CN103788470A - Long glass fiber-reinforced polypropylene composition product - Google Patents
Long glass fiber-reinforced polypropylene composition product Download PDFInfo
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- CN103788470A CN103788470A CN201210424913.7A CN201210424913A CN103788470A CN 103788470 A CN103788470 A CN 103788470A CN 201210424913 A CN201210424913 A CN 201210424913A CN 103788470 A CN103788470 A CN 103788470A
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- 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
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Abstract
The invention relates to a long glass fiber-reinforced polypropylene composition product. The product comprises polypropylene, long glass fiber processed by a coupling agent, an anti-oxidant and a compatilizer, in the product, the ratio of length of the long glass fiber processed by the coupling agent to length of the product is 0.1-1:1, the cantilever beam impact strength of the product is 280-780J/m, the tensile strength is 100-280MPa, the thermal deformation temperature is 150-200 DEG C, the bending strength is 8000-20000MPa, under 230 DEG C, the melt mass flux rate is 22-120g/10 min under the effect of 2.16kg of weight. The long glass fiber-reinforced polypropylene composition product has high fluidity and rigidity.
Description
Technical field
The present invention relates to the polypropene composition goods that a kind of long glass fibres (glass) strengthens.
Background technology
Common injection technique glass fibre used strengthens pellet and manufactures with extrusion composite technology, it is to adopt Bitruder by compound to glass fiber precursor and the melting in the barrel of forcing machine of thermoplastics melt, be extruded into material strip shape by die head, the short enhancing pellet that is cut into after water-cooled, again this pellet is added in injection moulding machine, again after melting, is expelled to the goods that form desired shape in mould.The length of this technique fiberglas chopped strand used is generally 3-6mm, after Bitruder, glass fibre is prescinded 0.75-1.5mm, when after injection moulding machine injection, in final enhancing goods, glass fibre length further shortens to 0.15-0.33mm.Because glass fibre length shortens dramatically, therefore reinforced effects is had a greatly reduced quality.
Long glass fibres pellet refers to the pellet that one-way fiber is arranged, and its staple length and pellet are equal in length, is generally greater than 5mm.Long-fiber-reinforced thermoplastics is use heat thermoplastic plastic melt coated glass fiber single filament equably; glass fibre adequately protects; form through infiltration, traction, cooling, pelletizing; in the time of injection molding because fiber is surrounded by plastics equably; staple length reduces the strong cutting action of screw in injection molding machine to fiber, therefore in final goods, can reach 0.64-2.9mm; even can reach 11.9mm, be the preparation of above-mentioned traditional technology glass fibre length 5-20 doubly.This enhancing goods are after burning erosion, and remaining glass fibre still can maintain the shape of goods.Compared with the glass fibre obtaining with traditional granulation and Shooting Technique, physical strength, high-temperature behavior, wearing character, surface luster and the creep-resistant property of long fiber reinforcement thermal plastic goods all improve a lot.
Long-fiber-reinforced thermoplastics (Long Fiber reinforced Thermoplastics, be called for short LFT) be the effective means that realizes general-purpose plastics through engineering approaches, engineering plastics functionalization, the length of its glass fibre is generally greater than 4-5mm, and more than can remaining on 8mm.In long fiber reinforcement thermoplastic material, consumption maximum is long glass fiber reinforced polypropylene PP Pipe Compound, accounts for the more than 80% of LFT material.LFT has following outstanding superiority: the ratio of (1) intensity/deadweight is very high.(2) because fiber in injection molding LFT goods forms network structure, the rigidity of product and toughness are improved simultaneously, injection molding short glass fiber strengthens goods and is difficult to accomplish this point.(3) in compared with large-temperature range, keep the performance of material, indeformable, and there is low-down creep properties.(4) low-temperature impact toughness of LFT material is even higher than corresponding virgin resin and SFT(short glass fiber reinforced thermoplastics(RTP)) material.(5) shrinking percentage of injection moulding LFT is very low, can injection molding size large, the accurate goods of dimensional requirement.The tensile modulus of the general polypropene composition containing 40% long glass fibres can reach 10000MPa, is 6-8 times of plain polypropylene, has good shock resistance simultaneously.This material is widely used in automobile, household electrical appliances, electromechanical industries, petrochemical complex and communication electronic enterprises.
CN101338051A discloses a kind of long glass fiber reinforced polypropylene material and preparation method thereof, the weight ratio of this polypropylene material component is: polypropylene 35～55 % by weight, long glass fibres 35～50 % by weight, coupling agent 0.3～0.8 % by weight, compatilizer 5～10 % by weight, flow ability modifying agent 2～4 % by weight, oxidation inhibitor 0.3～0.6 % by weight, lubricant 1～2 % by weight.In this invention, polyacrylic melt mass flow rate used is 10-25g/10min.The method has also further been introduced by double-screw extruding pelletizing, uses peroxide degradation polypropene composition, and to reach polyacrylic high workability, but the method exists the defects such as melt polypropylene mass flow rate is unstable, smell is large.
The commercial car cover plate of storage battery that CN101593817A long glass fiber reinforced polypropylene material is produced, by modified polypropylene material and heat-resistant aging agent, uvioresistant auxiliary agent, white oil, Masterbatch additive through being uniformly mixed after melting, with coextrusion after 40% glass fiber yarn of combing mixes, acrylic resin is coated on to glass fibre outside surface, and the cooling pellet that becomes after being cut off, can be used for making full-sized car cover plate of storage battery.This invention relates generally to the moulding into cover plate of storage battery, to not explanation in detail of composition.In the product making, glass fibre can be extruded machine and prescinds, the poor effect that therefore glass strengthens.
