CN108603030A - There is the polyarylene sulfide composition of excellent adhesion to metal - Google Patents
There is the polyarylene sulfide composition of excellent adhesion to metal Download PDFInfo
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- CN108603030A CN108603030A CN201780008608.0A CN201780008608A CN108603030A CN 108603030 A CN108603030 A CN 108603030A CN 201780008608 A CN201780008608 A CN 201780008608A CN 108603030 A CN108603030 A CN 108603030A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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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
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
Abstract
The present invention relates to it is a kind of with a small amount of outgassing and excellent whiteness, acid resistance and metallic adhesion polyarylene sulfide composition.The polyarylene sulfide composition of the present invention shows a small amount of outgassing and excellent whiteness, acid resistance and metallic adhesion, and the resin combination for the product that can be required to formed precision as manufacture.
Description
Technical field
The present invention relates to it is a kind of with a small amount of outgassing and excellent whiteness, acid resistance and metallic adhesion poly arylidene thio-ester
Composition.
Background technology
Currently, poly arylidene thio-ester (hereinafter referred to as " PAS ") is used as a kind of typical engineering plastics, since its is higher heat-resisting
Property, chemical resistance, anti-flammability and electrical insulating property and deposited in the product and various electronic goods that are used in high temperature and corrosive environment
In growing demand.Polyphenylene sulfide (hereinafter referred to as " PPS ") is unique commercially available poly arylidene thio-ester.PPS is because of its excellent machine
Tool, electricity, hot property and chemical resistance and be widely used in motor vehicle equipment, the electrically or electronically shell or major part of equipment.
The method for being widely used in PPS commodity productions is in the polar organic solvent of such as N-Methyl pyrrolidone to conduct
The paracide (hereinafter referred to as " pDCB ") and vulcanized sodium of raw material carry out polymerisation in solution, this is referred to as wheat Charon technique
(Macallum process).However, when PPS is by wheat Charon technique productions, the solution polymerization process of vulcanized sodium etc. is used
The by-product (for example, NaCl) of salt form can be generated.Since the by-product of salt form may damage the performance of electronic component, because
This need additional washing or drying process etc. with remove by-product and remaining organic solvent (referring to United States Patent (USP) 2,513,
188 and 2,583,941).
To solve the above-mentioned problems, it is proposed that a kind of by the reactant containing two iodo aromatic compounds and elementary sulfur
Melt polymerization is come the method for preparing the PAS of such as PPS.Since this method does not generate the by-product of salt form during preparing PAS
Object, and organic solvent is not used, therefore individual technique is not needed to remove by-product or organic solvent.
Meanwhile traditional PPS has the problem with metallic adhesion difference, this is because being generated in Injection Molding forward position big
Outgassing (ougas) (i.e. the oligomer of low molecular weight) is measured, this hinders micropore when PPS is adhered on metal and is filled, to
Reduce metallic adhesion.As improve PPS metallic adhesion one kind alternative it has been proposed that one kind pass through by
Prepared by PPS is mixed with the polyolefin containing polar group and bulking agent resin combination.It has been found, however, that using
This oligomer (such as polyolefin containing such bulking agent or polar group) reduces the mechanical performance of PPS or reduces it
Thermal characteristics.
Invention content
Technical problem
Therefore, it is necessary to develop a kind of PAS compositions with excellent metallic adhesion, and has in flow front and subtract
Few release quantity (this is a potential problems in conventional metals plastic adherent), and with the by-product of a small amount of such as chlorine
Object.
There is excellent whiteness, acid resistance and metallic adhesion it is an object of the present invention to provide a kind of, and flowing
The resin combination of a small amount of outgassing is generated in dynamic forward position.
Further, it is another object of the present invention to provide a kind of mould carrying out casting and forming manufacture by the resin combination
Mould product.
Technical means to solve problem
In order to achieve the above objectives, the present invention provides a kind of resin combinations, including poly arylidene thio-ester and poly terephthalic acid
Cyclohexalene dimethylene ester, it includes the repetitive unit that formula 1 indicates that the cyclohexanedimethanol, which supports dimethylene ester, wherein
Release quantity is 300ppm or less：
[formula 1]
In addition, the present invention also provides a kind of moulding articles carrying out casting and forming manufacture by above-mentioned resin combination.
Beneficial effects of the present invention
The resin combination of the present invention has excellent metal adhesion performance, the excellent mechanical proprietary without reducing PAS
Energy and hot property have a small amount of outgassing.Therefore, various applications are all possible, including one by insert injection molding
The electronic component of change is to auto parts.In addition, the resin combination includes the by-product of a small amount of salt form, and will not reduce
The performance of electronic product, and may be used as the internal material of portable phone (a cellular phone) or laptop
Performance without reducing electronic product.Reach higher white in addition, the resin combination in acid after handling
Degree, and exterior material application is also used as other than being used as internal material.
Description of the drawings
Fig. 1 is the office for indicating the resin combination manufacture using the present invention for testing the sample to the adhesion strength of metal
The schematic diagram of portion's process.
