CN103788445B - A kind of High molecular weight polyethylene composition - Google Patents
A kind of High molecular weight polyethylene composition Download PDFInfo
- Publication number
- CN103788445B CN103788445B CN201210426310.0A CN201210426310A CN103788445B CN 103788445 B CN103788445 B CN 103788445B CN 201210426310 A CN201210426310 A CN 201210426310A CN 103788445 B CN103788445 B CN 103788445B
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- high molecular
- weight polyethylene
- content
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of High molecular weight polyethylene composition, said composition contains High molecular weight polyethylene, oxidation inhibitor and stablizer, wherein, said composition is also containing flow ability modifying agent and processing aid, and described processing aid is selected from fluoropolymer additive and/or polycaprolactone; Described flow ability modifying agent be selected from ethylene bis stearic acid amide, methyl-silicone oil, polysiloxane and paraffin one or more, the viscosity-average molecular weight of described High molecular weight polyethylene is 500,000-150 ten thousand.High molecular weight polyethylene composition good rheological property provided by the invention, is particularly useful for melt-spinning operation and prepares high polymer polyethylene fiber.
Description
Technical field
The present invention relates to a kind of High molecular weight polyethylene composition.
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) (being often referred to the polyethylene of viscosity-average molecular weight 1,000,000-300 ten thousand) have excellent shock-resistant, wear-resistant, self-lubricating, resistance to chemical attack, health nontoxic, not easily adhere to, the not easily performance such as water suction, low temperature flexibility, thus purposes is very extensive.Current UHMWPE fiber is used widely in the field such as shellproof, energy-absorbing, high-tenacity cable, security textiles, engineering reinforcement, information, new forms of energy, medical treatment, Leisure Sport, has become the important High-tech Material being related to national security, Economic development.As on the net of the hawser, fishery, civil construction etc. of the civilian aspect of routine or the cloth of sheet material, chemical filter and separator or some matrix materials such as non-woven, motion dress material, require relatively low to the strength and modulus of polyethylene fibre, Given this, people attempt adopting melt-spinning technology, employing molecular weight is the High molecular weight polyethylene raw material between 50-100 ten thousand, preparation intensity is the fiber of 10-20cN/dtex, to meet the demand of civilian aspect, thus enhance productivity, reduce costs, the Application Areas of expansion fiber.
Because ultrahigh molecular weight polyethylene(UHMWPE) and High molecular weight polyethylene add, all to there is melt viscosity man-hour high, mobility extreme difference, and its melt flow index is almost nil, so be difficult to directly carry out extruding or injection molding.CN1539033A discloses the high-strength polyethylene fiber that a kind of intensity is more than 15N/dtex, this fiber be with weight-average molecular weight below 300000, the ratio of weight-average molecular weight and number-average molecular weight produces through melt-spinning for raw material at the polyethylene of below 4.0Wn/Mn, adopt this kind of production method, due to the hyperviscosity of melt, substantially cannot flow, thus cause difficulty in spinning, so the method described in this invention is difficult to realize suitability for industrialized production.
CN90107707.0 discloses and a kind ofly adopts solid state wax metallic substance plasticizing molecule amount to be 30-60's ten thousand
Polyvinyl resin produces the method for moulded parts after carrying out melting, by admixture plasticised mass in High molecular weight polyethylene resin, resin melt-flow can be extruded, the moulded parts obtained is stretched in the solvent of solid state wax pledge, after removing waxy substance, obtain the finished product.Add a large amount of thinners in the preparation process of the method, and then shaping rear removal thinner, exist complete processing complexity, cost high, to the disagreeableness problem of environment.
