CN104448815A - Thermoplastic resin composition and preparation method thereof - Google Patents
Thermoplastic resin composition and preparation method thereof Download PDFInfo
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- CN104448815A CN104448815A CN201410706055.4A CN201410706055A CN104448815A CN 104448815 A CN104448815 A CN 104448815A CN 201410706055 A CN201410706055 A CN 201410706055A CN 104448815 A CN104448815 A CN 104448815A
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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
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention provides thermoplastic resin composition and a preparation method thereof. The thermoplastic resin composition is characterized by comprising thermoplastic polyamide resin and alcohol amide, wherein the alcohol amide is a vinyl alcohol allyl monomer copolymer, polyol substitute amide or a combination of the vinyl alcohol allyl monomer copolymer and the polyol substitute amide. The alcohol amide is added to the polyamide composition and has the unexpected stabilizing effect (especially the long-term effect) on thermo-oxidative aging, coolants, oil, road salts and even light and weather.
Description
Technical field
The present invention relates to a kind of stable thermoplastic resin composition and preparation method thereof.
Background technology
Daiamid composition is owing to having excellent mechanical property, chemical-resistant, workability, heatproof air aging performance, them are made to be usually used in electronic apparatus, the motor vehicle industry harsher to operating environment requirements, wherein particularly common with the application of motor car engine periphery.Wherein, turbo-charging substitutes mechanical supercharging, improves air input of engine by air, thus improves power and the moment of torsion of engine, is the trend of development of automobile.But, require engine can stand turbo-charging work time more high pressure and temperature.This forces the thermal level for the material of engine periphery constantly to upgrade, and engine ambient temperature can reach the high temperature of 150 DEG C, even can the working temperature of more than 200 DEG C.Under daiamid composition is usually used in this use temperature, the mechanical property after long-time exposure can reduce usually, and this phenomenon is called thermal ageing.For in common knowledge in the industry, the heatproof air aging performance of daiamid composition can be improved by interpolation thermo-stabilizer also referred to as oxidation inhibitor, comprise interpolation or composite interpolation mantoquita, hindered phenol, many aromatic amines, hindered amine, phosphorous acid ester, thioesters etc. separately and improve the thermal-oxidative aging property of daiamid composition.In recent years, patent is also had openly to use polyvalent alcohol additive to improve the heat oxygen aging resistance level of daiamid composition.
The mode that US 20100029820A1 mentions polyvalent alcohol mixes with polymeric amide improves thermostability, points out that dipentaerythritol is as the most preferably polyvalent alcohol daiamid composition for the preparation of opposing long term thermal oxygen aging.CN102112549B discloses polyhydroxylated polymer and polyamide blended raising thermal oxidation stability performance, points out that this polyhydroxylated polymer is ethylene/vinyl alcohol copolymer and the polyvinyl alcohol that number-average molecular weight is at least 2000.But deposit or carry hot refrigerant to being used for; usually the contact with ethylene glycol and/or water can be related to; because daiamid composition is subject to the plastification of water or ethylene glycol; the freedom of motion of pars amorpha molecular chain in composition is improved; and regrettably; the molecule of these polyhydroxy structure, is being extracted composition, is being unfavorable for that the daiamid composition relating to this application keeps long term thermal oxidative stability after long-term alcoholysis test.
Known practices as the mode that polyvalent alcohol mixes with polymeric amide improved thermostability during an extrusion step, mentioned by patent US 20100029820A1.But, polyvalent alcohol adds in polymeric amide and improves thermostability existence restriction, and restricts its final practical application, namely in normal production inventory transport environment for use, especially, in high humid and warm environment or hot liquid, polyvalent alcohol occurs strongly to separate out phenomenon in polyamide compound.Described " hygrothermal environment ", refers to that temperature is higher than 25 DEG C, relative humidity higher than 50%, especially temperature higher than 80 DEG C, relative humidity higher than 80% environment.Described " precipitation phenomenon " refers to if known practices is by polyvalent alcohol and polyamide blendedly extrude prepared any type of article, in hygrothermal environment, deposit or use exceed certain time length after can be observed visually at article surface the removable material being different from article outward appearance, according to a reference examples, the fourier-transform infrared spectrogram of the polyvalent alcohol of the material that surface is separated out and interpolation fits like a glove, and confirms that polyvalent alcohol can exist serious precipitation phenomenon in production inventory transport use procedure.Therefore, this ability essence that polyvalent alcohol can be caused to serve as stablizer weakens, even disappear in production inventory transport use procedure, under the mechanical property cause its daiamid composition added, general who has surrendered produces irreversible having a strong impact on to the security of the lives and property of user.
According to prepared alcohol amide of the present invention, quite even can surmount polyvalent alcohol and to add those characteristics in daiamid composition in known practices mode by acquired character by join in polymeric amide, obtain simultaneously and stablize lasting performance, overcome situation about peeling off from component in any form in production inventory transport use procedure.Published patent CN 103597010A teaches polyvalent alcohol and adds during polymerizing polyamide, and the mode of being reacted by carboxylic end group and polyhydric alcohol obtains the polymeric amide of modification.Actually be in known practices as by polyvalent alcohol and the polyamide blended a kind of variant extruded, because heating and water move from the reversible balance extracting the esterification of alcohol and polymeric amide end carboxyl of system to positive dirction in blending extrusion process, though its level of response uncontrollable, it is the result can derived by limited experiment or existing experience that a certain proportion of polyvalent alcohol accounting for polyvalent alcohol total amount is had an effect with the mode of covalent linkage and polymeric amide.The polyvalent alcohol of indication of the present invention is in " in production inventory transport use procedure situation about peeling off from component " in any form, refer to polyvalent alcohol with any effort under the prerequisite of daiamid composition, reactive force comprises covalent linkage, ionic linkage, hydrogen bond and model ylid bloom action power, especially ionic linkage, hydrogen bond and model ylid bloom action power, in production inventory transport use procedure, the effect of polyvalent alcohol and other components meets with and destroys and situation about peeling off from component occurs, particularly there is the process that small molecules polar material and daiamid composition come in contact under the high temperature conditions.The stable polymeric amide that patent CN 103597010A tells about is because the phase carries out modification before polymerization, what it was maximum is limited in has obvious limitation to the products production processing conditions of practical application, wherein there is heat-staple polyamide-based lower in the substantial concentration of polyvalent alcohol, be not suitable for and carry out blending extrusion as stablizer and other systems and obtain further there is heat-staple product.