Preferred embodiment of the present invention
The present invention provides a kind of resin combinations, including poly arylidene thio-ester and cyclohexanedimethanol to support dimethylene
Ester, it includes the repetitive unit that formula 1 indicates that the cyclohexanedimethanol, which supports dimethylene ester,：
[formula 1]
The resin combination of the present invention has a small amount of outgassings of 300ppm or less, and it is viscous to obtain excellent metal
Attached performance.Specifically, the resin combination has the release quantity of 150-300ppm.
The chlorinity of the resin combination is 300ppm or less, and includes the by-product of a small amount of salt form, to not
The performance of electronic product can be reduced.Particularly, the chlorinity of the resin combination is 200ppm or less, 100ppm or more
It is few, for example, more than 0 to less than or be equal to 100ppm, be 50ppm or less more particularly.
It is 80MPa or higher, in particular 80- according to the tensile strength values of the resin combinations measured of ISO 527
150MPa。
According to the metal adhesion intensity value of the resin combinations measured of ASTM D 3163 be 60MPa or higher, especially
Ground is 60-80MPa.
In addition, including specular components (specular component-included, SCI) mould according to D65 light sources
The L values for the resin combination that formula measures are 89 or higher, in particular 90-93.L values are higher, and whiteness is better.
Metal adhesion intensity value of the resin combination measured according to ASTM D 3163 after anodic oxidation be
55MPa or higher, in particular 55-80MPa.
The resin combination measured according to the SCI patterns of D65 light sources is carrying out sun by using the chemical method of acid
L values after the oxidation of pole are 88 or higher, in particular 88-93.
Hereinafter, the present invention is described in detail.
The resin combination of the present invention includes poly arylidene thio-ester.
The poly arylidene thio-ester includes the iodine being bonded with its main chain and free-iodine, particularly, the iodine that is bonded with main chain and free
The amount of iodine can be 10-10,000ppm.The amount of the iodine and free-iodine that are bonded with main chain can be by being heat-treated poly- virtue at high temperature
It thioether sample and is measured using ion chromatography standard measure.Free-iodine is to polymerize two iodo aromatic compounds and element sulphur
It generates in the process, and includes iodine molecule, iodide ion, iodine free radical etc., general holding is mutually changed with the poly arylidene thio-ester finally generated
Credit from state.
Poly arylidene thio-ester can be by carrying out melt polymerization to the reactant comprising two iodo aromatic compounds and element sulphur
To prepare.The two iodo aromatic compounds that can be used in the polymerisation can be selected from diiodo-benzene (DIB), diiodonaphthalene,
At least one of the group that diiodide, diiodo- bis-phenol and diiodobenzophenone are constituted, but an embodiment of the present invention is not limited to
This.In addition, two iodo aromatic compounds may include wherein substituted base alkyl or two iodo aromatic series of sulfuryl substitution
Close two iodo aromatic compounds of the atom containing such as oxygen and nitrogen in object or aromatic radical.Further, two iodo aromatic series
Compound can have the various isomers of diiodide, and wherein change of the iodine in para-linkage according to the bonding position of iodine
Object is closed, for example, paradiiodobenzene, 2,6- diiodonaphthalenes and 4,4'- diiodides are more particularly suitable.
The form of the element sulphur reacted with two iodo aromatic compounds is not particularly limited.Element sulphur is usually with eight sulphur of ring
(S8) form exists, wherein 8 atoms connect at room temperature.If not this form, it is nonetheless possible to use commercially available solid or
The sulphur of liquid form and be not particularly limited.
In addition, the mixture of two iodo aromatic compounds and reactant can further include polymerization initiator, stabilizer
Or mixtures thereof.Polymerization initiator may include selected from 1,3-, bis- iodo- 4- nitrobenzenes, mercaptobenzothiazoler, 2,2'-, bis- thio benzos
At least one of the group that thiazole, cyclohexylbenzothiazole sulfenamide and butyl benzo thiazolesulfenamide are constituted, but it is unlimited
In this.
Stabilizer can use without limitation, as long as it is common stabilizer in resin polymerization reaction.
Meanwhile in melt polymerization process, polymerization quencher can be added.Polymerization quencher is not particularly limited, only
Want it that can remove the iodine group for including in the polymer of polymerization to stop polymerization.Specifically, polymerization quencher can be
Selected from diphenyl sulfide, diphenyl ether, diphenylbenzophenone, bisbenzothiazole disulphide, single iodine aryl compound, benzo thiophene
At least one of the group that azoles, benzothiazole sulfenamide, thiurams (thiurams) and dithiocarbamate are constituted.
More specifically, polymerization quencher can be selected from iodine biphenyl, iodophenol, Iodoaniline, iodobenzophenone, 2- sulfydryl benzo thiophenes
Azoles, 2,2'- dithiobisbenzothiazoles, N cyclohexyl 2 benzothiazole sulfenamide, the thio benzothiazole of 2- morpholinoes, N,
N- dicyclohexyls -2-[4-morpholinodithio sulfenamide, tetra methylthiuram list sulfide, tetramethyl thiuram disulfide, diformazan
At least one of the group that base zinc dithiocarbamate, zinc diethyl dithiocarbamate and diphenyl disulfide are constituted.
