CN107325551A - A kind of flexible nylon of resistance to alcohol material and preparation method thereof - Google Patents

A kind of flexible nylon of resistance to alcohol material and preparation method thereof Download PDF

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Publication number
CN107325551A
CN107325551A CN201710675034.4A CN201710675034A CN107325551A CN 107325551 A CN107325551 A CN 107325551A CN 201710675034 A CN201710675034 A CN 201710675034A CN 107325551 A CN107325551 A CN 107325551A
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nylon
resistance
alcohol
acid
impact modifier
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陈尚标
沈俊毅
胡瑞莉
殷炼伟
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WUXI YINDA NYLON CO Ltd
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WUXI YINDA NYLON CO Ltd
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Priority to CN201710675034.4A priority Critical patent/CN107325551A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of flexible nylon of resistance to alcohol and preparation method thereof, belong to preparation and the production field of nylon material.It at least contains nylon resin and anti-impact modifier；The preparation method of the described flexible nylon of resistance to alcohol is to obtain matrix resin by pre-polymerization, thickening two step method under certain temperature and pressure with diamines and diacid, further with anti-impact modifier blending and modifying, obtains the flexible nylon of resistance to alcohol.The flexible nylon of resistance to alcohol can be used for being used for the multilayer pipe of trandfer fluid on automobile, good with pliability, the characteristics of good barrier property, be particularly suitable for use in the conveying of alcohol blended fuel.The present invention uses Long carbon chain diamines and aromatic diacid as the raw material monomer of synthetic nylon, the characteristics of combining good long carbon chain nylon pliability and high phenyl ring rigidity, so that the nylon matrix resin of synthesis has preferable pliability and higher crystallinity, heatproof, resistance to alcohol and oil resistance are good.After anti-impact modifier is blended, pliability improves, and can be used for individual layer and multi-layered fluid transfer pipeline on motor vehicle.

Description

A kind of flexible nylon of resistance to alcohol material and preparation method thereof
Technical field
The present invention relates to a kind of flexible nylon of resistance to alcohol and preparation method thereof, belong to preparation and the production field of nylon material.
Background technology
With nylon 6, nylon66 fiber position represent crystallinity amorphous nylon resins, due to toughness, chemical proofing, electrically The excellent properties such as characteristic and the property for being easy to melt molding processing, are widely used in terms of fiber, engineering plastics.But Further investigation revealed that, these nylon are shown as under low temperature and dry state as fragility so that these nylon are at some to toughness Application in terms of higher field, such as tubing receives very big limitation.Long carbon chain nylon, such as nylon 11, nylon 12, due to have compared with Long carbochain, compared with conventional nylon, water absorption rate is lower, pliability is more preferable, after plasticization and modification, is widely used in motor vehicle On fluid delivery pipeline.
But in recent years, the requirement of the pipeline on motor vehicle for conveying fuel is increasingly improved.On the one hand it is to reduce The steam of gasoline and diesel oil reduces the discharge of volatile hydrocarbon by the infiltration of pipeline road；On the other hand, alcohol gasoline is obtained extensively General application.And nylon 11, nylon 12 these on transfer pipeline commonly use nylon resins can not entirely prevent the infiltration of alcohols, and And the infiltration of alcohols can cause the mechanical performance of oil pipe to decline, especially in terms of impact property.Another further aspect in order to reduce oil consumption, The burnup temperature of motor car engine increases, and this causes the temperature tolerance needs of material further to improve.
The content of the invention
The purpose of the present invention is to overcome above-mentioned weak point there is provided a kind of flexible nylon of resistance to alcohol and preparation method thereof.
Technical scheme, the invention provides a kind of flexible nylon of resistance to alcohol material.Wherein, the nylon material is at least Contain nylon resin and impact modifier.The mass ratio of nylon resin and anti-impact modifier can be 100:(1-60), preferably The mass ratio of ground, nylon resin and anti-impact modifier is 100:(1-50), it is highly preferred that nylon resin and anti-impact modifier Mass ratio be 100:(1-40).
