative example 1 is as shown in table 8 with stretching, bending, the shock strength contrast of embodiment 1, according to analyzing under 1600h warm water+thermooxidizing, the stretching of comparative example 1 material, bending, shock strength are all lower than embodiment 1, and the performance test results is in Table 8.
Table 8
(3) each stage after 2400h warm water immersion+thermooxidizing test, comparative example 1 is as shown in table 10 with stretching, bending, the shock strength contrast of embodiment 1, according to analyzing under 2400h warm water+thermooxidizing, the stretching of comparative example 1 material, bending, shock strength are all lower than embodiment 1, and the performance test results is in Table 9.
Table 9
(4) after 3200h warm water immersion+thermooxidizing test, each stage comparative example 1 is as shown in table 11 with stretching, bending, the shock strength contrast of embodiment 1, according to analyzing under 3200h warm water+thermooxidizing, the stretching of comparative example 1 material, bending, shock strength are all lower than embodiment 1, and the performance test results is in Table 10.
Table 10
By above-described embodiment 1 and the Experimental Comparison of external equivalent material, can find out, adopt the water boiling resistance of the present invention's proposition and the fiber glass reinforced polypropylene material of high resistance thermal oxidation, after test initial stage, poach 800h, 1600h, 2400h, 3200h, thermo-oxidative ageing is to efflorescence, from the time of experience and the performance of test, can find out, material of the present invention has better water boiling resistance and high heatproof air aging performance.
By above-described embodiment 1 and the Experimental Comparison of comparative example 1, can find out, anti-3114 and anti-300 add-on in reduction antioxidant system, even if increase the add-on of oxidation inhibitor DSTP, the antioxidant capacity of material also can obviously weaken, digestion time obviously shortens.
Embodiment 2
By 80 parts of block copolymerization polypropylenes, 3.0 parts of maleic anhydride inoculated polypropylenes, coupling agent KH-5501.5 part, 0.15 part of antioxidant 3114,0.25 part of antioxidant 300,0.3 part of oxidation inhibitor DSTP, 0.15 part of irgasfos 168,0.8 part of lubricant erucicamide, the Irganox MD1024 of 0.1 part of metal passivator Ciba joins in high mixer successively, mixes 3-5min;
Said mixture is joined and in twin screw extruder, carries out fusion plastification, and be injected in impregnation mold;
The continuous glass fibre of 13 parts is drawn in impregnation mold, in the polypropylene miser of melting, disperse after dipping, sizing mouth die drawing by 4.5mm goes out, cross water cooling, dry up the moisture on material strip surface, then be cut into the particle that length is 11 ~ 13mm, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of high rotating speed outer drum for drum washing machine;
Described forcing machine is twin screw extruder, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, mixed melting Temperature Setting is: 160 ~ 170 ℃ of first paragraphs, 170 ~ 180 ℃ of second segments, the 3rd section 180 ~ 190 ℃, the 4th section 190 ~ 200 ℃, the 5th section 200 ~ 210 ℃, 200 ~ 210 ℃ of melt temperatures, 215 ~ 225 ℃ of head temperatures;
Described impregnation mold temperature is 220 ~ 230 ℃.
Embodiment 3
By 85 parts of block copolymerization polypropylenes, 2.5 parts of maleic anhydride inoculated polypropylenes, coupling agent KH-5501.0 part, 0.25 part of antioxidant 3114,0.15 part of antioxidant 300,0.5 part of oxidation inhibitor DSTP, 0.25 part of irgasfos 168,0.6 part of lubricant erucicamide, the Irganox MD1024 of 0.5 part of metal passivator Ciba joins in high mixer successively, mixes 3-5min;
Said mixture is joined and in twin screw extruder, carries out fusion plastification, and be injected in impregnation mold;
The continuous glass fibre of 17 parts is drawn in impregnation mold, in the polypropylene miser of melting, disperse after dipping, sizing mouth die drawing by 4.5mm goes out, cross water cooling, dry up the moisture on material strip surface, then be cut into the particle that length is 11 ~ 13mm, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of high rotating speed outer drum for drum washing machine;
Described forcing machine is twin screw extruder, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, mixed melting Temperature Setting is: 160 ~ 170 ℃ of first paragraphs, 170 ~ 180 ℃ of second segments, the 3rd section 180 ~ 190 ℃, the 4th section 190 ~ 200 ℃, the 5th section 200 ~ 210 ℃, 200 ~ 210 ℃ of melt temperatures, 215 ~ 225 ℃ of head temperatures;
Described impregnation mold temperature is 220 ~ 230 ℃.