The molecular weight of target poly arylidene thio-ester can be considered to determine in the decanting point of polymerization quencher.For example, polymerization quencher
Can by reaction consume about 70-100wt% be included in initial reactant in two iodo aromatic compounds when
Carve injection.
In addition, the condition of melt polymerization is not particularly limited, as long as can cause comprising diiodo- aromatic compounds and sulphur member
The polymerization of the reactant of element.For example, melt polymerization can carry out at raised temperature and the pressure condition of reduction.At this
In the case of kind, the initial reaction condition held in the palm from 180-250 DEG C and 50-450 can increase temperature to 270-350 DEG C and can drop
The end reaction condition that low-pressure is held in the palm to 0.001-20, and the reaction can carry out about 1-30 hour.More specifically, this is poly-
It is carried out under the conditions of conjunction reaction can be about 280-300 DEG C in temperature, pressure is about the end reaction of 0.1-1 supports.
Meanwhile the method for preparing poly arylidene thio-ester can further comprise before melt polymerization：Melting mixing includes
Diiodo- from generation to generation the reactant of aromatic compound and element sulphur the step of.The condition of melting mixing is not particularly limited, as long as instead
Answer object that can be melt-mixed.For example, the melting mixing step can be at 130-200 DEG C, especially 160-190 DEG C of temperature
Degree is lower to carry out.The melting mixing step before melt polymerization can allow subsequent melt polymerization easily into
Row.
According to another implementation of the invention prepare the method for poly arylidene thio-ester, which can be with
It is carried out in the presence of nitrobenzene catalyst.In addition, when carrying out melting mixing in taking a step forward for above-mentioned melt polymerization
When step, nitrobenzene catalyst can be added in the melting mixing step.For example, nitrobenzene catalyst may include but
It is not limited to bis- iodo- 4- nitrobenzenes of 1,3- or the iodo- 4- nitrobenzenes of 1-.
Different from customary preparation methods, thus obtained poly arylidene thio-ester is nearly free from the by-product of salt form.For example, this
The chlorinity of the poly arylidene thio-ester of invention is 300ppm or lower, especially 200ppm or lower, more particularly 100ppm or lower.
The fusing point of the poly arylidene thio-ester can be about 265-290 DEG C, about 270-285 DEG C, or about 275-283 DEG C.In addition, this is poly-
The number-average molecular weight of aromatic sulfide can be about 5,000-50,000, about 8,000-40, and 000, or about 10,000-30,000.Into one
Step ground, the poly arylidene thio-ester can be defined as opposite with the dispersion degree of about 2.0-4.5, about 2.0-4.0, or about 2.0-3.5
In the weight average molecular weight of number-average molecular weight.
The melt viscosity of the poly arylidene thio-ester measured at 300 DEG C with rotatingdisc viscometer can be about 10-50,000
Pool, about 100-20,000 pool, or about 300-10,000 pool.
Meanwhile resin combination of the invention includes that cyclohexanedimethanol supports dimethylene ester (PCT).This is poly- to benzene
Dioctyl phthalate cyclohexalene dimethylene ester includes the repetitive unit that following formula 1 indicates.
[formula 1]
Including the PCT of the repetitive unit indicated by formula 1 can have 10,000-200,000 or 30,000-70,000 weight
The inherent viscosity (IV) of average molecular weight and 0.1-1dl/g or 0.5-0.8dl/g.In addition, when use spectrocolorimeter according to
When being measured comprising specular components pattern of D65 light sources, the L values of the PCT are 80 or higher, in particular 85 or more
It is high；B values are 10 or lower, in particular 6 or lower.
The PCT can be prepared by customary preparation methods, including by include germanium compound catalyst be injected into it is diolation
The step of closing in the mixture of object and dicarboxylic acids and stirring to carry out esterification and polycondensation reaction.
Based on the PAS of 100 parts by weight, the resin combination can include 0.5-50 parts by weight, 1-40 parts by weight or 3-
The PCT of 30 parts by weight.In the case where the amount based on 100 parts by weight PAS, PCT is 0.5 parts by weight or more, metallic adhesion
It may become excellent with whiteness, and be 50 parts by weight or less in the amount of the PCT, resin group may not occur
Close the deterioration of the mechanical strength of object.
According to embodiment of the present invention, the resin combination can obtain excellent whiteness and metal adhesion
Property, this is that traditional pas resin composition institute is inaccessiable, and can also obtain high whiteness after anodic oxidation and retain
Rate and high metal adhesiveness.
In addition, the resin combination of the present invention can also include selected from phenoxy resin (phenoxy resin), elasticity
Body, filler, shock absorber fluid (shock absorber), adhesiveness reinforcing agent, stabilizer, pigment, plasticizer, lubricant and nucleating agent
At least one of component.