CN101476170A discloses a kind of melt-spinning and prepares high strength, the method for high-modulus polyethylene fibres and device, the blend composition of High molecular weight polyethylene disclosed in it adopts organosilicon to form blend composition as the properties-correcting agent of High molecular weight polyethylene, its component comprises High molecular weight polyethylene 85-97%, organosilicon 3-15%, oxidation inhibitor 0.2-2%; The three-component blend of High molecular weight polyethylene disclosed in it forms by the component of following weight percent is blended, High molecular weight polyethylene 88-94%, organosilicon 3-7%, liquid crystal polymer 2-5%, calcium stearate 0.2-2%, oxidation inhibitor 0.1-1%.The molecular weight of this invention to High molecular weight polyethylene does not limit, and does not describe the performance such as intensity of the fiber that High molecular weight polyethylene blend composition is produced.
CN101230501A discloses a kind of method adopting High molecular weight polyethylene and Low Density Polyethylene blended melting to prepare high-strength polyethylene, and wherein poly molecular weight is 120-180 ten thousand, and Low Density Polyethylene molecular weight is 2.5-4 ten thousand.Adopt twin screw extruder blended melting, prepare nascent fibre and stretch, entering in two oil baths and stretch, enter the finish that water bath removes fiber surface, dry and make the production of high-tenacity polyethylene fibre.The method that the method adopts Low Density Polyethylene to carry out blending and modifying can improve flowing property, but it is wide to there is molecular weight distribution, there is the problem of lousiness, fracture of wire in rear draft process.
CN1488668A discloses a kind of employing and adds 1-10 % by weight hyper-branched polyester-amide polymer, significantly can improve the processing rheological property of High molecular weight polyethylene and significantly reduce the melting viscosity of ultra-high molecular weight.Wherein the molecular weight of High molecular weight polyethylene is 1,000,000-300 ten thousand.But hyper-branched polyester-amide polymer to be fuming problem melt extruding in process to exist, and has detrimentally affect to the performance of product.
In sum, the melt viscosity for ultra-high molecular weight, High molecular weight polyethylene is high, the shortcoming of mobility extreme difference, and prior art usually adopts and adds thinner or auxiliary agent or adopt blended method to improve its mobility.Add thinner, easily cause the volatilization of the thinner of ultra-high molecular weight in follow-up manufacturing procedure obtained, unfriendly to environment; Adopting blended method, the deficiency of lousiness fracture of wire in rear draft process can be there is when preparing high molecular weight polyethylene fiber; Adopting the method adding auxiliary agent, there is the problem of being fuming when preparing high molecular weight polyethylene fiber.
Summary of the invention
The deficiency that object of the present invention exists to overcome prior art, provides a kind of High molecular weight polyethylene composition that can improve High molecular weight polyethylene rheological property.
The invention provides a kind of High molecular weight polyethylene composition, said composition contains High molecular weight polyethylene, oxidation inhibitor and stablizer, wherein, said composition is also containing flow ability modifying agent and processing aid, and described processing aid is selected from fluoropolymer additive and/or polycaprolactone; Described flow ability modifying agent be selected from ethylene bis stearic acid amide, methyl-silicone oil, polysiloxane and paraffin one or more, the viscosity-average molecular weight of described High molecular weight polyethylene is 500,000-150 ten thousand.
High molecular weight polyethylene composition good rheological property provided by the invention, is applicable to melt-spinning operation and prepares high polymer polyethylene fiber.When for the preparation of polyethylene fibre, be processed in the operation of fiber in follow-up, without the need to thinner removing step, environmentally friendly.Obtained polyethylene fibre breaking tenacity, at more than 10CN/dex, can meet the requirement of civilian fibre product performance.
Embodiment
The invention provides a kind of High molecular weight polyethylene composition, said composition contains High molecular weight polyethylene, oxidation inhibitor and stablizer, wherein, said composition is also containing flow ability modifying agent and processing aid, and described processing aid is selected from fluoropolymer additive and/or polycaprolactone; Described flow ability modifying agent be selected from ethylene bis stearic acid amide, methyl-silicone oil, polysiloxane and paraffin one or more, the viscosity-average molecular weight of described High molecular weight polyethylene is 500,000-150 ten thousand.
In the present invention, fluoropolymer additive refers to the processing aid based on fluoropolymer for improving, improving polymer processing performance.