However, according to various specific needs, without prejudice in the range of the object of the invention, aging suppression can also be added Agent, light stabilizer, formability modifying agent, any one or a few combination of colouring agent are used as auxiliary agent.Relative to nylon resin 100 mass parts, the total mass parts of auxiliary agent are 0-1.
Wherein, nylon resin from diamine component construction unit mole accounting more than 70%, preferably more than 80%, more It is preferred that more than 90% comes from Long carbon chain diamines, mole accounting more than 70% of the construction unit of dicarboxylic acid component, preferably 80% Above, more preferably more than 90% comes from aromatic diacid.
Long carbon chain diamine is made up of bioanalysis or chemical method, and it, which is originated, to be oil, its biological spin-off.Long carbon chain Diamine include but is not limited to decamethylene diamine, 11 carbon diamines, 12 carbon diamines, 13 carbon diamines, 14 carbon diamines, 15 carbon diamines, 16 carbon diamines, 17 carbon diamines, preferably DC18, decamethylene diamine.
As the raw material diamine component beyond Long carbon chain diamines, Putriscine, 1,6- hexamethylene diamines, 1,8- can be exemplified Octamethylenediamine, 2- methyl isophthalic acids, 5- pentanediamines, 2,2,4- trimethyl -1,6- hexamethylene diamines, 2,4,4- trimethyl -1,6- hexamethylene diamines, 2- first Base -1,8- octamethylenediamine, 5- methyl isophthalic acids, the aliphatic diamine such as 9- nonane diamines, 1,3- double (aminomethyl) hexamethylene, Isosorbide-5-Nitraes-bis- (ammonia Methyl) the ester ring type diamines such as hexamethylene, cyclohexanediamine, methyl cyclohexane diamines, IPD, the aromatic series such as m-xylene diamine Diamines or their mixture, but it is not limited to this.
Aromatic dicarboxylic acid and its derivative include but is not limited to terephthalic acid (TPA), M-phthalic acid.Preferably to benzene two Formic acid.
As the raw material diacid beyond aromatic dicarboxylic acid, succinic acid, glutaric acid, adipic acid, heptan can be exemplified Diacid, suberic acid, azelaic acid, decanedioic acid, DC11, SL-AH, tridecanyldicarboxylic acid, 14 carbon binary Acid, 15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18 or their mixture, but not It is defined in this.
When preparing nylon resin, in order to adjust the molecular weight of nylon resin or improve its hot water resistance, nylon resin End-capping reagent can be further added in raw materials for production.End-capping reagent is monocarboxylic acid, monoamine, acid anhydrides, monoisocyanates, single acyl Any one or a few combination in halogen, monoesters class and monohydric alcohol.Wherein, acid anhydrides includes but is not limited to phthalic acid Acid anhydride.From the viewpoint of production stability, preferably monocarboxylic acid or monoamine is used as end-capping reagent.
As the monocarboxylic acid that can act as end-capping reagent, as long as there is the monocarboxylic acid of reactivity then without spy with amino Do not limit.Monocarboxylic acid includes but is not limited to aliphatic monocarboxylic acid, alicyclic monocarboxylic acid and aromatic series monocarboxylic acid etc..Its In, aliphatic monocarboxylic acid includes but is not limited to acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, laurate, tridecanoic acid, meat Myristic acid, palmitic acid, stearic acid, trimethylace tonitric and isobutyric acid.Alicyclic monocarboxylic acid includes but is not limited to hexane formic acid. Aromatic series monocarboxylic acid includes but is not limited to benzoic acid, toluic acid, α-naphthoicacid, β-naphthoic acid, methyl naphthoic acid and benzene The aromatic series monocarboxylic acid such as guanidine-acetic acid.
As the monoamine that can act as end-capping reagent, as long as the monoamine for having reactivity with carboxyl is not limited especially then System.Monoamine includes but is not limited to aliphatic mono, cycloaliphatic monoamines and aromatic monoamines etc..Wherein, aliphatic one First amine includes but is not limited to methylamine, ethamine, propylamine, butylamine, hexylamine, octylame, decyl amine, stearylamine, dimethylamine, diethylamine, dipropyl Amine and dibutyl amine.Cycloaliphatic monoamines include but is not limited to cyclohexylamine and dicyclohexyl amine.Aromatic monoamines include but is not limited to Aniline, toluidines, diphenylamines and naphthylamines.