The resin combination may further include phenoxy resin, and the phenoxy resin by further including
The metallic adhesion of the resin combination can be enhanced.Specifically, the weight average molecular weight of the phenoxy resin can be 10,
000-250,000, glass transition temperature is 50-130 DEG C.More specifically, the phenoxy resin can be indicated with following formula 2.
More specifically, the phenoxy resin may include bisphenol-A (BPA), and can be with 20,000-220,000 Weight-average molecular
Amount and 60-120 DEG C of glass transition temperature.
[formula 2]
In formula 2, n is the integer of 100-900.Specifically, n can be 100-700 integer, the integer of 100-500,
The integer of 100-300, the integer of 200-300 or the integer of 300-500.
The end of the phenoxy resin can be replaced by hydroxyl and/or carboxyl.
Based on the PAS of 100 parts by weight, the resin combination may include the phenoxy resin of 1-75 parts by weight.Particularly,
Based on the PAS of 100 parts by weight, the addition of the phenoxy resin can be 3-15 parts by weight.
Elastomer can be additionally incorporated in the resin combination of the present invention, it is tough to assign the resin combination
Property, and generate the effect prevented because leading to the interfacial separation between resin and metal after metal adhesion due to temperature change.Make
For elastomer, can use selected from polyvinyl chloride elastomer, ethylene octane copolymer, polyurethane elastomer, polyesters bullet
Property body, polyamide-based elastomer, polybutadiene elastomer and glycidyl methacrylate, methacrylate and
At least one of the group that the terpolymer of ethylene is constituted thermoplastic elastomer (TPE).Particularly, the elastomer can be methyl
The terpolymer of glycidyl acrylate, methacrylate and ethylene.
Based on the PAS of 100 parts by weight, the resin combination may include 1-75 parts by weight, especially 3-35 parts by weight
Elastomer.
As filler, it can use and be selected from glass fibre, carbon fiber, boron fibre, bead, sheet glass, talcum powder and carbon
At least one of the group that sour calcium is constituted, and glass fibre is preferred.The glass fibre can be the glass of silane treatment
Fiber, and the silane can be selected from epoxy silane and amino silane and combinations thereof, and particularly, can use at epoxy silane
The glass fibre of reason.
The filler can be the form of powder or thin slice, but not limited to this.
Based on the PAS of 100 parts by weight, the content of the filler can be 5-250 parts by weight, preferably 10-150 weight
Part.
The pigment can be organic or inorganic pigment well known in the art, and can be selected from, for example, zinc sulphide
(ZnS), zinc oxide (ZnO), titanium dioxide (TiO2) and combinations thereof.Particularly, the pigment can be zinc sulphide (ZnS).
Based on the PAS of 100 parts by weight, the content of the pigment can be 0.1-50 parts by weight, preferably 0.3-25 weight
Part.
The stabilizer can be, such as antioxidant, light stabilizer and combinations thereof.In addition, based on 100 parts by weight
The content of PAS, the stabilizer can be 0.1-10 parts by weight.
The example of antioxidant may include any material for assigning the resin combination high-fire resistance and thermal stability
Material is without especially limiting.It is, for example, possible to use phenol antioxidant, amine antioxidants, sulphur class antioxidant and Phosphorus anti-
Oxidant.As phenol antioxidant, it is preferable to use hindered phenol compound.The specific example of phenol antioxidant is four (sub-
Methyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester) methane, bis- [3- (3, the 5- di-t-butyl -4- hydroxyls of thio diethylene
Base phenyl) propionic ester], N, N'- it is bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine etc..It is Phosphorus anti-oxidant
The example of agent is three (2,4- di-tert-butyl-phenyls) phosphates, O, O'- octacosyl pentaerythrites bis- (phosphite esters), double
Bis- four oxygen of (2,4- di-t-butyls phenoxy group) -2,4,8,10- of (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, 3,9-
Miscellaneous -3,9- two phospha spiral shell [5.5] hendecane etc..
Light stabilizer can be any material that can be absorbed and stop ultraviolet light without especially limiting；And can be,
For example, benzophenone compound；Salicylic acid ester type compound；Benzotriazole compound；Acrylonitrile compound；With purple
Other compounds of outside line assimilation effect, such as conjugated compound；The compound of free radical, such as hindered amine compound can be captured
And hindered phenol compound, or combinations thereof.If simultaneously using with ultraviolet radiation absorption effect compound and can capture from
By the compound of base, then high ultraviolet radiation absorption and blocking effect can be obtained.
The resin combination can further include the lubricant for enhancing mouldability.Particularly, alkyl lubricates
Agent can be used for preventing the friction between resin and Mold Metal, and allow readily to be detached from (releasable property) etc. from mold.Hydrocarbon
Base lubricating agent can be selected from paraffin, polyester (PE) wax, polypropylene (PP) wax, oxidation polyester wax and combinations thereof without especially limiting.
In addition, the PAS based on 100 parts by weight, lubricant can be added to institute with 0.1-10 parts by weight, the amount of preferably 0.5-5 parts by weight
It states in resin combination.
Meanwhile the present invention can provide a kind of moulding article manufactured by above-mentioned resin combination.