According to the present invention, described High molecular weight polyethylene, oxidation inhibitor, stablizer, the consumption of flow ability modifying agent and processing aid can be the routine selection of this area.Usually, according to composition of the present invention, relative to the High molecular weight polyethylene of 100 weight parts, the content of described oxidation inhibitor is 0.05-1 weight part, the content of described stablizer is 0.05-0.5 weight part, the content of described processing aid is 0.01-0.5 weight part, and the content of described flow ability modifying agent is 0.5-10 weight part.Preferably, relative to the polyethylene of 100 weight parts, the content of described oxidation inhibitor is 0.3-0.5 weight part, and the content of described stablizer is 0.1-0.3 weight part, the content of described processing aid is 0.05-0.3 weight part, and the content of described flow ability modifying agent is 1-5 weight part.
As long as although the described processing aid of the present invention is selected from fluoropolymer additive and/or polycaprolactone; Described flow ability modifying agent be selected from ethylene bis stearic acid amide, methyl-silicone oil, polysiloxane and paraffin one or more just can realize the object of the invention, one of the present invention preferred embodiment in, described processing aid is fluoropolymer additive; The weight-average molecular weight of further preferred fluoropolymer processing aid is 200,000-30 ten thousand, and with the weight of fluoropolymer additive for benchmark, the content of fluorine element is 40-60 % by weight.The fluoropolymer additive meeting above-mentioned condition can be such as purchased from Shanghai Lanpoly Polymer Technology Co., Ltd., Minnesota Mining and Manufacturing Company's (trade mark can be FX-5920A, FX-5911 and FX-9614).As long as although the described processing aid of the present invention is selected from fluoropolymer additive and/or polycaprolactone; Described flow ability modifying agent be selected from ethylene bis stearic acid amide, methyl-silicone oil, ultra-high molecular weight polysiloxane and paraffin one or more just can realize the object of the invention, one of the present invention preferred embodiment in, wherein, described flow ability modifying agent is ultra-high molecular weight polysiloxane, the viscosity-average molecular weight of preferred described polysiloxane is 1,000,000-250 ten thousand, more preferably 1,500,000-220 ten thousand.In the present invention, the viscosity-average molecular weight of described polysiloxane adopts ASTMD4020-05 method to measure.Measuring temperature is 135 DEG C, and test solvent is decahydro how solvent.
According to the present invention, the viscosity-average molecular weight of High molecular weight polyethylene is generally 500,000-150 ten thousand, is preferably 600,000-90 ten thousand.In the present invention, the viscosity-average molecular weight of described High molecular weight polyethylene adopts ASTMD4020-05 method to measure.Measuring temperature is 135 DEG C, and test solvent is decahydro how solvent.
According to the present invention, the molecular weight distribution of High molecular weight polyethylene can be 3.5-5.5, is preferably 4-5.Described molecular weight distribution adopts the method specified in ISO16014-4:2003, and measuring temperature is 150 DEG C.
According to the present invention, wherein, the tensile strength of High molecular weight polyethylene can be more than 15MPa, is preferably 15-20MPa.Described tensile strength adopts the method specified in GB/T1040-2006, measures under draw speed 50m/min condition.
According to the present invention, wherein, the elongation at break of High molecular weight polyethylene can be more than 300%, is preferably 300-350%.Described elongation at break adopts the method specified in GB/T1040-2006, measures under draw speed 50m/min condition.