CN102127260A relates to a kind of toughening type long glass fiber reinforced polypropylene composition board-like material and preparation method thereof, includes polypropylene, long glass fibres, toughner, modified polypropene, oxidation inhibitor and colour batch.Polyacrylic melt mass flow rate used is 16-40g/10min, and its glass fibre adds from forcing machine middle part, and glass fibre is impaired to shorten, and cannot guarantee the glass fibre length requirement in long glass fiber reinforced polypropylene.
Hence one can see that, and the polypropylene product providing of the prior art, because polypropylene mobility is low, is unfavorable for the coated of glass fibre, there will be glass fibre to be exposed to the phenomenon of product surface; In addition, in prior art, often glass fibre and polypropylene basis resin is mixed together evenly in forcing machine, melting, glass fibre can, because the mechanicals efforts of forcing machine be prescinded, therefore cannot be applied to the field that some mobility to long glass fiber reinforced polypropylene and rigidity are had relatively high expectations.Under normal circumstances, be surrounded by the polypropylene articles of glass fibre, the length of glass fibre can only reach 0.01-0.07:1 with the ratio of the length of goods, therefore cannot be applied to the field that some mobility to long glass fiber reinforced polypropylene and rigidity are had relatively high expectations.
Summary of the invention
The object of the invention is in order to overcome the deficiencies in the prior art, a kind of polypropene composition goods that can strengthen with the long glass fibres of higher mobility and rigidity modulus are provided.
The invention provides the polypropene composition goods that a kind of long glass fibres strengthens, these goods are formed by a kind of mixture, described mixture contains acrylic resin, oxidation inhibitor, the long glass fibres of compatilizer and coupling agent treatment, in described goods, the length of the long glass fibres of coupling agent treatment is 0.1-1:1 with the ratio of the length of goods, the cantilever beam impact strength of described goods is 280-780J/m, tensile strength is 100-280MPa, heat-drawn wire is 150-200 ℃, flexural strength is 8000-20000MPa, at 230 ℃, melt mass flow rate under the effect of 2.16kg counterweight is 22-120g/10min.
In the present invention, because long glass fibres is extruded without forcing machine, so can not be extruded the high shear force of machine in forcing machine cuts off, because the direct blend composition after extruding of the long glass fibres through coupling agent treatment through traction contacts, because can control the length direction of long glass fibres and the length direction of goods is consistent, and can control the length of glass fibre in goods by controlling as the length of the long glass fibres of raw material or through the length of the long glass fibres of coupling agent treatment.And long glass fiber reinforced polypropylene composition article provided by the invention can have good mobility and rigidity concurrently.
Embodiment
The polypropene composition goods that strengthen according to long glass fibres of the present invention, these goods are formed by a kind of mixture, described mixture contains acrylic resin, oxidation inhibitor, the processing long glass fibres of compatilizer and coupling agent, in described goods, the length of the long glass fibres of coupling agent treatment is 0.1-1:1 with the ratio of the length of goods, the cantilever beam impact strength of described goods is 280-780J/m, tensile strength is 100-280MPa, heat-drawn wire is 150-200 ℃, flexural strength is 8000-20000MPa, at 230 ℃, melt mass flow rate under the effect of 2.16kg counterweight is 22-120g/10min.Preferably, the length of the long glass fibres of coupling agent treatment is 0.15-1:1 with the ratio of the length of goods, the shock strength of the socle girder of described goods is 300-750J/m, tensile strength is 112-242MPa, heat-drawn wire is 160-190 ℃, flexural strength is 8200-18000MPa, and the melt mass flow rate at 230 ℃, under the effect of 2.16kg counterweight is 25-85g/10min.
In the present invention, described melt mass flow rate (MFR) is to carry out according to standard A STM D1238-04, and particularly, probe temperature is 230 ℃, and load is 2.16 kilograms; Content of glass fiber (glass fiber content) is carried out according to standard A STM D2584-02; Tensile strength, elongation at break carry out according to standard A STMD638-08; Flexural strength, modulus in flexure are carried out according to standard A STM D790-07; Cantilever beam impact strength (IZOD notched Izod impact strength) carries out according to standard A STM D256-06; Rockwell hardness carries out according to standard A STM D785-08; Heat-drawn wire (1.82MPa) is carried out according to standard A STMD648-07; Molding shrinkage carries out according to standard A STM D955-08, and test, at the molding shrinkage being parallel and perpendicular in melt flow direction, is designated as respectively M
paralleland M
vertically; The length testing of the glass fibre in polypropene composition goods and goods that long glass fibres strengthens: carry out its length of rear measurement by standard GB/T9345.1-2008.
According to the present invention, preferably, in described mixture, with respect to the acrylic resin of 100 weight parts, the content of described oxidation inhibitor is that the content of 0.1-0.8 weight part, described compatilizer is that the content of the long glass fibres of 2-8 weight part, described coupling agent treatment is 30-70 weight part; Further preferably, with respect to the acrylic resin of 100 weight parts, the content of described oxidation inhibitor is that the content of 0.2-0.4 weight part, described compatilizer is that the content of 4-5 weight part, described coupling agent treatment long glass fibres is 30-50 weight part.
According to the present invention, the present invention does not have special requirement to the kind of long glass fibres, and preferably, described long glass fibres is alkali-free long glass fibres.
In the present invention, " acrylic resin " is take propylene as monomer, the thermoplastic resin forming through refining, catalyzed polymerization, granulation, and polypropylene wherein can be the homopolymer of propylene, can be also the multipolymer of propylene.Preferably, the melt mass flow rate of described acrylic resin at 230 ℃, under the effect of 2.16kg counterweight can be 35-320g/10min, further the melt mass flow rate of preferred described acrylic resin at 230 ℃, under the effect of 2.16kg counterweight is 45-300g/10min, and the mobility of the goods that obtain is like this stronger.