Resin combination can be subjected to casting and forming according to methods known in the art, such as twin shaft squeezes out, with manufacture
With excellent metallic adhesion, whiteness and acid proof moulding article, and can be used in various applications.
The moulding article can have various forms, including film, sheet material or fiber.The moulding article can be note
Mould product, extrudate or blow-molded article.In the case of injection molding, for crystallization, the temperature of mold can be about 130
DEG C or higher.In the case where moulding article is film, sheet-form, they can be made to various films or sheet material, such as
No yield point, uniaxial orientation or biaxially oriented film or sheet material.In the case where moulding article is fiber, the moulding article
It may be used as the fiber of No yield point, stretch fiber or super drawing fiber etc., it is also possible to make fabric, knitwear, non-woven fabrics (spunbond
Cloth, fusion spray cloth, staple fibre cloth), rope or net.
The above moulding article may be used as electrically or electronically part, such as need the computer fittings of metal adhesion, building
Material, auto parts, machine parts or basic item, and with chemicals or area that the industrial fiber with chemical resistance contacts
The coating in domain.
The embodiment of the present invention
The present invention is more fully described below in reference to each embodiment.Following implementation is intended to further illustrate this
Invention, but the scope of the present invention is not limited thereto.
Preparation example：Prepare PPS
Equipped with the thermocouple for measuring inside reactor temperature and the vacuum for filling nitrogen and manufacture vacuum
To include that the paradiiodobenzene (p-DIB) of 5,130g and the mixture of 450g sulphur are heated to 180 DEG C in the 5L reactors of pipeline,
To be completely melt and mix.By initiation reaction under conditions of 220 DEG C and 350 support, and it is stepped up temperature and reduces pressure 4
The final condition that hour holds in the palm to 300 DEG C and 0.6-0.9, and by injecting 7 sulphur and each 19g, make mixed reactant
Carry out polymerisation.When polymerisation proceeds to about 80% (degree of polymerisation by " (actual viscosity/target viscosities) ×
100 " determine), that is, relative ratios of the actual viscosity relative to target viscosities.It is measured by being sampled during polymerization current viscous
Degree, and target viscosities are set as 2,000 pool), the diphenyl disulfide of 35g is added as polymerization quencher, and in nitrogen atmosphere
Under carry out reaction 10 minutes.Pressure is down to 0.5 support or lower gradually to generate vacuum, and is terminated after reaching target viscosities anti-
It should be to synthesize poly arylidene thio-ester (PPS) resin in its main chain terminal not hydroxyl.Use small-sized pelleter (small strand
Cutter graininess) is made in resin after reaction.
The fusing point (Tm) of PPS resin, number-average molecular weight (Mn), polydispersity index (PDI) are measured by the following method and are melted
Body viscosity (hereinafter will be called " MV ").As measurement as a result, understand PPS resin Tm be 280 DEG C, Mn 17,420, PDI
It is moored for 2.8, MV 2,150, the content of the iodine and free-iodine that are bonded with main chain is 200ppm.
Fusing point (Tm)
Fusing point is measured using differential scanning calorimeter (DSC), while being increased temperature from 30 DEG C with 10 DEG C/min of rate
To 320 DEG C, 30 DEG C are cooled to, temperature is then increased to 320 DEG C from 30 DEG C with 10 DEG C/min of rate.
Number-average molecular weight (Mn) and polydispersity index (PDI)
So that PPS resin is dissolved in 1- chloronaphthalenes by being stirred 25 minutes at 250 DEG C, make its a concentration of 0.4wt%, prepares
Obtain sample.Later, by the poly arylidene thio-ester with different molecular weight with the flow rate of 1mL/min, and in High Temperature Gel Permeation
It is detached successively in the column of chromatography (GPC) system (210 DEG C), and corresponds to the poly arylidene thio-ester isolated using RI detectors measures
Molecular weight intensity.After preparing calibration curve using the standard sample (polystyrene) of known molecular amount, made from calculating
The opposite number-average molecular weight (Mn) and polydispersity index (PDI) of PPS resin.
Melt viscosity (Melt viscosity, MV)
Using rotatingdisc viscometer melt viscosity is measured at 300 DEG C.When being measured by frequency scanning method, angular frequency
Rate is measured as 0.6 to 500rad/s, and the viscosity at 1.84rad/s is defined as melt viscosity (MV).
The content (ppm) of the iodine and free-iodine that are bonded with main chain
Using the sample prepared by automatic conflagration stove (AQF) come measure the iodine being bonded with main chain in PPS resin and
The amount (ppm) of free-iodine wherein burning at 1000 DEG C PPS resin using smelting furnace, and by iodide ion and is dissolved in distilled water
In, and the calibration curve analyzed using ion chromatography is first passed through in advance.