Impact modifier is any one or a few the combination in polyolefin, olefin copolymer and elastomer.
When using polyolefin or olefin copolymer as impact modifier, the polyolefin or olefin copolymer are by ethene (PE) with least one of other alpha-olefins, alkadienes, ethylenically unsaturated carboxylic acids (simple function group or difunctional), olefinic not What any one or a few in the ester derivative of saturated carboxylic acid or the anhydride ester derivs of ethylenically unsaturated carboxylic acids was polymerized Copolymer, especially selects uniform linear copolymer.Wherein, the carbon atom number of a- alkene is preferably 2-20, more preferably 3- 8.When at least one of ethene and other alpha-olefins generation copolymer, comonomer include but is not limited to propylene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes or 1- octenes.When ethene and alkadienes, ethylenically unsaturated carboxylic acids (simple function group or Difunctional), in the anhydride ester derivs of the ester derivative of the unsaturated carboxylic of olefinic or the unsaturated carboxylic of olefinic any one or it is several When planting generation copolymer, comonomer includes but is not limited to acrylic acid, methacrylic acid, vinyl acetate or maleic anhydride.
Foregoing polyolefin, olefin copolymer preferably comprise the polyolefin with polar group functionalization, typical functional group Group includes carboxylic acid, carboxylate, acid anhydride, amine, acid amides, epoxides, maleimide and compatible with nylon by polyolefin is made other Any functional group.It is preferred that functional group be during being fused and mixed can with nylon react group, such as amine, epoxides, acid and Carboxylic acid.Typical functionalised polyolefin is maleated polyolefin.Maleated polyolefin is known in the art, typically Maleic acid is grafted in polyolefin backbone and obtained.Typical maleated polyolefin includes maleated a- alkene, such as Ethylene-octene copolymer, ethylene-hexene co-polymers and ethylene-heptene copolymer.
The maleated of polyolefin can be carried out in molten state, solution state or solid-state, can be using accomplished continuously or intermittently method. Various radical initiators including peroxide and azo-compound are used equally for promoting maleated effect.It is all These methods are all known, are fully described in the prior art.Maleate agent reagent includes acid anhydride and unsaturated binary carboxylic Acid anhydrides includes but is not limited to maleic anhydride.
When using elastomer as impact modifier, elastomer is natural rubber, polybutadiene, polyisoprene, poly- different Butylene, neoprene, polysulfide rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, silicon rubber, epichlorohydrin rubber, benzene Ethylene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-benzene Ethylene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymers (SEBS), styrene-isoprene Block copolymer (SIR), hydrogenated styrene isoprene block copolymer (SEP), styrene-isoprene-phenylethene block Copolymer (SIS), hydrogenated styrene isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymerization Thing, hydrogenated styrene-butadiene random copolymer, styrene ethylene-propylene random copolymer, styrene-ethylene-butadiene without Rule copolymer, ethylene-propylene copolymer (EPR), ethene-(1- butylene) copolymer, ethene-(1- hexenes) copolymer, ethene- (1- octenes) copolymer, ethylene-propylene-diene copolymer (EPDM) or butadiene-acrylonitrile-styrene core shell rubbers (ABS), MBS core shell rubbers (MBS), methyl methacrylate-butyl acrylate-benzene Ethene core shell rubbers (MAS), 2-ethyl hexyl acrylate-butadiene-styrene core shell rubbers (MABS), alkyl acrylate-butadiene- Acrylonitrile-styrene core shell rubbers (AABS), butadiene-styrene core shell rubbers (SBR), with methyl methacrylate-propylene Acid butyl ester siloxanes is any one or a few the group in the nucleocapsid type rubber materials such as the core shell rubbers of silicone-containing of representative Close.