Summary of the invention
The object of this invention is to provide a kind of thermoplastic resin composition with higher stability and preparation method thereof.
In order to achieve the above object, the invention provides a kind of thermoplastic resin composition, it is characterized in that, comprise thermoplastic polyamide resin and alcohol amide, described alcohol amide is one or both the combination in vinyl alcohol vinyl monomer multipolymer and polyvalent alcohol substituted amide, wherein, the structure of described polyvalent alcohol substituted amide is such as formula shown in (I) or (II):
Wherein, described vinyl monomer is for containing or not containing heteroatomic vinyl monomer; Described R is H or aliphatic, alicyclic or containing or not containing heteroatomic alkyl containing aromatic ring structure, described R1, R2 and R3 be selected from independently of each other replacement or unsubstituted aliphatic, alicyclic or containing aromatic ring structure containing or not containing heteroatomic alkyl, described R4 be H or replacement or unsubstituted aliphatic, alicyclic containing aromatic ring structure containing or not containing heteroatomic alkyl.
Preferably, described is vinyl cyanide or acrylamide containing heteroatomic vinyl monomer, and not containing heteroatomic vinyl monomer is ethene or propylene.
Preferably, described vinyl monomer comprises at least one in ethene, propylene, acrylamide, vinyl cyanide.
Preferably, described R comprises the aliphatic, alicyclic of 1-36 C atom or containing or not containing heteroatomic alkyl containing aromatic ring structure.More preferably, described R comprises the aliphatic, alicyclic of 2-28 C atom or containing or not containing heteroatomic alkyl containing aromatic ring structure.Particularly preferably, described R comprises the aliphatic, alicyclic of 3-20 C atom or containing or not containing heteroatomic alkyl containing aromatic ring structure.
Preferably, described R contains one or more heteroatomss in N, S, O and P.More preferably, described R is optionally containing O and N heteroatoms.
Preferably, described R1, R2, R3 and R4 are optionally containing one or more heteroatomss in N, S, O and P.R1, R2, R3, R4 have identical or different selectivity.
Preferably, described R1, R2, R3 and R4 optionally can contain n hydroxyl structure in structure shown in formula (I) outside terminal hydroxy group, n be more than or equal to 1 integer.More preferably, described n is 1-100, is more preferably 1-50, is particularly preferably 1-10.
More preferably, described hydroxyl is not on adjacent carbon atom.
More preferably, the total hydroxy that described primary hydroxyl number accounts for is not less than 10%, more preferably, primary hydroxyl number accounts for total hydroxy and is not less than 50%, and particularly preferably, primary hydroxyl number accounts for total hydroxy and is not less than 80%, especially preferably, the total hydroxy 100% that accounts for of primary hydroxyl number.
Preferably, described R1, R2, R3, R4 structure can identical or differently be selected not containing the hydroxyl structure outside terminal hydroxy group in structure shown in formula (I).
Preferably, described alcohol amide is N, N-bis-(hydroxyethyl) laurylamide (CAS:142-78-9), N, N-bis-(hydroxyethyl) eicosyl acid amides, 5-nitro-N, N '-two (2, 3-dihydroxypropyl)-1, 3-benzenedicarboxamide (CAS:76820-34-3), N, N-bis-(1, 2-dihydroxypropyl) eicosyl acid amides, N, N-bis-(2-hydroxypropyl)-dodecane acid amides (CAS:54914-38-4), N, N-bis-(2-hydroxyl butyl) eicosyl acid amides, N-(1, 5-dihydroxyl hexyl) adipamide, N, N-bis-(1, 5-dihydroxyl hexyl) stearylamide, N, N-bis-(1, 2-dihydroxypropyl) stearylamide, N, N-bis-(2, 4, 4-tri-(methylol) butyl) eicosyl acid amides, (Z, Z)-N, N-bis-(2-hydroxyethyl)-9, 12-octadecane diene amide (CAS:56863-02-6), N, N, N ', N '-four (2-hydroxyethyl) adipamide, N-(2, 3-dihydroxypropyl) at least one in t-butyl carbamate (CAS:137618-48-5).
The amount of described alcohol amide is preferably the 0.01-20wt% of the gross weight of this thermoplastic resin composition, is more preferably 0.05-15wt%, is more preferably 1-10wt%, is particularly preferably 1-5wt%.
The amount of described alcohol amide is preferably the 0.01-20wt% of the gross weight of thermoplastic polyamide resin, is more preferably 0.05-10wt%, is more preferably 2.5-5wt%.
The present invention relates to above-mentioned alcohol amide as daiamid composition to thermo-oxidative ageing, refrigerant, oil, road salt, the even purposes of illumination and weather stablizer.
Present invention also offers the preparation method of above-mentioned alcohol amide, it is characterized in that, comprise reacting to be formed via at least one dibasic alcohol, trivalent alcohol, polyvalent alcohol and/or their intermediate (as epoxy compounds) and amine and replace amine, again with aliphatic, alicyclic or containing the carboxylic acid reaction of aromatic ring structure, obtain alcohol amide; Or comprise at least one dibasic alcohol, trivalent alcohol, polyvalent alcohol and/or its intermediate (as the epoxy compounds that alcoholic extract hydroxyl group replaces) to react to be formed with amine and replace amine, again with aliphatic, alicyclic or containing the carboxylicesters generation transesterification reaction of aromatic ring structure, obtain alcohol amide; Or to comprise at least one dibasic alcohol, trivalent alcohol, polyvalent alcohol and/or its intermediate and acid amides by crosslinking reaction, obtain alcohol amide.The preparation method of described alcohol amide also can be that other obtain preparation method that is identical and/or analog structure by change intermediate, change synthesis sequential system.