In the present invention, the various oxidation inhibitor that described oxidation inhibitor can be commonly used for this area, are 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, can one or more for being selected from hindered phenol system oxidation inhibitor and amine system oxidation inhibitor; Described auxiliary antioxidant can hydroperoxide effectively in decomposing copolymer, prevent its homolysis from producing new free radical, cause the carrying out of Auto-oxidation reaction, such as can one or more for being selected from phosphorous acid ester system oxidation inhibitor and monothioester system oxidation inhibitor.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 (namely, 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 (namely, irgasfos 168), four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites, three nonylated phenyl phosphorous acid esters, two (2,4-DTBP) pentaerythritol diphosphites, the two octadecyl of thio-2 acid and Tyox B.From the angle improving further antioxidant property, described antioxidant preferably using described phenol system oxidation inhibitor and/or amine system oxidation inhibitor as primary antioxidant, using phosphorous acid ester and/or monothioester as auxiliary antioxidant.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 1:0.5-4.The consumption of described oxidation inhibitor can be the routine selection of this area, and such as: relative to propene polymer described in 100 weight parts, the content of described oxidation inhibitor can be 0.3-0.5 weight part, is preferably 0.35-0.45 weight part.Preferably, described oxidation inhibitor is Hinered phenols and/or phosphite ester kind antioxidant, be preferably four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, three (2,4-di-tert-butyl-phenyl) one or more in phosphorous acid ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites and 2,6-di-t-butyl-4-methylbenzene.
In the present invention, in use there is aging additive in the various products that can prevent that described stablizer can be commonly used for this area, comprises photostabilizer and thermo-stabilizer.The example of described photostabilizer can include but not limited to: benzophenone system stablizer, such as: ESCALOL 567 (UV-9), Octabenzone (UV-531), triazine system stablizer, such as: 2,4,6-tri-(2-hydroxyl-4-butoxy phenyl)-1,3,5-triazines (triazine-5), nickel salt quencher, such as: dithiocarbamic acid nickel salt and two (3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel (Irgastab-2002), benzotriazole system stablizer, such as: 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole (UV-P), 2 '-(2 '-hydroxyl-3 '-the tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole (UV-326), hindered amine system stablizer, such as: three (1, 2, 2, 6, 6-pentamethvl base) phosphorous acid ester (GW540), poly-succinic (4-hydroxyl-2, 2, 6, 6-tetramethyl--1-piperidine ethanol) ester (photostabilizer 622), poly-[(6-morpholinyl-1, 3, 5-triazine-2, 4-yl)-((2, 2, 6, 6-tetramethyl--4-piperidyl) imido) hexane-((2, 2, 6, 6-tetramethyl--4-piperidyl) imido)] (photostabilizer 3346) and poly-[[6-[(1, 1, 3, 3-tetramethyl butyl) amine]-1, 3, 5-triazine-2, 4-bis-base] [(2, 2, 6, 6-tetramethyl--4-piperidines) imines]-1, 6-bis-dihexyl [(2, 2, 6, 6-tetramethyl--4-piperidines) imines]]] (photostabilizer 944), salicylate system stablizer, such as: dihydroxyphenyl propane sasapyrin (UV Absorber BAD) and Whitfield's ointment-4-tertiary butyl phenyl ester (UV light absorber TBS).The example of described thermo-stabilizer can include but not limited to: metallic soap system stablizer, such as: hydrotalcite, sodium stearate, Magnesium Stearate, calcium stearate, strontium stearate, barium stearate, Zinic stearas, cadmium stearate, aluminum stearate, lithium stearate, lead stearate, cobalt stearate, aluminium hydroxy distearate, stearic acid sub-tin, calcium laurate, barium laurate, zinc laurate, cadmium laurate, calcium benzoate and Zinc dibenzoate.The amount of described stablizer can carry out appropriate selection according to the kind of the polymer product of final preparation and embody rule occasion.Preferably, described stablizer is calcium stearate and/or Zinic stearas.
Composition according to the present invention is applicable to prepare various high molecular weight polyethylene fiber, and, when adopting composition of the present invention to prepare high molecular weight polyethylene fiber, not only when the method by melt-spinning prepares high molecular weight polyethylene fiber, can carry out spinning at higher velocities, and the intensity of the high molecular weight polyethylene fiber of preparation can be 10-20cN/dtex.
In the present invention, the breaking tenacity of high molecular weight polyethylene fiber adopts GB-T14344-2003 to measure.