According to the present invention, in described mixture, can also contain nucleator, with respect to the acrylic resin of 100 weight parts, the content of described nucleator is 0.02-0.12 weight part, is preferably 0.05-0.07 weight part.In mixture, add nucleator, can more effectively improve cantilever beam impact strength, tensile strength and the flexural strength of goods.
According to the present invention, the various nucleators that can be used in acrylic resin that described nucleator can be known to the skilled person, as a rule, described nucleator can be dibenzoic acid aluminium, 2, one or more in 2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) sodium phosphate and aryl phosphate ester aluminium salt; Be preferably 2,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) sodium phosphate.
According to the present invention, wherein, the long glass fibres of described coupling agent treatment is by flooding 30-60 minute by long glass fibres in concentration is the silane coupling agent aqueous solution of 0.05-1.5 % by weight, then dry obtaining for 3-5 hour under the condition of 80-90 ℃.
According to the present invention, the various coupling agents of processing glass fibre that can be used in that described coupling agent can be known to the skilled person, as a rule, described coupling agent can be silane coupling agent, one or more in titanate coupling agent and aluminate coupling agent, preferred described coupling agent is γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570), γ-aminopropyl triethoxysilane (KH-550) and γ-(2, 3-epoxy the third oxygen) one or more in propyl trimethoxy silicane (KH-560), further preferred described coupling agent is γ-(methacryloxypropyl) propyl trimethoxy silicane.
According to the present invention, the long glass fibres that described long glass fibres can be known to the skilled person, preferably, the tensile yield strength of described long glass fibres is 40-80 MPa, tensile modulus is the lucky handkerchief of 5-10, the length >10 rice of monfil, fiber number is the 0.5-1.0 dawn, fusing point is >250 ℃.
According to the present invention, the present invention, to the special restriction useless of the working concentration of described coupling agent, can use described pure coupling agent, preferably uses the aqueous solution of coupling agent.Preferably use the aqueous solution of coupling agent.The present invention does not have special requirement to the concentration of coupling agent aqueous solution, and under preferable case, the concentration of described coupling agent solution can be 0.05-1.5 % by weight, more preferably 0.05-1 % by weight.
Method and the condition of the long glass fibres of the present invention to coupling agent treatment are not particularly limited, and can adopt the method for coupling agent treatment long glass fibres of the prior art to carry out.For example, long glass fibres in being the silane coupling agent aqueous solution of 0.05-1.5 % by weight, concentration can be flooded to 30-60 minute, then dry 3-5 hour under the condition of 80-90 ℃.
In the present invention, described oxidation inhibitor can, for the conventional various oxidation inhibitor in this area, be not particularly limited.Usually, described oxidation inhibitor can be the combination of primary antioxidant and auxiliary antioxidant, and wherein, described primary antioxidant has the function of catching polymkeric substance peroxy radical, and can be selected from hindered phenol is oxidation inhibitor; Described auxiliary antioxidant is the hydroperoxide in decomposing copolymer effectively, prevent the carrying out that its homolysis produces new free radical, causes Auto-oxidation reaction, for example, can be that oxidation inhibitor and monothioester are one or more in oxidation inhibitor for being selected from phosphorous acid ester.In the present invention, the example of described oxidation inhibitor can include but not limited to: 2, 6-di-tert-butyl-4-methy phenol, β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester is (, antioxidant 1010), two [the 3-(3 of sulfo-diethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, three (2-methyl-4-hydroxyl-5-tert.-butylbenzene) butane and 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol).Particularly, the example of described auxiliary antioxidant can be but be not limited to: three [2,4-di-tert-butyl-phenyl] phosphorous acid ester is (, irgasfos 168), four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites, three nonylated phenyl phosphites, two (2,4-DTBP) pentaerythritol diphosphites, the two stearyl alcohol esters of thio-2 acid and Tyox B.From the angle of further raising antioxidant property, described antioxidant is preferably that oxidation inhibitor is as primary antioxidant, using phosphorous acid ester and/or monothioester as auxiliary antioxidant using described phenol.The ratio of described primary antioxidant and described auxiliary antioxidant can be that the routine of this area is selected.Usually, the weight ratio of described primary antioxidant and described auxiliary antioxidant can be 1:0.5-2.The consumption of described oxidation inhibitor can be that the routine of this area is selected, for example: with respect to propene polymer described in 100 weight parts, the content of described oxidation inhibitor can be 0.15-0.8 weight part, is preferably 0.2-0.4 weight part.
According to the present invention, the various oxidation inhibitor that can be used in acrylic resin that described oxidation inhibitor can be known to the skilled person, described oxidation inhibitor can be one or more in Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant; Be preferably Hinered phenols antioxidant and phosphite ester kind antioxidant.In the time that described oxidation inhibitor is Hinered phenols antioxidant and phosphite ester kind antioxidant, although the present invention does not have special requirement to the weight ratio of described Hinered phenols antioxidant and phosphite ester kind antioxidant, under preferable case, the weight ratio of described Hinered phenols antioxidant and phosphite ester kind antioxidant is 1:0.5-4, more preferably 1:1-2.
According to the present invention, the various consistencies that can be used in acrylic resin that described consistency can be known to the skilled person, as a rule, described consistency can be one or more in maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene and acrylic acid-grafted polypropylene, is preferably maleic anhydride inoculated polypropylene.
According to the present invention, the maleic anhydride inoculated polypropylene of the various compatilizers that can be used in acrylic resin that described maleic anhydride inoculated polypropylene can be known to the skilled person, as a rule, the percentage of grafting of the maleic anhydride in described maleic anhydride inoculated polypropylene can be 1-5%, maleic anhydride inoculated polypropylene is 2-15g/10min at 230 ℃, the melt mass flow rate of 2.16kg counterweight, is preferably 6-10g/10min.