Preferably, described alcohol amide is THTAA, its synthetic method comprises: be 2.5-3.5: 2 by the mol ratio of oxyethane and ammonia, at room temperature stirring reaction 0.5-3h, , by the addition manner that arachic acid methyl esters and diethanolamine are 1: 1.5-2.5 in molar ratio, join in reactor, add sodium ethylate, the add-on of sodium ethylate is the 0.1-0.2wt% of the gross weight of arachic acid methyl esters and diethanolamine, temperature of reaction is 70-90 DEG C, reacting kettle inner pressure is lower than 60mmHg, after reaction 2-3h, neutralizing pH with hydrochloric acid is 7, underpressure distillation removes unreacted diethanolamine, obtain THTAA.
Preferably, described alcohol amide is PVA-a-St, and its synthetic method comprises: stearylamide is put into reactor, adds DMSO, it is heating for dissolving under the condition of 50-70 DEG C in temperature, add glutaraldehyde water solution as linking agent, reaction 2-4h, then drop into polyvinyl alcohol, the weight ratio of described stearylamide, DMSO, glutaraldehyde water solution, polyvinyl alcohol is 7.5: 75-85: 1-2: 10-12, under 110-130 DEG C of condition, react 2-4h, underpressure distillation, except desolventizing, obtains PVA-a-St.
Preferably, described alcohol amide is PVA-g-AM, its synthetic method comprises: polyvinyl alcohol is joined abundant infiltration in dimethyl sulfoxide (DMSO) swelling, obtaining concentration is 10wt% polyvinyl alcohol solution, inflated with nitrogen deoxygenation, add ceric ammonium nitrate and the vitriol oil successively, in the reaction system of gained, the concentration of ceric ammonium nitrate is 0.005-0.007mol/L, H
+concentration be 0.1-0.3mol/L, be react 1-3h under the condition of 50-70 DEG C in temperature, add acrylamide, the mass ratio of acrylamide and polyvinyl alcohol is 1: 3-5, react after 6-10 hour, fully wash with DMF and distilled water and remove inorganics and by product, the PVA-g-AM obtained, vacuum-drying is to constant weight.
Preferably, described alcohol amide is PVAL-g-AN, its synthetic method comprises: vinyl alcohol ethylene copolymer is joined abundant infiltration in dimethyl sulfoxide (DMSO) swelling, obtaining concentration is 10wt%PVAL solution, inflated with nitrogen deoxygenation, add ceric ammonium nitrate and the vitriol oil successively, in the reaction system of gained, the concentration of ceric ammonium nitrate is 0.005-0.007mol/L, H
+concentration be 0.1-0.3mol/L, be react 0.5-3h under the condition of 50-70 DEG C in temperature, add vinyl cyanide, the mass ratio of vinyl cyanide and PVAL is 1: 2-5, react after 3-8 hour, fully wash with DMF and distilled water and remove inorganics and by product, the PVAL-g-AN obtained, vacuum-drying is to constant weight.
Preferably, described dibasic alcohol is at least one in 1，2-ethandiol, 1,3-PD, 2,3-butanediol, 1,5-PD and 2，2-dimethyl-1，3-propanediol and polyether glycol class.
Preferably, described trivalent alcohol is glycerine, TriMethylolPropane(TMP), 2,3-bis-(2 '-hydroxyethyl) hexanaphthene-1-alcohol, 1,2,6-hexanetriol, 1,1,1-tri--(methylol) ethane, 3-(2 '-hydroxy ethoxy) propane-1,2-glycol, 3-(2 '-propoxyl) propane-1,2-glycol, 2-(2 '-hydroxy ethoxy) hexane-1,2-glycol, 6-(2 '-propoxyl) hexane-1,2-glycol, 1,1,1-tri-[(2 '-hydroxy ethoxy) methyl] ethane, 1,1,1-tri-[(2 '-propoxyl) methyl] propane, 1,1,1-tri-(4 '-hydroxyphenyl) ethane, 1,1,1-tri-(hydroxyphenyl) propane, 1,1,3-tri-(dihydroxyl-3-aminomethyl phenyl) propane, 1, Isosorbide-5-Nitrae-three (dihydroxy phenyl) butane, 1,1,5-tri-(hydroxyphenyl)-3-methylpentane, two (TriMethylolPropane(TMP)s), TriMethylolPropane(TMP) ethoxylate, TriMethylolPropane(TMP) propoxylated glycerine and and trihydroxy-polyethers (as glycol ether, triglycol) at least one.
Preferably, described polyvalent alcohol is 1,1,3,3-tetra-(methoxyl group) propane, tetramethylolmethane, dipentaerythritol, tripentaerythritol, and has at least one in the polyvinyl alcohol of certain polymerization degree, ethylene-vinyl alcohol copolymer.
More preferably, the hydroxyl on described polyvalent alcohol, not on adjacent carbon atom, prevents from, in building-up process, elimination reaction occurs, can not get desired action effect.
Preferably, described carboxylic acid is at least one in Whitfield's ointment, para-amino benzoic acid, a-or β-oxalic acid, propanedioic acid, succinic acid, hexanodioic acid, capric acid, sebacic acid, phthalic acid, terephthalic acid, m-phthalic acid, lauric acid, tetradecanoic acid, Palmiticacid, pearly-lustre resin acid, stearic acid, oleic acid, linolic acid, linolenic acid, eicosanoic acid, behenic acid, xylogen acid and montanic acid.