Embodiment 1：Prepare PPS resin composition
In biaxial screw extruder, in the PPS resin obtained into the preparation example of 100 parts by weight, 9 parts by weight are added
PCT resins (manufacturer：SK Chemicals, name of product：0302, weight average molecular weight：56,000, inherent viscosity (IV)：
0.65dl/g, and using spectrocolorimeter D65 light sources comprising the L values that specular component pattern measures be 90), 9 parts by weight
Phenoxy resin (manufacturer：InChem Co., ProductName：PKHH, weight average molecular weight：52,000, glass transition temperature：92
DEG C), the glass fibre (manufacturer of 25 parts by weight handled with epoxy silane：Owens corning Co., ProductName：V-
910), the ZnS (manufacturers as white pigment of 9 parts by weight：Sachtleben Co., ProductName：) and 13 Sachtolith
Elastomer (the manufacturer of parts by weight：Arkema Co., ProductName：Lotader AX-8900, glycidyl methacrylate,
The terpolymer of acrylate and ethylene), to prepare PPS resin composition.
Screw speed is 250rpm, feed rate is 60kg/ hours, barrel temperature is 280-300 DEG C and torque is
Under conditions of 60%, using the extruder (SM Platek) of a diameter of 40mm, L/D=44 as biaxial screw extruder.It uses
Three feeders inject raw material, wherein the first feeder is for disperseing and injecting PPS resin, PCT resins, phenoxy resin and bullet
Property body, the second feeder is for disperseing and injecting white pigment, and third feeder is for disperseing and implantation glass fiber is to make
Standby PPS resin composition.
Embodiment 2-5 and comparative example 1
PPS resin composition is prepared according to identical step described in embodiment 1, the difference is that component and its dosage
As shown in table 2 below.
Comparative example 2
PPS resin composition is prepared according to identical step described in embodiment 1, the difference is that using solution is passed through
PPS (manufacturers made from polymerisation：Celanese Co., ProductName：0205P4, line style PPS, hereinafter will be called
" PPS1 ") replace PPS obtained in preparation example as PPS resin.
Comparative example 3
PPS resin composition is prepared according to identical step described in embodiment 1, the difference is that using solution is passed through
PPS (manufacturers made from polymerisation：Solvay Co., ProductName：P6 is crosslinked PPS, hereinafter will be called " PPS2 ") conduct
PPS resin replaces PPS obtained in preparation example.
Comparative example 4
PPS resin composition is prepared according to identical step described in embodiment 1, the difference is that component and its dosage
As shown in table 2 below, and PCT resins are not used.
Comparative example 5
PPS resin composition is prepared according to identical step described in embodiment 1, the difference is that component and its dosage
As shown in table 2 below.
Comparative example 6
PPS resin composition is prepared according to identical step described in embodiment 1, the difference is that using poly- to benzene two
Formic acid glycol ester (PET, manufacturer：SK Chemicals Co., ProductName：BB 8055) replace PCT resins.
The manufacturer of component used in embodiment 1-5 and comparative example 1-6 is summarized and shown in the following table 1.
[table 1]
Experimental example
The physical property of PPS resin composition obtained in embodiment and comparative example is tested as follows.As a result as follows
Shown in table 2.
First, PPS resin composition obtained in embodiment and comparative example is prepared into injection molding examination at 310 DEG C by being molded
Sample (injection molded specimens).
(1) release quantity
By the aluminium sample (width of etched processing：70mm, length：18mm, height：Two steps 2mm) being placed in injection molding machine
The fixing mould of mold and between moving moulds.Each PPS resin composition obtained in embodiment and comparative example is provided
In the two steps mold, and insertion is injected into 80 tons of Engel extruders, injection rate 50mm/s, and injection pressure is
120MPa, mold temperature are 150 DEG C.Then, by sample and mold separation to manufacture the sample for measuring metal adhesion intensity
(width：70mm, length 10mm, height：3mm) (Fig. 1).Later, the injection-molded test specimens of 2g are placed in the sealed vial of 20mL.
After the bottle is sealed, it is heated 30 minutes at 260 DEG C using head space (head space, HS) equipment, and will thus produce
Raw gas is automatically transported in gas chromatograph-mass spectrometer (GC/MS) equipment.Then, with capillary column detach each component with into
Row qualitative analysis is used in combination benzothiazole as the constituent content in standard substance quantitative analysis sample.
(2) chlorinity
By each injection-molded test specimens of the 50mg of the PPS of preparation example and the PPS1 or PPS2 of the polymerisation in solution (injection molding of above-mentioned (1)
Sample) organic material while humidified at 1000 DEG C by its completely burned, and using automatic fast stove (AQF) by burning
In gas collection to absorbent solution (hydrogen peroxide of 900ppm).Acquired solution is automatically injected in ion chromatography, and is measured
The chlorinity of injection-molded test specimens.
(3) tensile strength
The tensile strength of injection-molded test specimens is measured according to 527 methods of ISO.
(4) metal adhesion intensity
The metal adhesion intensity of injection-molded test specimens is measured according to ASTM D 3163.
(5) L values
Specular components are included according to D65 light sources using spectrocolorimeter (Konica Minolta, 3600D)
(SCI) pattern measures L values.L values are higher, and whiteness is better.
