CN107903392B - A kind of Semi-aromatic polyamide resin and its moulding compound - Google Patents
A kind of Semi-aromatic polyamide resin and its moulding compound Download PDFInfo
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- CN107903392B CN107903392B CN201710955052.8A CN201710955052A CN107903392B CN 107903392 B CN107903392 B CN 107903392B CN 201710955052 A CN201710955052 A CN 201710955052A CN 107903392 B CN107903392 B CN 107903392B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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Abstract
The invention discloses a kind of Semi-aromatic polyamide resins, by constituting derived from repetitive unit below: (i) two acid unit；(ii) diamine unit；(iii) and optional one or more amino carboxylic acids and/or lactams；Based on the integral molar quantity of component (i), terephthalic acid units account for the 50-100mol% of component (i)；Based on the integral molar quantity of component (ii), the aliphatic diamine with 11-20 carbon atom accounts for the 50-100mol% of component (ii)；And component (iii) accounts for the 0-25mol% of the integral molar quantity of component (i)+(ii)+(iii)；Wherein, in the Semi-aromatic polyamide resin, the content of biology base carbon is 56-100mol%.By the present invention in that with Long carbon chain diamines, and pass through the content of control biology base carbon, low environmental impact can not only drop in the Semi-aromatic polyamide resin being prepared, its GanzWhiteness value can reach 50 or more, with good color level, the moulding compound being made of the Semi-aromatic polyamide resin also has a clear superiority in terms of color characteristics.
Description
Technical field
The present invention relates to polymeric material field, in particular to a kind of Semi-aromatic polyamide resin and its molding combination
Object.
Background technique
Polyamide is because having good comprehensive performance, including mechanical property, heat resistance, wear resistance, chemical resistance
And self-lubrication, and coefficient of friction is low, there is certain anti-flammability etc., is generally applied and is filled with glass fibre and other fillers
Enhancing is modified, improve performance and expand application range etc..In recent years semiaromatic polyamide composition due to its heat resistance and
Mechanical property is more excellent and by focus development.
However the raw material from petroleum cracking product that existing polyamide mainly uses in the synthesis process.Petroleum
With non-renewable, and these raw materials need to undergo complicated chemical process, consume big energy and generate and much cause
The by-product of environmental pollution.Since the raw material sources of biological poly amide are in plant, petroleum refining is needed not move through, can avoid
Big energy is consumed, therefore biological poly amide not will cause the additional increase of carbon dioxide in environment.Based on this, industry is to life
There are tight demands for object based polyamide.
The present inventor has now surprisingly been found that, not using Semi-aromatic polyamide resin obtained by biology base, Long carbon chain diamines
Low environmental impact can be only dropped, also unexpectedly there is good color level.
Summary of the invention
In consideration of it, the resin is not only the purpose of the present invention is to provide a kind of Semi-aromatic polyamide resin of biology base
Low environmental impact can be dropped, also there is good color level.
The present invention is achieved by the following technical solutions:
A kind of Semi-aromatic polyamide resin, by mole meter, by being constituted derived from repetitive unit below:
(i) two acid unit；
(ii) diamine unit；
(iii) and optional one or more amino carboxylic acids and/or lactams；
Wherein, it is based on the integral molar quantity of component (i), terephthalic acid units account for the 50-100mol% of component (i)；
Wherein, it is based on the integral molar quantity of component (ii), the aliphatic diamine with 11-20 carbon atom accounts for component (ii)
50-100mol%；And the 0-25mol% of the integral molar quantity of component (iii) Zhan Zufen (i)+(ii)+(iii)；
Wherein, in the Semi-aromatic polyamide resin, the content of biology base carbon is 56-100mol%；The biology base
The content of carbon is measured according to ASTM standard D6866-12/Method-B.
Preferably, in the Semi-aromatic polyamide resin, the content of biology base carbon is 65-100mol%；The biology
The content of base carbon is measured according to ASTM standard D6866-12/Method-B.
Preferably, it is based on the integral molar quantity of component (i), the content of terephthalic acid units is 100mol%.
Preferably, it is based on the integral molar quantity of component (ii), the content of the aliphatic diamine with 11-20 carbon atom is
100mol%.
Preferably, the aliphatic diamine with 11-20 carbon atom is selected from 1,11- hendecane diamines, 1,12- 12
One or more of alkane diamines, 1,13- tridecane diamine, 1,14- tetradecane diamines or 1,16- hexadecane diamines.