According to the present invention, the maleic anhydride grafted polyethylene of the various compatilizers that can be used in polyvinyl resin that described maleic anhydride grafted polyethylene can be known to the skilled person, as a rule, the percentage of grafting of the maleic anhydride in described maleic anhydride grafted polyethylene can be 1-5%, maleic anhydride grafted polyethylene is 2-15g/10min at 230 ℃, the melt mass flow rate of 2.16kg counterweight, is preferably 6-10g/10min.
According to the present invention, the acrylic acid-grafted polypropylene of the various compatilizers that can be used in acrylic resin that described acrylic acid-grafted polypropylene can be known to the skilled person, as a rule, acrylic acid percentage of grafting in described acrylic acid-grafted polypropylene can be 1-5%, acrylic acid-grafted polypropylene is 2-15g/10min at 230 ℃, the melt mass flow rate of 2.16kg counterweight, is preferably 6-10g/10min.
According to the present invention, various the invention provides containing acrylic resin in prior art, oxidation inhibitor, the mixture of compatilizer and coupling agent treatment long glass fibres is prepared the method for polypropene composition goods that growth coupling agent treatment long glass fibres strengthens all can be for the present invention, as long as it is 0.1-1:1 that described method can realize the ratio of the length of the long glass fibres in goods and the length of goods, the cantilever beam impact strength of described goods is 280-780J/m, tensile strength is 100-280MPa, heat-drawn wire is 150-200 ℃, flexural strength is 8000-20000MPa, at 230 ℃, melt mass flow rate under the effect of 2.16kg counterweight is 22-120g/10min.
A preferred embodiment of the invention, goods provided by the invention can be taked following methods preparation:
(1) blend composition that contains acrylic resin, oxidation inhibitor and compatilizer mixed in forcing machine, melting, extrude, obtain melt polypropylene steeping fluid;
(2) melt polypropylene steeping fluid is contacted with the coupling agent treatment long glass fibres in traction state;
(3) by product curing molding, pelletizing after contact,
Described blend composition contains acrylic resin, oxidation inhibitor and compatilizer, the melt mass flow rate of described acrylic resin at 230 ℃, under the effect of 2.16kg counterweight is 35-320g/10min, in described blend composition, with respect to the acrylic resin of 100 weight parts, the consumption of described oxidation inhibitor is that the consumption of 0.1-0.8 weight part, described compatilizer is 2-8 weight part; The weight ratio of described coupling agent treatment long glass fibres and described blend composition is 1:1.3-3.3.In order to make polypropene composition flow better and make to obtain the rigidity reinforced of polypropene composition, under preferable case, in described blend composition, with respect to the acrylic resin of 100 weight parts, the consumption of described oxidation inhibitor is that the consumption of 0.2-0.4 weight part, described compatilizer is 4-5 weight part, and the weight ratio of described coupling agent treatment long glass fibres and described blend composition is 1:1.6-2.5.
According to the present invention, method and condition that the blend composition that contains acrylic resin, nucleator, oxidation inhibitor and compatilizer is mixed are known to the skilled person.For example, the blend composition that contains acrylic resin, nucleator, oxidation inhibitor and compatilizer can be added in high-speed mixer and mixes.The condition of described mixing generally includes rotating speed, the temperature of mixing and the time of mixing of high-speed mixer, and the rotating speed of described agitator can be for example 100-500 rev/min, and the temperature of mixing can be for example 25-65 ℃, and the time of mixing can be 30-60 second; Under preferable case, under the rotating speed of 200-400 rev/min, stir 40-50 second at 25-65 ℃.
According to the present invention, method and the condition of the blend composition melting that contains acrylic resin, nucleator, oxidation inhibitor and compatilizer are known to the skilled person.For example, the above-mentioned blend composition that contains acrylic resin, nucleator, oxidation inhibitor and compatilizer mixing can be added to melting in forcing machine.Method, condition and the forcing machine used of described melting are conventionally known to one of skill in the art.For example, twin screw extruder can be adopted, also single screw extrusion machine can be adopted, screw speed is 80-300 rev/min, the temperature of the intake zone of forcing machine, compression zone, melting zone, homogenization zone is respectively 230-280 ℃, 240-290 ℃, 240-290 ℃, 230-280 ℃, and the vacuum tightness of each section is melting under the condition of 0.02 to 0.09 MPa.
According to the present invention, the blend composition after extruding, with after the coupling agent treatment long glass fibres of traction contacts, obtains infiltrating the long glass fibres of blend composition.Those skilled in the art is well known that, can carry out cooling, pelletizing to the long glass fibres that infiltrates blend composition, makes long glass fiber reinforced polypropylene goods.
According to the present invention, method and the condition of carrying out pelletizing to infiltrating the long glass fibres of blend composition are also known to the skilled person, and for example, can adopt tablets press to carry out granulation to the long glass fibres that infiltrates blend composition.
According to above-mentioned preparation method, because long glass fibres is extruded without forcing machine, so can not be extruded the high shear force of machine in forcing machine cuts off, because the direct blend composition after extruding of the long glass fibres through coupling agent treatment through traction contacts, because can control the length direction of long glass fibres and the length direction of goods is consistent, and can control the length of glass fibre in goods by controlling as the length of the long glass fibres of raw material or through the length of the long glass fibres of coupling agent treatment.
Below will describe the present invention by embodiment.