Elastomer preferably comprises the elastomer with polar group functionalization, and typical Functionalized elastomers are maleated Elastomer.Maleated elastomer is known in the art, and typically maleic acid is grafted on elastomer main chain and obtained.As One of part in toughening element, the grafting rate of above-mentioned polar group grafting is the 0.5%- of nylon resin (A) weight 8.0%, the preferably 1%-3% of nylon resin weight.The average grain diameter of elastomer is preferably 0.02-0.3 μm, more preferably 0.05μm-0.2μm.Relative to the amount part of foregoing nylons resin 100, the elastomeric impact modifier of foregoing use polar group functionalization The use level of agent is not particularly limited, preferably 1-50 mass parts, more preferably 1-40 mass parts.
The purpose of ageing inhibitor addition is for discoloration when preventing thermal degradation and heating, improves resistance to ag(e)ing and weather-proof Property.Ageing inhibitor include but is not limited to copper compound, phenol stabilizer, phosphite-type stabilisers, hindered amines stabilizer, Triazine type stabilizer, sulphur-containing stabilizer, compound of ultraviolet light absorbers and radical scavenger etc..Preparing nylon resin During, it can optionally add one or more of ageing inhibitors.
Copper compound includes but is not limited to cupric iodide.
Phenol stabilizer is two kinds in Hinered phenols primary antioxidant, phosphorous acid esters auxiliary anti-oxidant and mantoquita composite antioxidant Or a variety of compounds compounded according to a certain percentage.Wherein, Hinered phenols primary antioxidant includes but is not limited to four [β-(3,5- bis- Tert-butyl-hydroxy phenyl) propionic acid] pentaerythrite, β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecanol ester, N, N-1,6- hexylidenes-[3,5- di-t-butyl -4- hydroxypropanamides], N, N '-bis- [β-(3,5- di-tert-butyl-hydroxy phenyls) Propionyl] hydrazine, triethylene-glycol double [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester], (3,5- bis- of 1,3,5- tri- Tertiary butyl-4-hydroxy benzyl) isocyanuric acid, 1,3,5- trimethyls -2,4,6- (3,5- di-t-butyl -4- hydroxyphenylmethyls) benzene, 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone, 1, 3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid etc.；Phosphorous acid esters auxiliary anti-oxidant includes but is not limited to double ten Eight alkylol pentaerythritol diphosphites, three (2,4- DI-tert-butylphenol compounds) phosphite esters etc.；Mantoquita composite antioxidant is iodine Change the mixture of mixture either KBr and the cuprous iodide of potassium and cuprous iodide.When mantoquita composite antioxidant is KI During with the mixture of cuprous iodide, the mass fraction of KI is 50~90%, the mass fraction of cuprous iodide for 10%~ 40%.When mantoquita composite antioxidant is the mixture of KBr and cuprous iodide, the mass fraction of KBr is 50~90%, The mass fraction of cuprous iodide is 10%~40%.
UV absorbers mainly include benzotriazole or triazines UV absorbers, such as 2- (2'- hydroxyl -5'- first Base phenyl) BTA, 2- (2'- hydroxyls 3', 5'- di-tert-butyl-phenyl) -5- chlorinated benzotriazoles, (2'- hydroxyls -5'- is special by 2- Octyl phenyl) the parallel triazole of benzene；Radical scavenger is mainly hindered amines light derivative, such as (2,2,6,6- tetramethyl -4- piperidines Base) sebacate.
Formability modifying agent includes but is not limited to higher fatty acids, higher fatty acid metal salt, high-grade aliphatic ester and height Level fatty acid amide etc..During polyamide is prepared, one or more of formability improvement can be optionally added Agent.
Wherein, higher fatty acids include but is not limited to stearic acid, palmitic acid, behenic acids, sinapic acid, oleic acid, laurate and The saturation of the carbon number 8~40 of montanic acid etc. or undersaturated, straight or branched aliphatic monocarboxylic acid etc..It is preferred that lignite The metal salt and stearic metal salt of acid.