In the present invention, the fiber number of high molecular weight polyethylene fiber adopts GB-T14343-2003 to measure.
The present invention is described in detail below in conjunction with embodiment.
The testing method that following examples relate to is as follows:
1, the mensuration of polyethylene viscosity-average molecular weight: ASTMD4020-05(135 DEG C, decahydro how solvent)
2, poly molecular chain conformation: ISO16014-4:2003
3, the breaking tenacity of fiber: GB-T14344-2003
4, the elongation at break of fiber: GB-T14344-2003
5, fiber number: GB-T14343-2003
6, poly tensile strength: GB-/T1040-2006
Embodiment 1
Viscosity-average molecular weight is High molecular weight polyethylene 100 parts (the extra-high polyethylene that Beijing second auxiliary factory produces of 750,000, molecular weight distribution is 4.2, tensile strength 16MPa, elongation at break 320%), four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.1 part, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester 0.2 part, calcium stearate 0.2 part, (Shangyu Java Macromolecule Material Co., Ltd. produces polysiloxane powder resin, the trade mark is SG-100, viscosity-average molecular weight is 1,500,000) 2 parts, fluoropolymer additive (the FX-5920A that Minnesota Mining and Manufacturing Company produces, weight-average molecular weight 200,000, with the weight of fluoropolymer additive for benchmark, the content of fluorine element is 40 % by weight) 2 parts, 10-35 DEG C mix after, at 260 DEG C, evenly mixing on LAB-STATION torque rheometer, rotating speed is 5 revs/min, mixing 5-20 minute, torque value after record numerical stability.
Embodiment 2
Viscosity-average molecular weight is High molecular weight polyethylene (the extra-high polyethylene that Beijing second auxiliary factory produces of 900,000, molecular weight distribution is 5, tensile strength 20MPa, elongation at break 350%) 100 parts, 2, 6-di-t-butyl-4-methylbenzene 0.3 part, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester 0.2 part, (Shangyu Java Macromolecule Material Co., Ltd. produces polysiloxane powder resin 5 parts, the trade mark is SG-100, viscosity-average molecular weight is 1,800,000), fluoropolymer additive (the FX-5911 that Minnesota Mining and Manufacturing Company produces, weight-average molecular weight 250,000, with the weight of fluoropolymer additive for benchmark, the content of fluorine element is 50 % by weight) 0.05 part, 10-35 DEG C mix after, at 220 DEG C, evenly mixing on LAB-STATION torque rheometer, rotating speed is 20 revs/min, mixing 5-10 minute, torque value after record numerical stability.
Embodiment 3
Viscosity-average molecular weight is High molecular weight polyethylene 100 parts (the extra-high polyethylene that Beijing second auxiliary factory produces of 600,000, molecular weight distribution 4.5, tensile strength 17MPa, elongation at break 325%), four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.2 part, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester 0.2 part, (Shangyu Java Macromolecule Material Co., Ltd. produces polysiloxane powder resin, the trade mark is SG-100, viscosity-average molecular weight is 2,200,000) 5 parts, fluoropolymer additive (the FX-9614 that Minnesota Mining and Manufacturing Company produces, weight-average molecular weight 300,000, with the weight of fluoropolymer additive for benchmark, the content of fluorine element is 60 % by weight) 0.3 part, 10-35 DEG C mix after, at 220 DEG C, evenly mixing on LAB-STATION torque rheometer, rotating speed is 20 revs/min, mixing 5-10 minute, torque value after record numerical stability.
Embodiment 4
Except processing aid changes polycaprolactone (LG-DOW is produced, and the trade mark is 2363-75D, and number-average molecular weight is 2000) into, outward, all the other are with embodiment 1.
Embodiment 5
Except flow ability modifying agent changes ethylene bis stearic acid amide into, all the other are with embodiment 1.
Embodiment 6
Except flow ability modifying agent changes methyl-silicone oil into, all the other are with embodiment 1.