The testing method relating in following examples and comparative example is as follows:
1, melt mass flow rate (MFR): carry out according to standard A STM D1238-04, particularly, probe temperature is 230 ℃, and load is 2.16 kilograms;
2, content of glass fiber (glass fiber content): carry out according to standard A STM D2584-02;
3, tensile strength, elongation at break: carry out according to standard A STM D638-08;
4, flexural strength, modulus in flexure: carry out according to standard A STM D790-07;
5, cantilever beam impact strength (IZOD notched Izod impact strength): carry out according to standard A STM D256-06;
6, Rockwell hardness: carry out according to standard A STM D785-08;
7, heat-drawn wire (1.82MPa): carry out according to standard A STM D648-07;
8, molding shrinkage: carry out according to standard A STM D955-08, test, at the molding shrinkage being parallel and perpendicular in melt flow direction, is designated as respectively M
paralleland M
vertically.
9, the length testing of the glass fibre in long glass fiber reinforced polypropylene composition article and goods: undertaken by standard GB/T 9345.1-2008, the length of the long glass fibres of coupling agent treatment and the ratio of the length of goods are length and the former composition article length ratio of roving glass fiber after perfect combustion.
10, percentage of grafting: adopt determination of acid-basetitration, the method of test is specially: accurately weigh the graft polymerization matter sample 0.5g left and right after purifying, be dissolved in appropriate dimethylbenzene, after backflow 15min, be cooled to 70 ℃, then add the potassium hydroxide-ethanol of 0.1mol/L to carry out saponification backflow, after 1h, then use phenolphthalein-thymolphthalein mixture indicator, use while hot acetic acid-xylene solution back titration of 0.1mol/L to terminal.The calculation formula of percentage of grafting is:
Wherein, M is maleic anhydride molecular mass (98.06); N
hACfor the concentration (mol/L) of acetic acid-xylene solution; V
0the volume (mL) of the acetic acid-xylene solution that consumes during for blank titration; The volume (mL) of V acetic acid-xylene solution that titration consumes when containing product; W is the weight (g) of sample.
Embodiment 1
This embodiment is used for illustrating long glass fiber reinforced polypropylene composition article provided by the invention and preparation method thereof.
By the propylene homopolymer resins of 100 weight parts (melt mass flow rate is 45g/10min), (percentage of grafting is 2% to the polypropylene grafted maleic anhydride of 5 weight parts, melt mass flow rate is 8g/10min), 2 of 0.06 weight part, 2 '-methylene radical-bis-(4, 6-DI-tert-butylphenol compounds) sodium phosphate (NA-11), [β-(3 of 0.1 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2 of 0.2 weight part, 4-di-tert-butyl-phenyl) phosphorous acid ester adds in high-speed mixer fully and mixes, obtain blend composition, wherein the weight of propylene homopolymer resins is 5000g, then add aforementioned blend composition toward the main feeding device of twin screw extruder, blend composition is carried out to melting, the temperature in the each district of forcing machine is followed successively by 250 ℃, 260 ℃, 260 ℃, 250 ℃, obtains melt polypropylene steeping fluid.
By long glass fibres, (tensile yield strength is 60 MPas, tensile modulus is 8 lucky handkerchiefs, the length >10 rice of monfil, fiber number was 0.8 dawn, fusing point is >250 ℃) 150g floods 30 minutes in the silane coupled agent concentration of KH570 is the aqueous solution of 0.8 % by weight, then in the baking oven of 80 ℃, be dried 4 hours, obtain the long glass fibres of coupling agent treatment.
Draw through silane coupling agent KH570 dipping dry long glass fibres by up-coiler, with perpendicular to cross-head direction by being arranged on the immersion slot of head of forcing machine, cooling, pelletizing after the propylene melt impregnation liquid that makes 5000g melting contacts 0.05 minute with the 150g long glass fibres after traction in immersion slot, makes glass fiber reinforced polypropylene compositions goods.The composition of the glass fiber reinforced polypropylene compositions of preparation and character are shown in table 1.
Comparative example 1
Adopt the method for embodiment 1 to prepare long glass fiber reinforced polypropylene composition article, different, the melt mass flow rate of acrylic resin is 30g/10min.The composition of the glass fiber reinforced polypropylene compositions goods of preparation and character are shown in table 1.
Comparative example 2
Adopt the method for embodiment 1 to prepare long glass fiber reinforced polypropylene composition article, different, add in the lump the main feeding device melting of twin screw extruder through silane coupling agent KH570 dipping dry long glass fibres and blend composition.The composition of the glass fiber reinforced polypropylene compositions goods of preparation and character are shown in table 1.
Embodiment 2
This embodiment is used for illustrating long glass fiber reinforced polypropylene composition article provided by the invention and preparation method thereof.
By the propylene homopolymer resins of 100 weight parts (melt mass flow rate is 100g/10min), (percentage of grafting is 2% to the polypropylene grafted maleic anhydride of 5 weight parts, melt mass flow rate is 8g/10min), 2 of 0.05 weight part, 2 '-methylene radical-bis-(4, 6-DI-tert-butylphenol compounds) sodium phosphate (NA-11), [β-(3 of 0.1 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2 of 0.2 weight part, 4-di-tert-butyl-phenyl) phosphorous acid ester and 0.2 weight part Tyox B add in high-speed mixer and fully mix, obtain blend composition, wherein the weight of propylene homopolymer resins is 5000g, then add aforementioned blend composition toward the main feeding device of twin screw extruder, blend composition is carried out to melting, the temperature in the each district of forcing machine is followed successively by 250 ℃, 260 ℃, 260 ℃, 250 ℃, obtains propylene melt impregnation liquid.
By long glass fibres, (tensile yield strength is 60 MPas, tensile modulus is 8 lucky handkerchiefs, the length >10 rice of monfil, fiber number was 0.8 dawn, fusing point is >250 ℃) 200g floods 30 minutes in the silane coupled agent concentration of KH570 is the aqueous solution of 0.8 % by weight, and then in the baking oven of 80 ℃ dry 4 hours.