Higher fatty acid metal salt is the metal salt of higher fatty acids.Metallic element in higher fatty acid metal salt is preferred The race's element of the periodic table of elements the 1st, 2,3, zinc and aluminium etc., more preferably the race's element of calcium, sodium, potassium and magnesium etc. the 1st, 2 and aluminium etc..It is senior Fatty acid metal salts include but is not limited to calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, montanic acid calcium and montanic acid Sodium, calcium palmitate etc..It is preferred that the metal salt of montanic acid and stearic metal salt.
High-grade aliphatic ester is the carboxylate of higher fatty acids and alcohol.High-grade aliphatic ester, preferably carbon number are 8~40 Aliphatic carboxylic acid and carbon number for 8~40 ester, the ester of aliphatic alcohol etc..Aliphatic alcohol includes but is not limited to lipidol, mountain Yu alcohol and laruyl alcohol etc..High-grade aliphatic ester includes but is not limited to stearate, behenic acid esters.
Higher fatty acid amides are the amide compounds of higher fatty acids.Higher fatty acid amides include but is not limited to acyl Amine, oleamide, mustard seed acid amides, ethylenebisstearamide, ethylenebisoleoamide, N- stearyl stearamides, N- stearyls Mustard seed acid amides etc..The preferred stearmide of higher fatty acid amides, mustard seed acid amides, ethylenebisstearamide and N- stearyl mustard Sub- acid amides, more preferably ethylenebisstearamide and N- stearyl mustard seed acid amides.
Colouring agent includes but is not limited to dyestuff, pigment, metallic and metallic pigments etc..Wherein, dyestuff includes but not limited In amido black；Pigment includes but is not limited to titanium oxide and carbon black；Metallic include but is not limited to aluminium, coloring aluminium, nickel, tin, copper, Gold, silver, platinum, iron oxide, stainless steel and titanium；Metallic pigments include but is not limited to mica pearlescent pigment, painted graphite, color glass Glass fiber and stained glass thin slice etc..
The preparation method to the flexible nylon of the resistance to alcohol material of the present invention elaborates below.
Because nylon matrix resin contains phenyl ring, fusing point is higher, it is impossible to conventional nylon synthesizing mean.
In two steps, the first step, using water as solvent, carries out polymerisation in solution, obtains pre- synthetic nylon matrix resin in reactor Aggressiveness.The mass ratio of nylon resin and water is 100:(50~300), preferably 100:(100~300), more preferably 100:(100~ 200), while adding catalyst and end-capping reagent；Under 220~240 DEG C of reaction temperature, reaction pressure 2.5-3MPa pressure, during reaction Between 2-3 hours.
Nylon performed polymer is sent into the extrusion equipment with exhaust outlet by second step, and melting increasing is carried out under conditions of vacuumizing Viscous, thickening temperature is 290~310 DEG C, and the residence time is 1~15 minute, and vacuum is 0.09~-0.1MPa, obtains nylon base Body resin.
Obtained nylon matrix resin, impact modifier and above-mentioned ageing inhibitor as needed, formability are changed Good dose, colouring agent kneaded.Typically, by all components, batch mixing produces the blending of the present invention in mixing arrangement such as extruder Thing.Mixed using mechanical mixing apparatus such as ribbon mixer, solution mixing or other any suitable devices and technology.
It can enumerate for example：All components such as polyamide, impact modifier and other materials as needed enter Row mixing, and it is supplied to the method kneaded in melting mixing machine；Single screw rod or double screw extruder with decompressor In be formed as in the polyamide of molten condition coordinating impact modifier and other materials as needed from side feeder Method etc..
Melt blending temperature should be carried out on the fusing point of polyamide, but also should be ensured that polyamide bending melting again will not It is set to be selected in the range of decomposing.It should be sufficiently mixed simultaneously, but excessive shearing may cause undesirable high temperature, be worth noting Be that in this complicated blend batch mixing, all components are assigned especially as the equal bleeding formation of impact modifier of toughness reinforcing It is required that the structure of performance, can be sea-island structure or inierpeneirating network structure and semi-intercrossing network, to keep the toughened polymer of the present invention Amide resin composite has good toughness, and keeps higher intensity.
Melting mixing temperature is preferably more than 30 DEG C of the fusing point relative to nylon matrix resin.The melting mixing time is preferably About 1~8 minute.