Embodiment 4
81 parts high crystallization homo-polypropylene, 2.2 parts of maleic anhydride inoculated polypropylenes, 0.5 part of coupling agent KH-550,0.15 part of antioxidant 3114,0.15 part of antioxidant 300,0.3 part of oxidation inhibitor DSTP, 0.15 part of irgasfos 168,0.7 part of lubricant erucicamide and 0.3 part of metal passivator Irganox MD1024 are joined in high mixer successively, mixing time is 3 ~ 5 minutes, then mixed material is added in the hopper of forcing machine standby;
Said mixture is joined and in twin screw extruder, carries out fusion plastification, and be injected in impregnation mold;
The continuous glass fibre of 14 parts is drawn in impregnation mold, in the polypropylene miser of melting, disperse after dipping, sizing mouth die drawing by 4.5mm goes out, cross water cooling, dry up the moisture on material strip surface, then be cut into the particle that length is 11 ~ 13mm, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of high rotating speed outer drum for drum washing machine;
Forcing machine is twin screw extruder, screw diameter is 65mm, the length-to-diameter ratio of screw rod is 40:1, mixed melting Temperature Setting is: 160 ~ 170 ℃ of first paragraphs, 170 ~ 180 ℃ of second segments, the 3rd section 180 ~ 190 ℃, the 4th section 190 ~ 200 ℃, the 5th section 200 ~ 210 ℃, 200 ~ 210 ℃ of melt temperatures, 215 ~ 225 ℃ of head temperatures.
Impregnation mold temperature is 220 ~ 230 ℃.
Embodiment 5
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 of antioxidant 3114,0.25 part of antioxidant 300,0.5 part of oxidation inhibitor DSTP, 0.25 part of irgasfos 168,0.6 part of lubricant erucicamide and 0.4 part of metal passivator Irganox MD1024 are joined in high mixer successively, mixing time is 3 ~ 5 minutes, then mixed material is added in the hopper of forcing machine standby;
Said mixture is joined and in twin screw extruder, carries out fusion plastification, and be injected in impregnation mold;
The continuous glass fibre of 16 parts is drawn in impregnation mold, in the polypropylene miser of melting, disperse after dipping, sizing mouth die drawing by 4.5mm goes out, cross water cooling, dry up the moisture on material strip surface, then be cut into the particle that length is 11 ~ 13mm, particle diameter is 4.5mm, obtains being exclusively used in the long glass fiber-reinforced polypropylene materials of high rotating speed outer drum for drum washing machine;
Forcing machine is twin screw extruder, screw diameter is 65mm, the length-to-diameter ratio of screw rod is 40:1, mixed melting Temperature Setting is: 160 ~ 170 ℃ of first paragraphs, 170 ~ 180 ℃ of second segments, the 3rd section 180 ~ 190 ℃, the 4th section 190 ~ 200 ℃, the 5th section 200 ~ 210 ℃, 200 ~ 210 ℃ of melt temperatures, 215 ~ 225 ℃ of head temperatures.
Impregnation mold temperature is 220 ~ 230 ℃.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (10)
1. a long glass fiber-reinforced polypropylene materials, is characterized in that: this material is made by the component that comprises following weight part:
80 ~ 85 parts of polypropylene,
2.0 ~ 3.0 parts of maleic anhydride inoculated polypropylenes,
13 ~ 17 parts, 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 metal passivator.