Thermoplastic polyamide resin of the present invention be by the dicarboxylic acid of at least one aliphatics or alicyclic or aromatic yl aliphat or with the polycondensation of the diamines of aliphatic or alicyclic or aromatic yl aliphat obtain polyamide-based (as polymeric amide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 1010, polyamide 6 T (terephthalic acid), polyamide 6 I (m-phthalic acid), polyamide 9T, polymeric amide 10T, polymeric amide MXD6 (MXD is sub-dimethylphenylene diamine between being) and blend), poly-naphthyl methylene amides is (as PA10N, PA11N, PA12N), polyaramide class (as aramid fiber), or its blend and copolyamide are (such as: PA6T/6I, PA6T/6I/66, PAMXD6/MXDI), or for by by least one amino acid or lactan and the polymeric amide that itself carries out polycondensation and obtain, possible for this seed amino acid is opened by the hydrolysis of lactam nucleus and produce (as PA6, PA7, PA11, PA12 or PA13), or its blend and its copolyamide (such as PA66/6, PA6/12, PA6/10).
Preferably, described thermoplastic polyamide resin is the composition of PA6, PA66 and/or PA10T.
Preferably, described thermoplastic resin composition also comprises at least one in weighting agent, fire retardant, other thermo-stabilizer or antioxidant, static inhibitor, whipping agent, lubricant, nucleator, releasing agent, chainextender, anti-impact modifier, uv-absorbing agent, hindered amine as light stabilizer and tinting material.
More preferably, other described thermo-stabilizer or antioxidant are at least one in CuI and KI composite thermal stabilizer, hindered phenol, phosphorous acid ester, thioether and many aromatic amines.
Wherein according to a kind of variant, described thermoplastic resin composition contains relative said composition gross weight by weight from 0.05-2%, more preferably from 0.1-1.5%, particularly preferably from CuI and the KI composite thermal stabilizer of 0.3-1%.
According to another kind of variant, described hot attribute tree oil/fat composition contains minute quantity even CuI and the KI composite thermal stabilizer of zero content.
Thermoplastic resin composition of the present invention also can comprise at least one in the minute quantity even hindered phenol of zero content, phosphorous acid ester, thioether and many aromatic amines.
Term " minute quantity " refers to and be less than or equal to 0.5% by weight for the gross weight of described thermoplastic resin composition, is particularly less than or equal to 0.3%, is especially less than or equal to 0.1%, or even be less than or equal to 0.05%.
More preferably, described hindered phenol is 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (CAS:1843-03-4), 1, 3, 5-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide (CAS:27676-62-6), 4, 4 '-butylidene two (6-tert-butyl-m-cresol) (CAS:85-60-9), β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester (CAS:2082-79-3) of propionic acid, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (CAS:6683-19-8), 3, 9-two [1, 1-dimethyl-2-[(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] ethyl]-2, 4, 8, 10-tetra-oxaspiro [5.5] undecane (CAS:90498-90-1) and 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) at least one in benzene (CAS:1709-70-2).
More preferably, described phosphorous acid ester is distearyl pentaerythritol diphosphite (CAS:3806-34-6), two (2, 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate (CAS:80693-00-1), 2-2 '-methylene-bis (4, 6-dibutyl-benzyl)-2-ethylhexyl phosphorous acid ester (CAS:126050-54-2), tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester (CAS:31570-04-4), trisnonyl phenyl phosphite (CAS:26523-78-4) and 4, 4 '-split at least one in isopropyl diphenyl base C12-15-alcohol phosphorous acid ester (CAS:96152-48-6).
More preferably, described thioesters is tetramethylolmethane four (3-lauryl thiopropionate) (CAS:29598-76-3).
More preferably, described many aromatic amines are 4,4 '-two (propyloxy phenyl base) pentanoic (CAS:10081-67-1).
More preferably, described nucleator be grain diameter be less than the inorganic nucleator of 1 μm and organic nucleating agent and composite nucleating agents of one or both compositions, the usage quantity of described nucleator is 0.1 ~ 0.6wt% (taking thermoplastic resin composition as benchmark).Described inorganic nucleator is preferably talcum powder, at least one in polynite and calcium carbonate.Described organic nucleating agent is Sodium Benzoate, at least one in sorbyl alcohol dibenzyl ester and carboxylic acid sodium salt.
More preferably, described weighting agent is at least one in fibrous filler, Non-fibrous weighting agent and polymer-filled agent.Described fibrous filler is preferably at least one in glass fibre, carbon fiber and organic fibre.Described Non-fibrous weighting agent be granular, stratiform weighting agent, nano-filled dose, be preferably at least one in aluminum oxide, carbon black, clay, zirconium phosphate, kaolin, calcium carbonate, copper, diatomite, graphite, mica, silica, titanium dioxide, zeolite, talcum and wollastonite.Described polymer-filled agent is at least one in granulated glass sphere and glass powder.
Particularly preferably, described weighting agent is glass fibre, can be at least one of glass chopped strands and long glass fiber, be especially applicable to the glass chopped strands adding widespread use, this fiber has the diameter between 7 μm and 14 μm and is less than the length of 5mm.
More preferably, the consumption of described weighting agent is 5% to 60% of thermoplastic resin composition's gross weight, and particularly preferably, the consumption of described weighting agent is the 10%-40% of thermoplastic resin composition's gross weight.
More preferably, at least one that described anti-impact modifier carries out in the product that the polymkeric substance of modification and elastomer matrix formed by grafting or the special functional group of copolymerization for can be used as elastomer matrix.It is described that to can be used as the polymkeric substance that elastomer matrix carries out modification be polyethylene, polypropylene, polybutene, polyisoprene, ethylene-propylene rubber (EPR), Ethylene-Propylene-Diene (EPDM) rubber, ethylene butylene rubber, ethylene-acrylate rubber, Afpol, butadiene-propylene acid esters rubber, Ethylene-octene rubber, acrylonitrile butadiene rubber, ethylene-acrylic acid (EAA) product, ethane-acetic acid ethyenyl ester (EVA) product, ethylene-acrylate (EAE) product, acrylonitrile-butadiene-styrene (ABS) (ABS) multipolymer, styrene ethylene butadiene-vinylbenzene (SEBS) segmented copolymer, styrene-butadiene-styrene (SBS) multipolymer, core/the shell elastomer of metacrylate-butadiene-vinylbenzene (MBS) type, or more at least two kinds of elastomeric mixtures listing.The functional group of the product that described elastomer matrix is formed by grafting or the special functional group of copolymerization is used for realizing elastomer matrix and polyamide component generation certain effect, improve the consistency of elastomer matrix and polymeric amide, comprise: carboxylic acid, carboxylate salt, ester such as acrylate and methacrylic ester, ionic polymer, glycidyl is epoxide group such as, glycidyl ester, acid anhydride is maleic anhydride ， oxazoline such as, maleimide, or its mixture.Particularly, described anti-impact modifier can be selected from: ethylene-acrylate-glycidyl methacrylate trimer, ethylene-butyl acrylate copolymer, ethylene/n-butyl acrylate-glycidyl methacrylate copolymer, ethylene maleic acid anhydride copolymer, the ethylene-propylene-diene copolymer of maleic anhydride graft, the styrene-maleimide multipolymer of maleic anhydride graft, maleic anhydride modified styrene-ethylene-butylene-styrene multipolymer, the styrene-acrylonitrile copolymer of maleic anhydride graft, the acrylonitrile-butadiene-styrene copolymer of maleic anhydride graft, and their hydrogenated form.