(6) anodic oxidation reactions
Molded sample in above-mentioned (1) is immersed in sodium hydroxide (NaOH) solution 30 seconds at 50 DEG C, is placed in volume
Than being 1:2 minutes in the mixed solution of the aqueous sulfuric acid of 7 98wt% and the phosphate aqueous solution of 84wt%.Later, by
So that the electric current of 20V is flowed 20 minutes in dilution heat of sulfuric acid to carry out oxidation process at room temperature, and carries out washing process.By with
(1) identical method measures metal adhesion intensity in, and measures L values by the identical method with (5), and measures anodic oxidation
Difference between the two front and back values.As can be seen that the difference is smaller, acidity is better.
[table 2]
As shown in table 2, the metal adhesion intensity of resin combination of the invention is 60-70MPa, and is significantly better than and includes
The resin combination 1-50MPa of the comparative example 1 of excess glass fiber.In addition, with comparative example 2 and 3 phases comprising PPS1 or PPS2
Than, including in preparation example PPS obtained embodiment 1-5, the release quantity shown reduces about four times.Further, implement
The chlorinity of example 1-5 is 35ppm or less, but the chlorinity of comparative example 2 is higher and be 891ppm, and the chlorinity of comparative example 3 is
1562ppm.In addition, for embodiment 1-5, the L values after anodic oxidation are 90 or higher, but comparative example 2 be 90 or
It is lower, and its whiteness reduces rapidly.
Moreover, when compared with the comparative example 4 not comprising PCT resins, the resin combination of embodiment 1-5 shows to improve
Metallic adhesion, metal adhesion intensity be 60-70MPa.However, the metal adhesion intensity of comparative example 4 is 55MPa, and right and wrong
It is often low.
In addition, the tensile strength of the comparative example 5 of excess PCT resins, which is wherein added, to be reduced.Meanwhile wherein comprising PCT is replaced
The comparative example 6 of the PET resin of resin shows high metallic adhesion but low L values.Compared with embodiment 1-5, anodic oxidation
The L values afterwards significantly reduce.
Therefore, resin combination of the invention shows the release quantity, excellent whiteness, acid resistance and the metal adhesion that reduce
Property, therefore can be used for various fields, including portable phone, electronic component, auto parts etc., they can by insert injection moulding at
Type and it is integrated.
Claims (20)
1. a kind of resin combination, which is characterized in that support dimethylene ester, institute including poly arylidene thio-ester and cyclohexanedimethanol
It includes the repetitive unit that formula 1 indicates to state cyclohexanedimethanol and support dimethylene ester, wherein the outgassing of the resin combination
Amount is 300ppm or less：
[formula 1]
2. resin combination as described in claim 1, which is characterized in that the poly arylidene thio-ester based on 100 parts by weight, it is described
The content that cyclohexanedimethanol supports dimethylene ester is 0.5-50 parts by weight.
3. resin combination as described in claim 1, which is characterized in that the cyclohexanedimethanol supports dimethylene ester
Weight average molecular weight be 10000-200000.
4. resin combination as described in claim 1, which is characterized in that the poly arylidene thio-ester includes the iodine being bonded with its main chain
Or free-iodine, the amount of the iodine being bonded with its main chain or the free-iodine is 10-10000ppm.
5. resin combination as described in claim 1, which is characterized in that the poly arylidene thio-ester includes that content is 300ppm or more
Low chlorine.
6. resin combination as described in claim 1, which is characterized in that the resin combination further includes being selected from phenoxy group tree
In fat, elastomer, filler, shock absorber fluid, adhesiveness reinforcing agent, stabilizer, pigment, plasticizer, lubricant and nucleating agent at least
A kind of component.
7. resin combination as claimed in claim 6, which is characterized in that the weight average molecular weight of the phenoxy resin is
10000-250000, glass transition temperature are 50-130 DEG C.
8. resin combination as claimed in claim 6, which is characterized in that the phenoxy resin is indicated by formula 2：
[formula 2]
Wherein, n is the integer of 100-900.
9. resin combination as claimed in claim 6, which is characterized in that the elastomer be selected from polyvinyl chloride elastomer,
Ethylene octane copolymer, polyurethane elastomer, polyester elastomer, polyamide-based elastomer, polybutadiene elastomer, with
And at least one in the group of the terpolymer elastomer composition of glycidyl methacrylate, methacrylate and ethylene
Kind thermoplastic elastomer (TPE).
10. resin combination as claimed in claim 6, which is characterized in that the filler is selected from glass fibre, carbon fiber, boron
At least one of the group that fiber, bead, sheet glass, talcum powder and calcium carbonate are constituted.
11. resin combination as claimed in claim 10, which is characterized in that the glass fibre is the glass fibers of silane treatment
Dimension, wherein the silane is one or more in epoxy silane and amino silane.
12. resin combination as described in claim 1, which is characterized in that the resin combination includes that content is 300ppm
Or lower chlorine.
13. resin combination as described in claim 1, which is characterized in that the resin combination measured according to ISO 527
Tensile strength values be 80MPa or higher.