Device on carrying out melting mixing is not particularly limited, and can use known device, such as single screw rod or double The melting mixing machines such as screw extruder, banbury mixers and mixing roller.
Carried out in aforementioned melt kneading machine after melting mixing, from nozzle plus filler polymer.Strands are 300~350 DEG C of height Temperature state, it is impossible to directly crushed and cut with the cutting roller of granulator, therefore be cooled to below the fusing point of polyamide.Generally Water is used in the cooling, the strands extruded from nozzle are cooled down in water.Strands after cooling are cut in granulator, by This obtains the flexible nylon of the resistance to alcohol material that can obtain present embodiment.
Beneficial effects of the present invention：The present invention is former as the monomer of synthetic nylon using Long carbon chain diamines and aromatic diacid Material, the characteristics of combining good long carbon chain nylon pliability and high phenyl ring rigidity so that the nylon matrix resin of synthesis has preferably Pliability and higher crystallinity, heatproof, resistance to alcohol and oil resistance are good.After anti-impact modifier is blended, pliability Improve, can be used for individual layer and multi-layered fluid transfer pipeline on motor vehicle.
Embodiment
Hereinafter, the present invention is specifically described by embodiment, comparative example, but the present invention is not limited in following realities Apply example.The evaluation method used in embodiment and comparative example is as follows：
(1) relative viscosity
Accurate weighing 1g polyamides, are added in 96% sulfuric acid of 100mL mass concentrations, in 20-30 DEG C of stirring Dissolving.After being completely dissolved, take solution to be placed in Ubbelohde viscometer, after 25 DEG C of thermostats are placed 10 minutes, determine lower reduction of speed Spend (t).In addition, decrease speed (the t of the same sulfuric acid of measure 96%0).According to the following formula by t and t0Calculate relative viscosity.
Relative viscosity=t/t0
(2) mechanical performance
Melted in injection (mo(u)lding) machine, at a temperature of 30 DEG C of the fusing point higher than polyamide, in injection pressure 600kgf/cm2, injection time 1.0sec, obtain being injected into matrix under conditions of 100 DEG C of mold temperature.Obtained injection moulding Piece is implemented at 25 DEG C after the annealing of 24 hours, and tests below has been carried out in the state of adiabatic drying.
Tensile strength, elongation at break are determined by ISO527-2 methods.Bending strength, bending modulus are surveyed by ISO178 methods It is fixed.Izod notched impact strength is determined by ISO180 methods.
(3) ethanol petrol resistant is tested
Under the conditions of 23 DEG C ± 2 DEG C of water temperature, determined and tried by water method of replacing according to regulation in GB/T 1033.1-2008 Sample initial volume, is accurate to 0.001g.Dry sample and be placed into the container equipped with oil.Prize container device is placed in 72 DEG C ± 2 DEG C 70h in baking oven, then makes sample be cooled in test test ambient temperature, takes out sample and surfaces externally and internally is wiped with filter paper Only, the final volume of sample is measured for above-mentioned identical method.Material ethanol petrol resistant is characterized according to the change of volume Ability.
Embodiment 1
By 2.58kg 14 carbon diamines, 1.66kg terephthalic acid (TPA)s acid, 4kg deionized water, 2g glacial acetic acid, 2g phosphorous Acid and 1g antioxidant 1010s are added in reactor, are warming up to temperature and are reached 240 DEG C, when pressure reaches 3.0MPa, discharge vapor Pressure is maintained 3.0MPa, after reacting 2 hours, obtain nylon 14T performed polymers.Obtained nylon 14T performed polymers are sent into band There is the extrusion equipment of exhaust outlet, melting thickening is carried out under conditions of vacuumizing, thickening temperature is 300 DEG C, and the residence time is 5 points Clock, vacuum is 300Pa, obtains nylon 14T resins.Detection thickening nylon 14T relative viscosities 2.2.