Embodiment 7
Except flow ability modifying agent change into viscosity-average molecular weight be 1,000,000 polysiloxane (Guangzhou Science and Technology Ltd. of Fu Yuangui section produce, the trade mark is FY-R50, and viscosity-average molecular weight is 1,000,000) outward, all the other are with embodiment 1.
Comparative example 1
Except not adding except fluoropolymer additive, all the other are with embodiment 1.
Comparative example 2
Except not adding except polysiloxane, all the other are with embodiment 1.
Comparative example 3
Except not adding polysiloxane and fluoropolymer additive, all the other are with embodiment 1.
The torque value that above embodiment and comparative example are recorded by LAB-STATION torque rheometer is as shown in table 1.Wherein, torque value rangeability shows that more greatly mobility is better.
Table 1 High molecular weight polyethylene rheological property is analyzed
| Experiment numbers | Blend melt moment of torsion (N.m) | Torque value rangeability (%) |
| Embodiment 1 | 28 | 46 |
| Embodiment 2 | 36 | 30 |
| Embodiment 3 | 24 | 54 |
| Embodiment 4 | 39 | 25 |
| Embodiment 5 | 39 | 25 |
| Embodiment 6 | 37 | 29 |
| Embodiment 7 | 43 | 17 |
| Comparative example 1 | 40 | 23 |
| Comparative example 2 | 41 | 21 |
| Comparative example 3 | 52 | 0 |
As can be seen from the data of table 1, the High molecular weight polyethylene composition that method according to the present invention provides, flowing property is improved, and can meet in melt-spinning processing the requirement of polymer processing flowing property.Compare known by the data of embodiment 1 and embodiment 4, fluoropolymer additive can obtain the better composition of change in torque amplitude further compared with other processing aids.Compare known by the data of embodiment 1 and embodiment 5, embodiment 6, ultra-high molecular weight polysiloxane is other flow promoters comparatively, can obtain the better composition of change in torque amplitude further.And in comparative example 1, owing to not adding fluoropolymer additive, the mobility of the High molecular weight polyethylene composition obtained is lower than embodiment 1.Owing to not adding ultra-high molecular weight polysiloxane flow ability modifying agent in comparative example 2, the flowing property of the High molecular weight polyethylene composition obtained is lower than embodiment 1.And in comparative example 3, owing to not adding fluoropolymer additive and ultra-high molecular weight polysiloxane, the mobility of the High molecular weight polyethylene composition obtained is lower than embodiment 1.
Test case 1-7
Test case 1-7 prepares high molecular weight polyethylene fiber when being used for melt-spinning for illustration of composition provided by the invention.
After respectively the composition in embodiment 1-7 and comparative example 1-3 being mixed, add melt extruded in singe screw spinning-drawing machine, carry out melt-spinning after filtering, the temperature of melt-spinning controls at 230-265 DEG C, the speed of melt-spinning is 3 ms/min, the time of melt-spinning is 6 minutes, obtains polyethylene fiber precursor, is cooled to 10-20 DEG C.Then carry out spinning drawing, first carry out preliminary draft (first stage drawing-off) to polyethylene fiber precursor, longitudinal stretching 2 times, the temperature of preliminary draft is 10-35 DEG C; Once heat at 80 DEG C again, carry out low power stretching (drawing-off of subordinate phase) that draw ratio is 8, carry out the super drawing (drawing-off of subordinate phase) that draw ratio is 30 times after carrying out second-heating again at 110 DEG C, obtain high polymer polyethylene fiber.Its detected result is as shown in table 2 below.