More preferably, the consumption of described anti-impact modifier is 0% to 20% of thermoplastic resin composition's gross weight, and particularly preferably, the consumption of described anti-impact modifier is the 0%-10% of thermoplastic resin composition's gross weight.
Present invention also offers the preparation method of above-mentioned thermoplastic resin composition, it is characterized in that, concrete steps comprise: alcohol amide or its precursor and thermoplastic polyamide resin or its precursor are carried out blended and twin-screw extrusion, obtains thermoplastic resin composition.
Preferably, the precursor of described alcohol amide is at least one that polyvalent alcohol replaces in amine, carboxylic acid, carboxylate salt, polynary alkohol and amine.
Preferably, the precursor of described thermoplastic polyamide resin is salt or monomer.
Thermoplastic resin composition involved in the present invention obtains participating in each component in the composition mode by some or all components cold premixing and/or melt blending, according to the character of each component, each component in mixing process by a certain extent heating and shearing.Usual use extrusion equipment carries out extruding the heating and melting mixing of material, and wherein each component can or be introduced in sequence simultaneously.Each component can participate in mixing with any existence form, comprises the solid form of solid, liquid, different outward appearance, comprises powder, particle, laminated structure, threadiness, acicular structure etc.According to embodiment, twin-screw extrusion equipment by each component after simultaneously or in a sequence heating and melting mixing shear extrusion, after cooling, be cut into pellet obtain this thermoplastic resin composition, send molding device acquisition moulded product by this pellet of melting and by the composition after thawing to.Wherein mold forming process can comprise: injection molding, extrude, extrusion-blown modling is molded, or roational molding.
Shaping the obtained article of thermoplastic resin composition involved in the present invention are for being exposed to high temperature, being particularly more than or equal to the use temperature of 90 DEG C, especially be more than or equal to the use temperature of 150 DEG C, be more particularly more than or equal to the use temperature of 180 DEG C.According to conventional embodiment, the invention still further relates to shaping the obtained article of thermoplastic resin composition for being exposed to ultrahigh-temperature, being particularly more than or equal to the use temperature of 210 DEG C, be especially more than or equal to the use temperature of 230 DEG C.The application of environment for use.Its by the thick test rod of the 4mm of molded and shaped preparation after being exposed to the hot air aging 1000h of 180 DEG C, test according to ISO 527-2/1A, with have same composition and shape without the contrast exposed without comparing, measured stretching strength retentivity is higher than 50%.Particularly, the thick test rod of prepared 4mm, after being exposed to the hot air aging 800h of 210 DEG C, is tested according to ISO 527-2/1A, with have same composition and shape without the contrast exposed without comparing, measured stretching strength retentivity is higher than 50%.Especially, the thick test rod of prepared 4mm, after being exposed to the hot air aging 500h of 230 DEG C, is tested according to ISO 527-2/1A, and has comparing without the contrast exposed of same composition and shape, and measured stretching strength retentivity is higher than 50%.
The present invention relates to shaping the obtained article of thermoplastic resin composition for being chronically exposed to relative humidity higher than under the high thermal environment of 50%, described high thermal environment refers to the operating ambient temperature of more than 25 DEG C, after improving composition molding, there is good outward appearance, especially resist and cause the component of composition to separate out by described hygrothermal environment or by extracting, anti-precipitation or anti-extracting are measured according to the judgement of the whether removable material in surface or article density.
Statement involved in the present invention " is exposed to high temperature, is particularly more than or equal to the use temperature of 90 DEG C " and is often referred to composition and is applied to as comprising or carrying the gas of high temperature or liquid and the article manufactured, and other gases with high temperature or liquid directly do not contact but has the article close to environment for use temperature.Concrete environment for use to comprise for long-term exposure in water/glycol-cooled loop, the environment of oil return line or air loop.Concrete article comprise: the pipeline of intake manifold, cooler for recycled exhaust gas, charge air cooler, exhaust snubber, turbo charged air pipe, resonator, engine support, food tray, purolator, cylinder cover, variator, front shroud, scatterer tank, thermostatted, water tank and the Storing and conveying gas be associated, oil, cooling fluid or product.
Specific term is employed to help to understand principle of the present invention in this specification sheets.But should be appreciated that did not come round uses these specific terms to limit scope of the present invention.Term "and/or" comprises " with ", the every other possible combination of the implication of "or" and the key element with this term associated.