5kg thickening nylon 14T, 1kg EPDM-g-MA, 10g antioxidant 1098 is added into high mixer, in 400r/min bar Stir 5 minutes, after material is mixed thoroughly, be at the uniform velocity added to by feeder in double screw extruder under part.Through double spiral shells Bar melting mixing is uniformly extruded, cooled down, granulating, drying afterwards, packaging, when last finished product.
Embodiment 2
By 2.30kg 12 carbon diamines, 1.66kg terephthalic acid (TPA)s acid, 5kg deionized water, 5g benzoic acid, 1g phosphorous Acid and 2g antioxidant 1010s are added in reactor, are warming up to temperature and are reached 230 DEG C, when pressure reaches 2.5MPa, discharge vapor Pressure is maintained 2.5MPa, after reacting 3 hours, obtain nylon 12T performed polymers.Obtained nylon 12T performed polymers are sent into band There is the extrusion equipment of exhaust outlet, melting thickening is carried out under conditions of vacuumizing, thickening temperature is 290 DEG C, and the residence time is 8 points Clock, vacuum is 300Pa, obtains nylon 12T resins.Detection thickening nylon 14T relative viscosities 2.3.
5kg thickening nylon 12T, 1kg SEBS-g-MA, 10g antioxidant 1098 is added into high mixer, in 400r/min bar Stir 5 minutes, after material is mixed thoroughly, be at the uniform velocity added to by feeder in double screw extruder under part.Through double spiral shells Bar melting mixing is uniformly extruded, cooled down, granulating, drying afterwards, packaging, when last finished product.
Embodiment 3
By 2.02kg decamethylene diamine, 1.66kg terephthalic acid (TPA)s acid, 5kg deionized water, 5g decanedioic acid, 1g ortho phosphorous acids Sodium and 2g antioxidant 1010s are added in reactor, are warming up to temperature and are reached 230 DEG C, when pressure reaches 2.5MPa, discharge vapor Pressure is maintained 2.5Mpa, after reacting 3 hours, obtain nylon 12T performed polymers.Obtained nylon 10T performed polymers are sent into band There is the extrusion equipment of exhaust outlet, melting thickening is carried out under conditions of vacuumizing, thickening temperature is 290 DEG C, and the residence time is 7 points Clock, vacuum is 300Pa, obtains nylon 10T resins.Detection thickening nylon 14T relative viscosities 2.4.
5kg thickening nylon 10T, 1kg POE-g-MA, 10g antioxidant 1098 is added into high mixer, in 400r/min bar Stir 5 minutes, after material is mixed thoroughly, be at the uniform velocity added to by feeder in double screw extruder under part.Through double spiral shells Bar melting mixing is uniformly extruded, cooled down, granulating, drying afterwards, packaging, when last finished product.
Embodiment 1-3 test results are as shown in table 1.
Table 1
According to upper table it can be seen that, flexible nylon of the invention while higher mechanical strength is kept, pliability compared with Good, ethanol petrol can not almost permeate, and can apply on automobile convey the pipeline of alcohol blended fuel.
The above-mentioned description to embodiment is that this hair is understood that and used for ease of those skilled in the art It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein General Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, Those skilled in the art are according to the announcement of the present invention, and not departing from improvement and modification that scope made all should be in this hair Within bright protection domain.

Claims (9)

1. a kind of flexible nylon of resistance to alcohol material, it is characterized in that formula rate is as follows：It include nylon resin, anti-impact modifier, End-capping reagent and auxiliary agent, nylon resin：Anti-impact modifier：End-capping reagent：Auxiliary agent mass ratio is 100: 1-60 : 0.01-0.5 : 0-1。
2. the flexible nylon of resistance to alcohol material as claimed in claim 1, it is characterized in that：The nylon resin：Anti-impact modifier：End-blocking Agent：Auxiliary agent mass ratio is 100: 1-50 : 0.05-0.5 : 0-1.
3. the flexible nylon of resistance to alcohol material as claimed in claim 1, it is characterized in that：The nylon resin：Anti-impact modifier：End-blocking Agent：Auxiliary agent mass ratio is 100: 1-40 : 0.05-0.5 : 0-1.