The performance test results of table 2 high molecular weight polyethylene fiber
As can be seen from the data of table 2, the High molecular weight polyethylene composition that method according to the present invention provides contains specific flow ability modifying agent and processing aid, and its flowing property is improved, and can meet the requirement to polymkeric substance spinning property in melt-spinning processing.Compare known by the data of test case 1, test case 4, fluoropolymer additive, compared with other processing aids, can improve the melt surface fracture in extrusion further, improve spinning property.And in test comparison example 1, owing to not adding fluoropolymer additive, the High molecular weight polyethylene composition obtained is when melt-spinning, spinning property is poor, the surface irregularity of precursor, fracture of wire.In test comparison example 2, owing to not adding ultra-high molecular weight polysiloxane, spinning property is poor, and the thickness of precursor is uneven, and drawing-off easily produces lousiness.And in test comparison example 3, owing to not adding fluoropolymer additive and ultra-high molecular weight polysiloxane, precursor material strip melt flow property is poor, difficult forming.
Claims (8)
1. a High molecular weight polyethylene composition, said composition contains High molecular weight polyethylene, oxidation inhibitor and stablizer, it is characterized in that, said composition is also containing flow ability modifying agent and processing aid;
Wherein, described processing aid is selected from fluoropolymer additive and/or polycaprolactone, and the weight-average molecular weight of described fluoropolymer additive is 200,000-30 ten thousand, with the weight of fluoropolymer additive for benchmark, the content of fluorine element is 40-60 % by weight;
Wherein, described flow ability modifying agent be selected from ethylene bis stearic acid amide, methyl-silicone oil, polysiloxane and paraffin one or more, and the viscosity-average molecular weight of described polysiloxane is 1,000,000-250 ten thousand;
Wherein, the viscosity-average molecular weight of described High molecular weight polyethylene is 600,000-90 ten thousand, and molecular weight distribution is 3.5-5.5, and tensile strength is more than 15MPa, and elongation at break is more than 300%.
2. composition according to claim 1, wherein, relative to the High molecular weight polyethylene of 100 weight parts, the content of described oxidation inhibitor is 0.05-1 weight part, the content of described stablizer is 0.05-0.5 weight part, the content of described processing aid is 0.01-0.5 weight part, and the content of described flow ability modifying agent is 0.5-10 weight part.
3. composition according to claim 2, wherein, relative to the High molecular weight polyethylene of 100 weight parts, the content of described oxidation inhibitor is 0.3-0.5 weight part, the content of described stablizer is 0.1-0.3 weight part, the content of described processing aid is 0.05-0.3 weight part, and the content of described flow ability modifying agent is 1-5 weight part.
4. the composition according to claim 1 or 3, wherein, described processing aid is fluoropolymer additive.
5. the composition according to claim 1 or 3, wherein, described flow ability modifying agent is polysiloxane.
6. the composition according to claim 1 or 3, wherein, described oxidation inhibitor is Hinered phenols and/or phosphite ester kind antioxidant.
7. composition according to claim 6, wherein, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, three (2,4-di-tert-butyl-phenyl) one or more in phosphorous acid ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites and 2,6-di-t-butyl-4-methylbenzene.