14. resin combination as described in claim 1, which is characterized in that the resin group measured according to ASTM D 3163
The metal adhesion intensity value for closing object is 60MPa or higher.
15. resin combination as described in claim 1, which is characterized in that it is according to D65 light sources includes specular components
(SCI) the L values for the resin combination that pattern measures are 89 or higher.
16. resin combination as described in claim 1, which is characterized in that the resin group measured according to ASTM D 3163
It is 55MPa or higher to close metal adhesion intensity value of the object after anodic oxidation.
17. resin combination as described in claim 1, which is characterized in that it is according to D65 light sources includes specular components
(SCI) L value of the resin combination that pattern measures after anodic oxidation is 88 or higher.
18. a kind of moulding article, which is characterized in that by casting claim 1-17 any one of them resin combinations
It causes type and is made.
19. moulding article as claimed in claim 18, which is characterized in that the moulding article is need metal adhesion electrical
Or electronic component.
20. moulding article as claimed in claim 18, which is characterized in that the moulding article is the automobile for needing metal adhesion
Part.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2016-0017133 | 2016-02-15 | ||
| KR1020160017133A KR20170095569A (en) | 2016-02-15 | 2016-02-15 | Polyarylene sulfide composition having improved adhesion to metal |
| PCT/KR2017/000612 WO2017142217A1 (en) | 2016-02-15 | 2017-01-18 | Polyarylene sulfide composition having excellent adhesion to metals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108603030A true CN108603030A (en) | 2018-09-28 |
| CN108603030B CN108603030B (en) | 2021-06-29 |
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|---|---|---|---|
| CN201780008608.0A Active CN108603030B (en) | 2016-02-15 | 2017-01-18 | Polyarylene sulfide composition having excellent adhesion to metal |
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| Country | Link |
|---|---|
| JP (1) | JP6707655B2 (en) |
| KR (1) | KR20170095569A (en) |
| CN (1) | CN108603030B (en) |
| TW (1) | TW201800486A (en) |
| WO (1) | WO2017142217A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329906A (en) * | 1993-05-20 | 1994-11-29 | Toray Ind Inc | Poly(phenylene sulfide) resin composition and molded composite |
| JP2000204341A (en) * | 1999-01-11 | 2000-07-25 | Nkk Corp | Adhesive for thermoplastic film-laminated metal plate |
| CN102822240A (en) * | 2010-03-10 | 2012-12-12 | Sk化学株式会社 | Polyarylene sulfide having reduced outgassing and preparation method thereof |
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|---|---|---|---|---|
| JPH02209953A (en) * | 1989-02-09 | 1990-08-21 | Mitsubishi Rayon Co Ltd | Polyarylene sulfide resin composition |
| JPH04132765A (en) * | 1990-09-25 | 1992-05-07 | Dainippon Ink & Chem Inc | Resin composition |
| KR950008900B1 (en) * | 1991-12-31 | 1995-08-09 | 주식회사선경인더스트리 | Polyester resin composition |
| US20050269011A1 (en) * | 2004-06-02 | 2005-12-08 | Ticona Llc | Methods of making spunbonded fabrics from blends of polyarylene sulfide and a crystallinity enhancer |
| JP5278367B2 (en) * | 2010-04-12 | 2013-09-04 | 新日鐵住金株式会社 | Organic resin laminated steel sheet |
| JP2013181043A (en) * | 2012-02-29 | 2013-09-12 | Dic Corp | Polyarylene sulfide resin composition, and molding |
| KR101890915B1 (en) * | 2012-07-04 | 2018-09-28 | 에스케이케미칼 주식회사 | Polyarylene sulfide resin composition and formed article |
| WO2015020142A1 (en) * | 2013-08-09 | 2015-02-12 | Dic株式会社 | Polyarylene sulfide resin composition and molded article of same |
-
2016
- 2016-02-15 KR KR1020160017133A patent/KR20170095569A/en not_active Application Discontinuation
-
2017
- 2017-01-18 JP JP2018543169A patent/JP6707655B2/en not_active Expired - Fee Related
- 2017-01-18 CN CN201780008608.0A patent/CN108603030B/en active Active
- 2017-01-18 WO PCT/KR2017/000612 patent/WO2017142217A1/en active Application Filing
- 2017-01-25 TW TW106102906A patent/TW201800486A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329906A (en) * | 1993-05-20 | 1994-11-29 | Toray Ind Inc | Poly(phenylene sulfide) resin composition and molded composite |
| JP2000204341A (en) * | 1999-01-11 | 2000-07-25 | Nkk Corp | Adhesive for thermoplastic film-laminated metal plate |
| CN102822240A (en) * | 2010-03-10 | 2012-12-12 | Sk化学株式会社 | Polyarylene sulfide having reduced outgassing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017142217A1 (en) | 2017-08-24 |
| KR20170095569A (en) | 2017-08-23 |
| TW201800486A (en) | 2018-01-01 |
| JP6707655B2 (en) | 2020-06-10 |
| JP2019504921A (en) | 2019-02-21 |
| CN108603030B (en) | 2021-06-29 |
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