4. the flexible nylon of resistance to alcohol material as claimed in claim 1, it is characterized in that：The nylon resin is accounted for by Long carbon chain diamines mole Than being prepared from the raw material diamines more than 70% with raw material dicarboxylic acids of the aromatic diacid mole accounting more than 70%.
5. the flexible nylon of resistance to alcohol material as claimed in claim 1, it is characterized in that：The impact modifier is polyolefin, alkene is common Any one or a few combination in polymers and elastomer.
6. the flexible nylon of resistance to alcohol material as claimed in claim 1, it is characterized in that：The end-capping reagent is monocarboxylic acid, monoamine, acid Any one or a few combination in acid anhydride, monoisocyanates, single carboxylic acid halides, monoesters or monohydric alcohol.
7. the flexible nylon of resistance to alcohol material as claimed in claim 1, it is characterized in that：The auxiliary agent is ageing inhibitor, formability changes One or more of combinations in good dose and colouring agent.
8. the preparation method of one of the claim 1-7 flexible nylon of the resistance to alcohol materials, it is characterized in that step is as follows：First with water It polymerize synthetic nylon performed polymer for solvent solution, the melt polycondensation of nylon performed polymer or solid phase polycondensation obtain nylon resin；By Buddhist nun Imperial resin, impact modifier, end-capping reagent and auxiliary agent are that raw materials for production carry out melting mixing, and melting mixing temperature compares polyamide Fusing point it is high 10 ~ 30 DEG C, the melting mixing time be 1 ~ 8 minute, the strands extruded after melting mixing cool downs in water, cutting Granulating, obtains the flexible nylon of resistance to alcohol.
9. the preparation method of the flexible nylon of resistance to alcohol material as claimed in claim 8, it is characterized in that step is as follows：
（1）The preparation of nylon performed polymer：Raw material diamines, raw material dicarboxylic acids, water, end-capping reagent and catalyst are added into reactor first In, heating reaches 220-240 DEG C, and pressure is 2.5-3.0MPa, and discharge vapor maintains pressure, after reaction 2-3h, obtains Buddhist nun Imperial performed polymer；
（2）Thickening：Gained nylon performed polymer is sent into the extrusion equipment with exhaust outlet, melted under conditions of vacuumizing Thickening, thickening temperature is 290-310 DEG C, and the residence time is 1-15 minutes, and vacuum is 0.09 ~ -0.1MPa, obtains nylon tree Fat；
（3）The preparation of the flexible nylon of resistance to alcohol material：By nylon resin：Anti-impact modifier：Auxiliary agent mass ratio is 100: 1-60 ：0-1 ratio adds high mixer, is stirred 4-6 minutes under 350-450r/min speed, after material is mixed thoroughly, At the uniform velocity be added to by feeder in double screw extruder, through twin-screw melting mixing it is uniform after extrusion, cooling, granulation, dry Dry, packaging, when the last finished product flexible nylon of resistance to alcohol material.
CN201710675034.4A 2017-08-09 2017-08-09 A kind of flexible nylon of resistance to alcohol material and preparation method thereof Pending CN107325551A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110885442A (en) * 2019-12-17 2020-03-17 郑州大学 Synthetic method of copolymerized semi-aromatic nylon
CN111690130A (en) * 2019-03-15 2020-09-22 鞍山七彩化学股份有限公司 High-temperature-resistant nylon resin and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102617850A (en) * 2012-03-30 2012-08-01 金发科技股份有限公司 High-temperature resistant nylon and nylon composite material with good fracture toughness

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102617850A (en) * 2012-03-30 2012-08-01 金发科技股份有限公司 High-temperature resistant nylon and nylon composite material with good fracture toughness

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111690130A (en) * 2019-03-15 2020-09-22 鞍山七彩化学股份有限公司 High-temperature-resistant nylon resin and preparation method thereof
CN111690130B (en) * 2019-03-15 2022-10-14 鞍山七彩化学股份有限公司 High-temperature-resistant nylon resin and preparation method thereof
CN110885442A (en) * 2019-12-17 2020-03-17 郑州大学 Synthetic method of copolymerized semi-aromatic nylon

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