2. long glass fiber-reinforced polypropylene materials according to claim 1, it is characterized in that: described polypropylene is one or more in high crystallization homo-polypropylene or block copolymerization polypropylene, polyacrylic melt flow rate (MFR) is 25 ~ 65g/10min, preferably 25 ~ 45g/10min; Wherein: the comonomer of block copolymerization polypropylene is that ethylene-vinyl content is 5 ~ 8mol%, and the degree of crystallinity of high crystallization homo-polypropylene is more than or equal to 75%, and degree of isotacticity is more than or equal to 95%.
3. long glass fiber-reinforced polypropylene materials according to claim 1, is characterized in that: the density of described maleic anhydride inoculated polypropylene is 0.89 ~ 0.91g/cm
3, fusing point is 160 ~ 180 ℃, and melt flow rate (MFR) is 30 ~ 120g/10min, is preferably 60 ~ 100g/10min, and the percentage of grafting of maleic anhydride is 0.5 ~ 1.5%.
4. long glass fiber-reinforced polypropylene materials according to claim 1, is characterized in that: described glass fibre is alkali-free glass fiber, and Fibre diameter is 10 ~ 17 microns, and linear density is 1200 ~ 2400tex.
5. long glass fiber-reinforced polypropylene materials according to claim 1, is characterized in that: described coupling agent is γ-aminopropyl-triethoxyl silane.
6. long glass fiber-reinforced polypropylene materials according to claim 1, it is characterized in that: described composite antioxidant comprise mass percent be 15 ~ 25% 1,3,5, three (3,5-di-t-butyl, 4-hydroxybenzyl) s-triazine, mass percent are 15 ~ 25% 4, three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester that the oxidation inhibitor DSTP that 4'-thiobis (the 6-tertiary butyl-3-methylphenol), mass percent are 35 ~ 45% and mass percent are 15 ~ 25%.
7. long glass fiber-reinforced polypropylene materials according to claim 1, is characterized in that: described lubricant is erucicamide;
Described metal passivator is hydrazide derivatives, is preferably Irganox MD1024;
The pelletizing length of described long glass fiber-reinforced polypropylene materials is 11 ~ 13mm, and particle diameter is 4.5mm.
8. the preparation method of the arbitrary described long glass fiber-reinforced polypropylene materials of claim 1 to 7, is characterized in that: the method comprises the following steps:
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 of oxidation inhibitor, 0.5 ~ 0.8 part of lubricant and 0.1 ~ 0.5 part of metal passivator are joined in high mixer successively, mixing time is 3 ~ 5 minutes, then mixed material is added in the hopper of forcing machine standby; 13 ~ 17 parts of glass fibre are drawn in impregnation mold; glass fibre disperses solvent impregnated resin under the effect of tensioning roller; by the shape size of mouthful mould of selection; adjust engine speed and the rate of feeding of forcing machine simultaneously; it is 13 ~ 17 parts that fibre content is controlled; the cutting knife rotating speed of adjusting dicing machine, prepares long glass fiber-reinforced polypropylene materials.
9. the preparation method of long glass fiber-reinforced polypropylene materials according to claim 8, it is characterized in that: described forcing machine is twin screw extruder, screw diameter is 65mm, and the length-to-diameter ratio of screw rod is 40:1, and mixed melting Temperature Setting is: 160 ~ 170 ℃ of first paragraphs, 170 ~ 180 ℃ of second segments, the 3rd section 180 ~ 190 ℃, the 4th section 190 ~ 200 ℃, the 5th section 200 ~ 210 ℃, 200 ~ 210 ℃ of melt temperatures, 215 ~ 225 ℃ of head temperatures;
Described impregnation mold temperature is 220 ~ 230 ℃.
10. the arbitrary described long glass fiber-reinforced polypropylene materials of claim 1 to 7 is as the purposes of outer drum for drum washing machine.
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