Traction is through silane coupling agent KH570 dipping dry long glass fibres, cooling, pelletizing after the propylene melt impregnation liquid of 5000g melting is contacted to 0.05 minute with the 200g long glass fibres after traction in immersion slot, makes glass fiber reinforced polypropylene compositions goods.The composition of the glass fiber reinforced polypropylene compositions goods of preparation and character are shown in table 1.
Embodiment 3
This embodiment is used for illustrating long glass fiber reinforced polypropylene composition article provided by the invention and preparation method thereof.
By the propylene homopolymer resins of 100 weight parts (melt mass flow rate is 100g/10min), (percentage of grafting is 1.5% to the polypropylene grafted maleic anhydride of 5 weight parts, melt mass flow rate is 8g/10min), 2 of 0.06 weight part, 2 '-methylene radical-bis-(4, 6-DI-tert-butylphenol compounds) sodium phosphate (NA-11), [β-(3 of 0.1 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2 of 0.2 weight part, 4-di-tert-butyl-phenyl) phosphorous acid ester and 0.2 weight part Tyox B add in high-speed mixer and fully mix, obtain blend composition, wherein the weight of acrylic resin is 5000g, then add aforementioned blend composition toward the main feeding device of twin screw extruder, blend composition is carried out to melting, the temperature in the each district of forcing machine is followed successively by 250 ℃, 260 ℃, 260 ℃, 250 ℃, obtains propylene melt impregnation liquid.
By 40 weight part long glass fibress, (tensile yield strength is 60 MPas, tensile modulus is 8 lucky handkerchiefs, the length >10 rice of monfil, fiber number was 0.8 dawn, fusing point is >250 ℃) 250g floods 30 minutes in the silane coupled agent concentration of KH570 is the aqueous solution of 0.08 % by weight, and then in the baking oven of 80 ℃ dry 4 hours.
Traction is through silane coupling agent KH570 dipping dry long glass fibres, cooling, pelletizing after the propylene melt impregnation liquid of 5000g melting is contacted to 0.05 minute with the 250g long glass fibres after traction in immersion slot, makes glass fiber reinforced polypropylene compositions goods.The composition of the glass fiber reinforced polypropylene compositions goods of preparation and character are shown in table 1.
Embodiment 4
This embodiment is used for illustrating long glass fiber reinforced polypropylene composition article provided by the invention and preparation method thereof.
By the propylene homopolymer resins of 100 weight parts (melt mass flow rate is 200g/10min), (percentage of grafting is 1.5% to the polypropylene grafted maleic anhydride of 5 weight parts, melt mass flow rate is 10g/10min), 2 of 0.05 weight part, 2 '-methylene radical-bis-(4, 6-DI-tert-butylphenol compounds) sodium phosphate (NA-11), [β-(3 of 0.1 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2 of 0.2 weight part, 4-di-tert-butyl-phenyl) phosphorous acid ester adds in high-speed mixer fully and mixes, obtain blend composition, wherein the weight of propylene homopolymer resins is 5000g, then add aforementioned blend composition toward the main feeding device of twin screw extruder, blend composition is carried out to melting, the temperature in the each district of forcing machine is followed successively by 250 ℃, 260 ℃, 260 ℃, 250 ℃, obtains propylene melt impregnation liquid.
By long glass fibres, (tensile yield strength is 60 MPas, tensile modulus is 8 lucky handkerchiefs, the length >10 rice of monfil, fiber number was 0.8 dawn, fusing point is >250 ℃) 250g floods 30 minutes in the silane coupled agent concentration of KH570 is the aqueous solution of 0.8 % by weight, and then in the baking oven of 80 ℃ dry 4 hours.
Traction is through silane coupling agent KH560 dipping dry long glass fibres, cooling, pelletizing after the propylene melt impregnation liquid of 5000g melting is contacted to 0.05 minute with the 250g long glass fibres after traction in immersion slot, makes glass fiber reinforced polypropylene compositions goods.The composition of the glass fiber reinforced polypropylene compositions goods of preparation and character are shown in table 1.
Embodiment 5
This embodiment is used for illustrating long glass fiber reinforced polypropylene composition article provided by the invention and preparation method thereof.
By the propylene homopolymer resins of 100 weight parts (melt mass flow rate is 200g/10min), (percentage of grafting is 2% to the polypropylene grafted maleic anhydride of 5 weight parts, melt mass flow rate is 10g/10min), 2 of 0.06 weight part, 2 '-methylene radical-bis-(4, 6-DI-tert-butylphenol compounds) sodium phosphate (NA-11), [β-(3 of 0.1 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2 of 0.2 weight part, 4-di-tert-butyl-phenyl) phosphorous acid ester adds in high-speed mixer fully and mixes, obtain blend composition, wherein the weight of acrylic resin is 5000g, then add aforementioned blend composition toward the main feeding device of twin screw extruder, blend composition is carried out to melting, the temperature in the each district of forcing machine is followed successively by 250 ℃, 260 ℃, 260 ℃, 250 ℃, obtains propylene melt impregnation liquid.
By long glass fibres, (tensile yield strength is 60 MPas, tensile modulus is 8 lucky handkerchiefs, the length >10 rice of monfil, fiber number was 0.8 dawn, fusing point is >250 ℃) 200g floods 30 minutes in the silane coupled agent concentration of KH550 is the aqueous solution of 0.8 % by weight, and then in the baking oven of 80 ℃ dry 4 hours.
Traction is through Silane coupling agent KH550 dipping dry long glass fibres, cooling, pelletizing after the propylene melt impregnation liquid of 5000g melting is contacted to 0.05 minute with the 200g long glass fibres after traction in immersion slot, makes glass fiber reinforced polypropylene compositions goods.The composition of the glass fiber reinforced polypropylene compositions goods of preparation and character are shown in table 1.
Embodiment 6
This embodiment is used for illustrating long glass fiber reinforced polypropylene composition article provided by the invention and preparation method thereof.