Compared with prior art, the invention has the beneficial effects as follows:
Alcohol amide of the present invention contains higher molecular weight, by the molecular structure giving the higher molecular weight of polyvalent alcohol and incomplete polarity, polyvalent alcohol had in daiamid composition to reduce, limit and even prevent production inventory to transport in use procedure situation about peeling off from component in any form, with the liquid comes into contact or hygrothermal environment of heat in especially seem useful.The relatively low part of this alcohol amide structure Semi-polarity contributes to the wetting ability to a certain degree reducing daiamid composition.This alcohol amide occurs to a certain degree to be distributed in an orderly manner in the surface structure of daiamid composition in moulding process, not only regulating effect is played to the surface tension of daiamid composition, and make the polyol structure of alcohol amide in the surface structure generation enrichment of daiamid composition, when adding the alcohol amide of small proportion, add alcohol amide polyol structure still there is the stabilization of equal or higher effect, wherein, the thermo-oxidative ageing of daiamid composition and the corrosive nature of any mode via externally to inner phenomenon of carrying out expanding in common knowledge in the industry.Therefore, the alcohol amide that the present invention relates to is added into daiamid composition to thermo-oxidative ageing, refrigerant, oil, road salt, and even illumination and weather have unexpected stabilization (particularly long term).
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Each raw material used in embodiment and comparative example is as follows:
Polyamide 66 (PA66), relative viscosity is 2.5-3.0; (Luo Diya, PA66 27AEXX)
Polymeric amide 10T (PA10T) refers to the homopolyamide formed by decamethylene diamine and terephthalic acid polycondensation; (golden hair science and technology, Vincyl series)
Chopped glass fiber (Taiwan must become, HP3786 32MM)
Black race (Britain height Lay COLLOIDS, PE48)
OP WAX (Clariant, Licowax OP)
Dipentaerythritol, is called DPE, purchased from Paasche holder company of Sweden;
Ethylene vinyl alcohol copolymer, purchased from Kuraray company, is also called EVAL;
Polyvalent alcohol substituted amide: N, N-bis-(hydroxyethyl) eicosyl acid amides, is called THTAA;
Polyvalent alcohol substituted amide: polyvinyl alcohol-stearylamide alkylate (PVA alkylated byStearicamide), claims PVA-a-St;
Vinyl alcohol vinyl monomer multipolymer: vinyl alcohol acrylamide copolymer, is called PVA-g-AM;
Vinyl alcohol vinyl monomer multipolymer: vinyl alcohol ethylene, propylene lonitrile copolymer, becomes PVAL-g-AN
Embodiment 1-14
Synthesis THTAA: the ammoniacal liquor being 25% by oxyethane and concentration joins in reactor, and the mol ratio of oxyethane and ammonia is 3: 2, and at room temperature stirring reaction 1h, obtains diethanolamine according to different boiling rectifying; By the addition manner that arachic acid methyl esters and diethanolamine are 1: 2 in molar ratio, join in reactor, add sodium ethylate, the add-on of sodium ethylate is the 0.15wt% of the gross weight of arachic acid methyl esters and diethanolamine, and temperature of reaction is 80 DEG C, and vacuumizes and make reacting kettle inner pressure lower than 60mmHg, after reaction 2.5h, neutralizing pH with the hydrochloric acid of 0.1mol/L is 7, removes unreacted diethanolamine, obtain THTAA by underpressure distillation.
Synthesis PVA-a-St: stearylamide (accounting for gross weight 7.5wt%) is put into reactor, add DMSO (accounting for the 80wt% of gross weight), it is heating for dissolving under the condition of 60 DEG C in temperature, add (accounting for gross weight 1.5wt%) 50% glutaraldehyde water solution as linking agent, reaction 3h, (viscosity is 20-50 to drop into polyvinyl alcohol again, alcoholysis degree is 99%, purchased from Kuraray company) (accounting for gross weight 11%), 3h is reacted under 120 DEG C of conditions, underpressure distillation is except desolventizing, obtain PVA-a-St, impurity in product can by extracting at follow-up extrusion, therefore without the need to being further purified.
Synthesis PVA-g-AM: (viscosity is 20-50 by polyvinyl alcohol, alcoholysis degree is 99%, purchased from Kuraray company) to join in dimethyl sulfoxide (DMSO) fully infiltrate swelling, obtaining concentration is 10wt% polyvinyl alcohol solution, inflated with nitrogen deoxygenation, add ceric ammonium nitrate and the vitriol oil successively, in the reaction system of gained, the concentration of ceric ammonium nitrate is 0.006mol/L, H
+concentration be 0.2mol/L, be react 2h under the condition of 60 DEG C in temperature, add acrylamide (mass ratio of acrylamide and polyvinyl alcohol is 1/4), react after 8 hours, fully wash with DMF and distilled water and remove inorganics and by product, the PVA-g-AM obtained, vacuum-drying is to constant weight.System is made to keep homogeneous and nitrogen atmosphere in building-up process by the mode stirred or vibrate.
Synthesis PVAL-g-AN, vinyl alcohol ethylene copolymer is joined abundant infiltration in dimethyl sulfoxide (DMSO) swelling, obtaining concentration is 10wt%PVAL solution, inflated with nitrogen deoxygenation, add ceric ammonium nitrate and the vitriol oil successively, in the reaction system of gained, the concentration of ceric ammonium nitrate is 0.006mol/L, H
+concentration be 0.2mol/L, be react 0.5h under the condition of 70 DEG C in temperature, add vinyl cyanide, the mass ratio of vinyl cyanide and PVAL is 1: 2, reacts after 6 hours, fully washs remove inorganics and by product with DMF and distilled water, the PVAL-g-AN obtained, vacuum-drying is to constant weight.
A kind of thermoplastic resin composition, is made up of the composition on the E1-E14 hurdle in table 1-3.
The preparation method of above-mentioned thermoplastic resin composition is:
Before extrusion, by polymeric amide pellet drying to moisture content lower than 1500ppm, after by blended for each components in certain proportion and drop into the main feeder of twin screw extruder, through double-screw extruding pelletizing, processing conditions is: district's temperature 240 DEG C, two district's temperature 260 DEG C, three district's temperature 260 DEG C, four district's temperature 260 DEG C, five district's temperature 260 DEG C, six district's temperature 270 DEG C, seven district's temperature 270 DEG C, eight district's temperature 275 DEG C, nine district's temperature 280 DEG C; Engine speed 350 revs/min.Thermoplastic resin composition's pellet is formed through extruding cooling granulation.Before carrying out injection molding, these pellets are carried out being dried to moisture content lower than 1500ppm.