Preferably, the content of component (iii) is 0.
Preferably, the Semi-aromatic polyamide resin is at 25 DEG C ± 0.01 DEG C, and 98% concentrated sulfuric acid, measuring concentration is
Under conditions of 10mg/ml, relative viscosity 1.7-2.8, preferably 1.85-2.45, more preferably 2.0-2.3.
Preferably, the fusing point of the Semi-aromatic polyamide resin be 260-340 DEG C, preferably 280-330 DEG C, more preferably
295-325 DEG C, wherein fusing point is tested to obtain referring to ASTM D3418-2003.
Preferably, only one fusing point of the Semi-aromatic polyamide resin.
The present invention also provides a kind of moulding compounds comprising above-mentioned Semi-aromatic polyamide resin, in parts by weight
Meter, including following component:
30-99 parts of Semi-aromatic polyamide resin；
0-70 parts of reinforcing filler；
0-50 parts of additive.
Wherein the content of reinforcing filler is preferably 10~50 parts, more preferably 15-40 parts.
Filer content is too low, causes daiamid composition mechanical property poor；Filer content is excessively high, daiamid composition system
Product surface floating fiber is serious, influences product appearance.
The shape of the reinforcing filler is threadiness, average length 0.01-20mm, preferably 0.1~6mm；It is grown
Diameter ratio be 5:1~2000:1, preferably 30:1~600:1, when threadiness reinforcing filler content within the above range when, polyamides
The high temperature rigid that amine composition will show high heat distortion temperature and increase.
The reinforcing filler is inorganic reinforcing filler or organic reinforcing fillers.
Wherein, the inorganic reinforcing filler is selected from glass fibre, potassium titanate fibre, the glass fibre of clad, ceramics
Fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, asbestos fibre, alumina fibre, silicon carbide fibre, stone
The one or more of cream fiber or boron fibre, preferably glass fibre；Daiamid composition not only can be improved using glass fibre
Mouldability, and mechanical property such as tensile strength, bending strength and bending modulus can be improved, and improve heat resistance for example
Heat distortion temperature when thermoplastic resin composition molds.
Wherein, the organic reinforcing fillers are selected from aramid fibre and/or carbon fiber.
The shape of the reinforcing filler is Non-fibrous, such as powdered, graininess, plate, needle-shaped, fabric or felted,
Its average grain diameter is 0.001~100 μm, preferably 0.01~50 μm.
When the average grain diameter of reinforcing filler will lead to the poor melt processable of polyamide less than 0.001 μm；Work as enhancing
The average grain diameter of filler is greater than 100 μm, will lead to undesirable injection-molded article appearance.
The average grain diameter of above-mentioned reinforcing filler is measured by absorption method, can be selected from potassium titanate crystal whisker, ZnOw,
Aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophillite, bentonite, montmorillonite, lithium cover
De- soil, synthetic mica, asbestos, alumino-silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, iron oxide, calcium carbonate,
Magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride,
The one or more of silicon carbide or silica.These reinforcing fillers can be hollow；In addition, being covered for montmorillonite, lithium de-
The swellabilities phyllosilicate such as soil can be used and interlayer ion is carried out to the illiteracy that organises after cationic exchange using organic ammonium salt
De- soil.
In order to make daiamid composition obtain more excellent mechanical performance, can be used coupling agent to inorganic reinforcing filler into
Row functional processing.
Wherein coupling agent is selected from isocyanates based compound, organosilan based compound, organic titanate based compound, has
Machine borine based compound, epoxide；Preferably organosilan based compound；
Wherein, the organosilan based compound is selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group, contains sulfydryl
Alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group,
Alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl, the alkane containing carbon-to-carbon unsaturated group containing end amido
The one or more of oxysilane compound, alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group.