By the propylene homopolymer resins of 100 weight parts (melt mass flow rate is 300g/10min), (percentage of grafting is 2 to the polypropylene grafted maleic anhydride of 5 weight parts, melt mass flow rate is 10g/10min), 2 of 0.05 weight part, 2 '-methylene radical-bis-(4, 6-DI-tert-butylphenol compounds) sodium phosphate (NA-11), [β-(3 of 0.1 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three (2 of 0.2 weight part, 4-di-tert-butyl-phenyl) phosphorous acid ester adds in high-speed mixer fully and mixes, obtain blend composition, wherein the weight of propylene homopolymer resins is 5000g, then add aforementioned blend composition toward the main feeding device of twin screw extruder, blend composition is carried out to melting, the temperature in the each district of forcing machine is followed successively by 250 ℃, 260 ℃, 260 ℃, 250 ℃, obtains propylene melt impregnation liquid.
By long glass fibres, (tensile yield strength is 60 MPas, tensile modulus is 8 lucky handkerchiefs, the length >10 rice of monfil, fiber number was 0.8 dawn, fusing point is >250 ℃) 200g floods 30 minutes in the silane coupled agent concentration of KH570 is the aqueous solution of 0.8 % by weight, and then in the baking oven of 80 ℃ dry 4 hours.
Traction is through silane coupling agent (KH550) dipping dry long glass fibres, cooling, pelletizing after the propylene melt impregnation liquid of 5000g melting is contacted to 0.05 minute with the 200g long glass fibres after traction in immersion slot, makes glass fiber reinforced polypropylene compositions goods.The composition of the glass fiber reinforced polypropylene compositions goods of preparation and character are shown in table 1.
Embodiment 7
Adopt the method identical with embodiment 1 to prepare long glass fiber reinforced polypropylene composition, different, in blend composition, do not add nucleator.
Embodiment 8
Adopt the method identical with embodiment 1 to prepare long glass fiber reinforced polypropylene composition, different, the coupling agent in blend composition is KH560.
Table 1
Continued 1
From the data of table 1, the length of glass fibre and the Length Ratio of goods in the similar polypropylene articles of the length of the coupling agent treatment long glass fibres in long glass fiber reinforced polypropylene composition article prepared by the inventive method and the Length Ratio prior art of goods are large, and good combination property.
Claims (12)
1. the polypropene composition goods that long glass fibres strengthens, it is characterized in that, these goods are formed by a kind of mixture, described mixture contains acrylic resin, oxidation inhibitor, the long glass fibres of compatilizer and coupling agent treatment, in described goods, the length of the long glass fibres of coupling agent treatment is 0.1-1:1 with the ratio of the length of goods, the cantilever beam impact strength of described goods is 280-780J/m, tensile strength is 100-280MPa, heat-drawn wire is 150-200 ℃, flexural strength is 8000-20000MPa, at 230 ℃, melt mass flow rate under the effect of 2.16kg counterweight is 22-120g/10min.
2. goods according to claim 1, wherein, in described goods, the length of the long glass fibres of coupling agent treatment is 0.15-1:1 with the ratio of the length of goods, the shock strength of the socle girder of described goods is 300-750J/m, and tensile strength is 112-242MPa, and heat-drawn wire is 160-190 ℃, flexural strength is 8200-18000MPa, and the melt mass flow rate at 230 ℃, under the effect of 2.16kg counterweight is 25-85g/10min.
3. goods according to claim 1 and 2, wherein, in described mixture, with respect to the acrylic resin of 100 weight parts, the content of described oxidation inhibitor is that the content of 0.1-0.8 weight part, described compatilizer is that the content of the long glass fibres of 2-8 weight part, described coupling agent treatment is 30-70 weight part; Preferably, with respect to the acrylic resin of 100 weight parts, the content of described oxidation inhibitor is that the content of 0.2-0.4 weight part, described compatilizer is that the content of 4-5 weight part, described coupling agent treatment long glass fibres is 30-50 weight part.
4. goods according to claim 1, wherein, the melt mass flow rate of described acrylic resin at 230 ℃, under the effect of 2.16kg counterweight is 35-320g/10min, is preferably 45-300g/10min.
5. according to the goods described in any one in claim 1-4, wherein, described mixture also contains nucleator, and with respect to the acrylic resin of 100 weight parts, the content of described nucleator is 0.02-1.2 weight part, is preferably 0.05-0.07 weight part.
6. goods according to claim 5, wherein, described nucleator is selected from dibenzoic acid aluminium, 2, one or more in 2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) sodium phosphate and aryl phosphate ester aluminium salt, are preferably 2,2 '-methylene radical-bis-(4,6-DI-tert-butylphenol compounds) sodium phosphate.
7. goods according to claim 1, wherein, the long glass fibres of described coupling agent treatment is by flooding 30-60 minute by long glass fibres in concentration is the silane coupling agent aqueous solution of 0.05-1.5 % by weight, then dry obtaining for 3-5 hour under the condition of 80-90 ℃.
8. according to the goods described in claim 1 or 7, wherein, described coupling agent is one or more in silane coupling agent, titanate coupling agent and aluminate coupling agent, preferred described coupling agent is one or more in γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-aminopropyl triethoxysilane and γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane.
9. according to the goods described in claim 1 or 7, wherein, the tensile yield strength of described long glass fibres is 40-80 MPa, tensile modulus is the lucky handkerchief of 5-10, the length >10 rice of monfil, fiber number is the 0.5-1.0 dawn, fusing point is >250 ℃.
10. goods according to claim 1, wherein, described oxidation inhibitor is selected from one or more in Hinered phenols antioxidant, phosphite ester kind antioxidant and sulphur ester antioxidant; Be preferably Hinered phenols antioxidant and phosphite ester kind antioxidant.