Comparative example 1-6
A kind of thermoplastic resin composition, it is made up of the composition on the C1-C6 hurdle shown in 1-3.
The preparation method of above-mentioned thermoplastic resin composition is identical with embodiment 1-14.
Hot air aging:
According to ISO 527-2/1A, by the thick test rod of the 4mm of molded and shaped preparation, width 10mm, test speed 5mm/min, test 23 DEG C aerial aging before and aging back draft intensity (TS) and elongation at break (EL) (mean value of at least 5 same compositions and shaped samples test result).Hot air aging uses thermal aging oven, and regulate temperature to be 180 DEG C and 230 DEG C and carry out, after reaching the different digestion times of setting, sample takes out from ageing oven, uses aluminium foil bag heat seal after being cooled to room temperature, prevents from absorbing any moisture before evaluation mechanical property.With aging front corresponding mechanical performance compare, calculate the conservation rate of tensile strength and elongation at break, and represent with per-cent.
Separate out performance evaluation:
By the light face side plate of molded and shaped preparation 100mm × 100mm × 4mm, being positioned over temperature is 90 DEG C, relative humidity is that in the climatic chamber of 90%, hydrothermal aging, through 4h, takes out drying at room temperature, by the brightness L using Minolta desk-top color difference meter CM3600D to record aging rear plate
0value, records the brightness L (L value be the steady state value recorded after washing drying) at the same position place of cleaning rear plate by drying at room temperature behind plate surface, washed with de-ionized water side, calculates the luminance difference Δ L=L-L washing front and back with color difference meter
0, according to absolute value | whether whether Δ L| be greater than the 0.02 aging rear surface of judgement containing the removable material be different from tabula rasa clean surface, according to | the size of Δ L|, is divided into several grade by precipitation phenomenon: seriously, generally, not separate out.
In following table 1, mechanical property and the characteristic of the embodiment (E) after aging to 180 DEG C and reference examples (C) contrast:
Table 1
Except conservation rate, these per-cents (%) are stated in weight.
Therefore can observe and compare with using the daiamid composition of polyvalent alcohol DPE with CuI/KI, use the daiamid composition of alcohol amide of the present invention, at the stretching yield stress after 180 DEG C aging and elongation at break, there is higher conservation rate, and precipitation evaluation means having thus described the invention can be observed, add the precipitation phenomenon that polyvalent alcohol is as serious in DPE there occurs.And there is larger molecular weight due to alcohol amide such as THTAA or PVA-a-St or PVAL-g-AN, and the long chain alkane base of alcohol amide or the water repellency of St segment or AN segment and winding chain molecular structure make alcohol amide can resist high humid and warm environment, stable existence is in daiamid composition.
In following table 2, mechanical property and the characteristic of the embodiment (E) after aging to 230 DEG C and reference examples (C) contrast
Table 2
| C3 | C4 | E7 | E8 | E9 | |
| PA66(％) | 44.8 | 46.8 | 47.8 | 46.8 | 44.8 |
| PA10T(％) | 15 | 15 | 15 | 15 | 15 |
| Chopped glass fiber (%) | 35.0 | 35.0 | 35.0 | 35.0 | 35.0 |
| Black race (%) | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 |
| OPWAX | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| DPE(％) | 4.0 | ||||
| EVAL(％) | 2.0 | ||||
| THTAA(％) | 1.0 | 2.0 | 4.0 | ||
| Before aging | |||||
| TS(MPa) | 220 | 225 | 220 | 225 | 230 |
| EL(％) | 5.0 | 4.5 | 5.0 | 5.0 | 4.9 |
| After 230 DEG C of aging 500h | |||||
| TS(MPa) | 145 | 150 | 219 | 223 | 227 |
| EL(％) | 3.2 | 3.0 | 4.9 | 4.9 | 4.9 |
| TS conservation rate | 65.9％ | 66.7％ | 99.5％ | 99.5％ | 98.7％ |
| EL conservation rate | 64.0％ | 66.7％ | 98.0％ | 98.0％ | 100％ |
| After 230 DEG C of aging 1000h | |||||
| TS(MPa) | 95 | 100 | 142 | 160 | 167 |
| EL(％) | 2.6 | 2.0 | 3.1 | 3.2 | 3.3 |
| TS conservation rate | 43.1％ | 44.4％ | 64.8％ | 71.7％ | 73.6％ |
| EL conservation rate | 56.5％ | 45.5％ | 63.3％ | 65.3％ | 67.3％ |
| Precipitation situation | Seriously | Do not separate out | Do not separate out | Do not separate out | Do not separate out |
Except conservation rate, these per-cents (%) are stated in weight.
Therefore can observe and compare with using the daiamid composition of polyvalent alcohol DPE with EVAL, use the daiamid composition of alcohol amide, at the stretching yield stress after 230 DEG C aging and elongation at break, there is higher conservation rate, and precipitation evaluation means having thus described the invention can be observed, add the precipitation phenomenon that polyvalent alcohol is as serious in DPE there occurs.And there is larger molecular weight due to alcohol amide such as THTAA, and the water repellency of the long chain alkane base of alcohol amide and winding chain molecular structure make alcohol amide can resist high humid and warm environment, stable existence is in daiamid composition.
Resistance to alcoholysis performance evaluation:
According to ISO 527-2/1A, by the thick test rod of the 4mm of molded and shaped preparation, width 10mm, test speed 5mm/min, tests before 23 DEG C of aerial alcoholysis and alcoholysis back draft intensity (TS) and elongation at break (EL) (mean value of at least 5 same compositions and shaped samples test result).Alcoholysis by adding the mixing solutions that glycol/water ratio is 1: 1 in autoclave, add molded and shaped test rod, regulate temperature to be 130 DEG C to test, test rod is taken out after autoclave temperature being cooled to room temperature after the different alcoholysis times reaching setting, by the solvent rub on its surface, use aluminium foil bag heat seal, prevent from carrying out humidity exchange with air before evaluation mechanical property.Corresponding mechanical performance compare with before alcoholysis, calculates the conservation rate of tensile strength and elongation at break, and represents with per-cent.