8. the composition according to claim 1 or 3, wherein, described stablizer is calcium stearate and/or Zinic stearas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210426310.0A CN103788445B (en) | 2012-10-30 | 2012-10-30 | A kind of High molecular weight polyethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210426310.0A CN103788445B (en) | 2012-10-30 | 2012-10-30 | A kind of High molecular weight polyethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103788445A CN103788445A (en) | 2014-05-14 |
| CN103788445B true CN103788445B (en) | 2016-02-24 |
Family
ID=50664528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210426310.0A Active CN103788445B (en) | 2012-10-30 | 2012-10-30 | A kind of High molecular weight polyethylene composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103788445B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801986A (en) * | 2016-05-05 | 2016-07-27 | 日丰科技有限公司 | Processing aid master batch for PE-RT pipe and preparation method for processing aid master batch |
| CN107011622A (en) * | 2017-04-28 | 2017-08-04 | 东莞市耐格美塑胶制品有限公司 | A kind of super abrasive POM/PTFE sheet materials and preparation method thereof |
| CN109306098A (en) * | 2017-07-26 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of polyethylene composition and preparation method and applications and plate |
| CN109306541B (en) * | 2018-09-14 | 2020-06-05 | 上海化工研究院有限公司 | Preparation method of high-strength high-modulus polyethylene fiber |
| CN109440215B (en) * | 2018-11-28 | 2021-02-09 | 上海化工研究院有限公司 | Preparation method of high-performance polyethylene fiber |
| CN113150424B (en) * | 2021-04-22 | 2022-12-06 | 长春联塑实业有限公司 | Low-sag high-finish polyethylene composition and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401694A (en) * | 2002-03-27 | 2003-03-12 | 上海化工研究院 | Special material for modifying extrusion or blow-moulding-class super-high molecular weight polyethylene and preparing process thereof |
| CN102382344A (en) * | 2010-09-01 | 2012-03-21 | 中国石油化工股份有限公司 | Composition for preparing polyethylene pipe with superhigh molecular weight and preparation method thereof |
-
2012
- 2012-10-30 CN CN201210426310.0A patent/CN103788445B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401694A (en) * | 2002-03-27 | 2003-03-12 | 上海化工研究院 | Special material for modifying extrusion or blow-moulding-class super-high molecular weight polyethylene and preparing process thereof |
| CN102382344A (en) * | 2010-09-01 | 2012-03-21 | 中国石油化工股份有限公司 | Composition for preparing polyethylene pipe with superhigh molecular weight and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103788445A (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788445B (en) | A kind of High molecular weight polyethylene composition | |
| CN102108205B (en) | Low-smell toughening polyamide (PA) 6 material and preparation method thereof | |
| EP2245077B1 (en) | Monofilament fibers comprising ground calcium carbonate | |
| CN101759920B (en) | Polypropylene composite material with improved scraping and wiping resistance performance and preparation method thereof | |
| CN103589069A (en) | High-shock resistance polypropylene/polybutylene composite material as well as preparation method and purposes thereof | |
| US7825180B2 (en) | Thermoplastic blend compositions as soft coupling agents | |
| CN111454545A (en) | Degradable high-fluidity modified polyester alloy material and preparation method and application thereof | |
| CN103627056B (en) | The polyolefin blend of UV stable | |
| CN103789860A (en) | High molecular weight polyethylene fiber, preparation method and application thereof | |
| CN112063049B (en) | Cold-resistant polypropylene and preparation method thereof | |
| CN101759922A (en) | Light aging resistant polypropylene composition and preparation method thereof | |
| DE602004002957T2 (en) | ROTATIONAL FORMATION METHOD WITH REDUCED CYCLE TIME | |
| US20220281150A1 (en) | Filament composition | |
| CN110105724A (en) | The composite material and preparation method of anti-flammability | |
| EP2826808B1 (en) | Polyester fibres and filaments prepared by use of pmma pigment masterbatch, production method thereof and use | |
| JP2008163505A (en) | Oxymethylene conjugate fiber | |
| CN102532692A (en) | Wollastonite modified polypropylene composite material | |
| KR20180078960A (en) | Method for manufacturing high strength dyed-polyethylene terephthalate fiber and dyed fiber produced therefrom | |
| CN115286867A (en) | Nano compatibilized polypropylene polystyrene composition and preparation method thereof | |
| KR20130001770A (en) | Polypropylene resin composition for high tenacity fiber and high tenacity fiber manufactured by using the same | |
| JPH05209311A (en) | Polypropylene-based fiber | |
| EP1092747B1 (en) | Additive composition for organic polymers and its use | |
| CN109867917A (en) | A kind of toughness PET antimicrobial composite material and preparation method thereof | |
| CN114426737B (en) | Flame-retardant antibacterial long glass fiber reinforced polypropylene composite material and preparation method and application thereof | |
| JP2801666B2 (en) | Polypropylene resin composition and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170222 Address after: 100029 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee after: China Petroleum Chemical Co Patentee after: Beijing Yanshan Petrochemical High-Tech Technology Co., Ltd Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee before: China Petroleum Chemical Co |