11. goods according to claim 10, wherein, described oxidation inhibitor is Hinered phenols antioxidant and phosphite ester kind antioxidant; The weight ratio of described Hinered phenols antioxidant and phosphite ester kind antioxidant is 1:0.5-4.
12. goods according to claim 1, wherein, described compatilizer is selected from one or more in maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene and acrylic acid-grafted polypropylene, is preferably maleic anhydride inoculated polypropylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107286463A (en) * | 2017-06-17 | 2017-10-24 | 常州帝君金属构件厂 | A kind of TRPP pellet |
| CN108864562A (en) * | 2017-05-11 | 2018-11-23 | 神华集团有限责任公司 | Polypropene composition, enhancing anti-flaming anti-static electricity polypropylene and preparation method thereof and product |
| CN111801375A (en) * | 2018-03-02 | 2020-10-20 | 提克纳有限责任公司 | Weather resistant fiber reinforced propylene compositions |
| CN111875878A (en) * | 2020-06-28 | 2020-11-03 | 浙江飞碟汽车制造有限公司 | Long glass fiber reinforced PP material and preparation method thereof |
| WO2020221764A1 (en) | 2019-04-29 | 2020-11-05 | Ineos Styrolution Group Gmbh | Polymer compositions that contain a semi-crystalline polymer, and process of preparation |
| CN112126123A (en) * | 2020-08-18 | 2020-12-25 | 北京协同创新研究院 | Continuous basalt fiber surface treating agent and preparation method thereof |
| CN112341711A (en) * | 2020-11-26 | 2021-02-09 | 江苏金发科技新材料有限公司 | Special glass fiber reinforced polypropylene composition for automobile intake manifold and preparation method thereof |
| WO2021239694A1 (en) * | 2020-05-27 | 2021-12-02 | Borealis Ag | Reinforced polyolefin composition comprising recycled plastic material |
| WO2022129016A1 (en) | 2020-12-16 | 2022-06-23 | Ineos Styrolution Group Gmbh | Filler-containing thermoplastic polymer composite material reinforced with continuous fibers and having good surface smoothness |
| WO2022129045A1 (en) | 2020-12-16 | 2022-06-23 | Ineos Styrolution Group Gmbh | Process for producing a thermoplastic polymer-containing fiber-reinforced composite material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108269A (en) * | 1993-12-28 | 1995-09-13 | 川崎制铁株式会社 | Reinforcing polypropylene resin with high containing of glasfibres and products of same |
| US20030104191A1 (en) * | 2001-11-29 | 2003-06-05 | Ts Tech Co., Ltd. | Long-fiber-reinforced thermoplastice resin sheets, production process thereof, and composite structures reinforced by the sheets |
| CN1548469A (en) * | 2003-05-22 | 2004-11-24 | 上海杰事杰新材料股份有限公司 | Long fiber reinforced polypropylene/PPE alloy material and its prepn and application |
-
2012
- 2012-10-30 CN CN201210424913.7A patent/CN103788470A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108269A (en) * | 1993-12-28 | 1995-09-13 | 川崎制铁株式会社 | Reinforcing polypropylene resin with high containing of glasfibres and products of same |
| US20030104191A1 (en) * | 2001-11-29 | 2003-06-05 | Ts Tech Co., Ltd. | Long-fiber-reinforced thermoplastice resin sheets, production process thereof, and composite structures reinforced by the sheets |
| CN1548469A (en) * | 2003-05-22 | 2004-11-24 | 上海杰事杰新材料股份有限公司 | Long fiber reinforced polypropylene/PPE alloy material and its prepn and application |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864562A (en) * | 2017-05-11 | 2018-11-23 | 神华集团有限责任公司 | Polypropene composition, enhancing anti-flaming anti-static electricity polypropylene and preparation method thereof and product |
| CN107286463A (en) * | 2017-06-17 | 2017-10-24 | 常州帝君金属构件厂 | A kind of TRPP pellet |
| CN111801375A (en) * | 2018-03-02 | 2020-10-20 | 提克纳有限责任公司 | Weather resistant fiber reinforced propylene compositions |
| US11931973B2 (en) | 2018-03-02 | 2024-03-19 | Ticona Llc | Weatherable fiber-reinforced propylene composition |
| WO2020221764A1 (en) | 2019-04-29 | 2020-11-05 | Ineos Styrolution Group Gmbh | Polymer compositions that contain a semi-crystalline polymer, and process of preparation |
| WO2021239694A1 (en) * | 2020-05-27 | 2021-12-02 | Borealis Ag | Reinforced polyolefin composition comprising recycled plastic material |
| CN111875878A (en) * | 2020-06-28 | 2020-11-03 | 浙江飞碟汽车制造有限公司 | Long glass fiber reinforced PP material and preparation method thereof |
| CN112126123A (en) * | 2020-08-18 | 2020-12-25 | 北京协同创新研究院 | Continuous basalt fiber surface treating agent and preparation method thereof |
| CN112341711A (en) * | 2020-11-26 | 2021-02-09 | 江苏金发科技新材料有限公司 | Special glass fiber reinforced polypropylene composition for automobile intake manifold and preparation method thereof |
| WO2022129016A1 (en) | 2020-12-16 | 2022-06-23 | Ineos Styrolution Group Gmbh | Filler-containing thermoplastic polymer composite material reinforced with continuous fibers and having good surface smoothness |
| WO2022129045A1 (en) | 2020-12-16 | 2022-06-23 | Ineos Styrolution Group Gmbh | Process for producing a thermoplastic polymer-containing fiber-reinforced composite material |
| US11732120B2 (en) | 2020-12-16 | 2023-08-22 | Ticona Llc | UV stable fiber-reinforced polymer composition |
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