Density before and after alcoholysis characterizes:
According to ISO 1183-1-2004, get test rod dry before and after alcoholysis, the test rod wherein after alcoholysis is positioned over 120 DEG C of baking ovens and carries out drying after 4h, carries out density measurement.
In following table 3, the mechanical property of the embodiment (E) after 130 DEG C of alcoholysis and reference examples (C) and characteristic are contrasted
Table 3
Except conservation rate, these per-cents (%) are stated in weight
Because ethylene glycol and polyvalent alcohol such as DPE, EVAL have the character of similar compatibility, the density of polyhydric alcohols as DPE, EVAL that contains after alcoholysis is made to there occurs obvious reduction, be made the molecule in composition enliven degree of freedom increase because water in alcoholysis process and ethylene glycol have carried out plasticising, hydrolysis or alcoholysis to daiamid composition, wherein polyvalent alcohol DPE and EVAL receives the extracting of aqueous glycol solution and cuts open in vitro system.Because THTAA and PVA-a-St or PVAL-g-AN has longer hydrophobic alkyl, and there is relatively large molecular weight structural, with polarity ethylene glycol or the aqueous solution, not there is the structure of complete similar compatibility, can stable existing in Amilan polyamide resin composition in alcoholysis process.
Claims (10)
1. a thermoplastic resin composition, it is characterized in that, comprise thermoplastic polyamide resin and alcohol amide, described alcohol amide is one or both the combination in vinyl alcohol vinyl monomer multipolymer and polyvalent alcohol substituted amide, wherein, the structure of described polyvalent alcohol substituted amide is such as formula shown in (I) or (II):
Wherein, described vinyl monomer is for containing or not containing heteroatomic vinyl monomer; Described R is H or aliphatic, alicyclic or containing or not containing heteroatomic alkyl containing aromatic ring structure, described R1, R2 and R3 be selected from independently of each other replacement or unsubstituted aliphatic, alicyclic or containing aromatic ring structure containing or not containing heteroatomic alkyl, described R4 be H or replacement or unsubstituted aliphatic, alicyclic containing aromatic ring structure containing or not containing heteroatomic alkyl.
2. thermoplastic resin composition as claimed in claim 1, it is characterized in that, described alcohol amide is N, N-bis-(hydroxyethyl) laurylamide, N, N-bis-(hydroxyethyl) eicosyl acid amides, 5-nitro-N, N '-two (2, 3-dihydroxypropyl)-1, 3-benzenedicarboxamide, N, N-bis-(1, 2-dihydroxypropyl) eicosyl acid amides, N, N-bis-(2-hydroxypropyl)-dodecane acid amides, N, N-bis-(2-hydroxyl butyl) eicosyl acid amides, N-(1, 5-dihydroxyl hexyl) adipamide, N, N-bis-(1, 5-dihydroxyl hexyl) stearylamide, N, N-bis-(1, 2-dihydroxypropyl) stearylamide, N, N-bis-(2, 4, 4-tri-(methylol) butyl) eicosyl acid amides, (Z, Z)-N, N-bis-(2-hydroxyethyl)-9, 12-octadecane diene amide, N, N, N ', N '-four (2-hydroxyethyl) adipamide, N-(2, 3-dihydroxypropyl) at least one in t-butyl carbamate.
3. thermoplastic resin composition as claimed in claim 1, it is characterized in that, the amount of described alcohol amide is the 0.01-20wt% of the gross weight of this thermoplastic resin composition.
4. thermoplastic resin composition as claimed in claim 1, it is characterized in that, the preparation method of described alcohol amide comprises reacting to be formed via at least one dibasic alcohol, trivalent alcohol, polyvalent alcohol and/or their intermediate and amine and replaces amine, again with aliphatic, alicyclic or containing the carboxylic acid reaction of aromatic ring structure, obtain alcohol amide; Or comprise at least one dibasic alcohol, trivalent alcohol, polyvalent alcohol and/or its intermediate and amine to react to be formed and replace amine, then with aliphatic, alicyclic or containing the carboxylicesters generation transesterification reaction of aromatic ring structure, obtain alcohol amide; Or to comprise at least one dibasic alcohol, trivalent alcohol, polyvalent alcohol and/or its intermediate and acid amides by crosslinking reaction, obtain alcohol amide.
5. thermoplastic resin composition as claimed in claim 1, it is characterized in that, described thermoplastic resin composition also comprises at least one in weighting agent, fire retardant, other thermo-stabilizer or antioxidant, static inhibitor, whipping agent, lubricant, nucleator, releasing agent, chainextender, anti-impact modifier, uv-absorbing agent, hindered amine as light stabilizer and tinting material.
6. thermoplastic resin composition as claimed in claim 1, it is characterized in that, other described thermo-stabilizer or antioxidant are at least one in CuI and KI composite thermal stabilizer, hindered phenol, phosphorous acid ester, thioether and many aromatic amines.
7. thermoplastic resin composition as claimed in claim 1, it is characterized in that, described nucleator be grain diameter be less than the inorganic nucleator of 1 μm and organic nucleating agent and composite nucleating agents of one or both compositions, the usage quantity of described nucleator is the 0.1 ~ 0.6wt% of thermoplastic resin composition.
8. thermoplastic resin composition as claimed in claim 1, it is characterized in that, described weighting agent is at least one in fibrous filler, Non-fibrous weighting agent and polymer-filled agent.
9. thermoplastic resin composition as claimed in claim 1, it is characterized in that, at least one that described anti-impact modifier carries out in the product that the polymkeric substance of modification and elastomer matrix formed by grafting or the special functional group of copolymerization for can be used as elastomer matrix.
10. the preparation method of the thermoplastic resin composition according to any one of claim 1-9, it is characterized in that, concrete steps comprise: alcohol amide or its precursor and thermoplastic polyamide resin or its precursor are carried out blended and twin-screw extrusion, obtains thermoplastic resin composition.
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