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group is selected from γ-glycidoxypropyltrime,hoxysilane, γ-
The one or more of epoxy propoxy propyl triethoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing sulfydryl is selected from γ mercaptopropyitrimethoxy silane and/or γ-sulfydryl
Propyl-triethoxysilicane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing urea groups is selected from γ-ureidopropyltriethoxysilane, γ-ureido-propyl
The one or more of trimethoxy silane, the end γ-(2- urea groups ethyl) aminocarbonyl propyl trimethoxy silane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing isocyanate group is selected from γ-isocyanate group propyl-triethoxysilicane
Alkane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group hydroxypropyl methyl dimethoxysilane, γ-isocyanic acid
Ester group hydroxypropyl methyl diethoxy silane, γ-isocyanate group ethyl dimethoxysilane, γ-isocyanate group propyl
Ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan one or more；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing end amido is selected from γ-(end 2- amido ethyl) and holds aminocarbonyl propyl methyl two
Methoxy silane, γ-(end 2- amido ethyl) hold aminocarbonyl propyl trimethoxy silane, γ-end aminocarbonyl propyl trimethoxy silane
One or more；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing hydroxyl is selected from γ-hydroxypropyl trimethoxy silane and/or γ-hydroxyl
Propyl-triethoxysilicane；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing carbon-to-carbon unsaturated group is selected from γ-methacryloxypropyl front three
Oxysilane, vinyltrimethoxysilane, N- β-(the N- vinyl benzyl cardinal extremity amido ethyl) end-γ-aminocarbonyl propyl trimethoxy
The one or more of base silane hydrochloride；
The alkoxysilane compound containing trialkylsilyl group in molecular structure containing anhydride group is selected from 3- trimethoxy-silylpropyl succinic anhydride；
The organosilan based compound is preferably γ-methacryloxypropyl trimethoxy silane, (end 2- γ-
Amido ethyl) end aminocarbonyl propyl methyl dimethoxysilane, γ-(end 2- amido ethyl) end aminocarbonyl propyl trimethoxy silane,
γ-end aminocarbonyl propyl trimethoxy silane or 3- trimethoxy-silylpropyl succinic anhydride.
Conventionally inorganic reinforcing filler can be surface-treated using above-mentioned organosilan based compound,
Then it is subjected to melting mixing with polyamide again, to prepare the daiamid composition.
Organosilicon methane series chemical combination can also be added directly while inorganic reinforcing filler and polyamide melting mixing
Object carries out in-situ blending.
Wherein, the dosage of the coupling agent is 0.05~10wt% relative to inorganic reinforcing filler weight, preferably 0.1
~5wt%.
When the dosage of coupling agent is less than 0.05wt%, the effect of apparent improved mechanical properties is not achieved；Work as coupling
When the dosage of agent is greater than 10wt%, inorganic reinforcing filler is easy to happen cohesion, and disperses undesirable wind in polyamide
Danger, eventually leads to mechanical performance and declines.
The additive is selected from the one or more of fire retardant, impact modifying agent, other polymer, processing aid；It is described
Other polymer are preferably fatty polyamide, polyolefin homopolymer, ethene-alpha-olefin copolymer, ethylene-acrylate copolymers
The one or more of object；The processing aid be selected from antioxidant, heat-resisting stabilizing agent, weather resisting agent, release agent, lubricant, pigment,
The one or more of dyestuff, plasticizer, antistatic agent.
The fire retardant is fire retardant or fire retardant and the fire-retardant composition for assisting agent, content is preferably 10~
40wt%；Flame retardant agent content is too low to cause flame retardant effect to be deteriorated, and flame retardant agent content is excessively high to cause material mechanical performance to decline.
The fire retardant is halogenated flame retardant or halogen-free flame retardants；
The halogenated flame retardant is selected from brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, bromination benzene
Ethylene maleic acid anhydride copolymer, brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, bromination are poly-
The one or more of carbonic ester, three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer, preferably brominated Polystyrene；
The halogen-free flame retardants is selected from one kind or several of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus fire retardant
Kind；Preferably phosphonium flame retardant.
The phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, phosphorus
Triphenyl phosphate ester, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphate, butylbenzene system phosphate or phosphinates
It is one or more of；Preferably phosphinates；
Phosphinate salt compound is using the compound for for example descending formula (I) and/or (II) to indicate as representative.
In formula (I) and formula (II), R1And R2It may be the same or different, respectively indicate the C1 of straight-chain or branch-like
~C6- alkyl, aryl or phenyl；R3C1~C10- alkylidene of expression straight-chain or branch-like, C6~C10- arlydene, C6~
C10- alkyl arylene or C6~C10- aryl alkylene；M indicates calcium atom, magnesium atom, aluminium atom and/or zinc atom；M is 2
Or 3, n is 1 or 3, and x is 1 or 2.
The more specific example of phosphinate salt compound includes dimethylphosphinic acid calcium, dimethylphosphinic acid magnesium, dimethyl
Phosphonic acids aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethylimethyphosphinic acid magnesium, ethylimethyphosphinic acid aluminium, ethyl
Methyl-phosphinic acid zinc, diethyl phosphinic acids calcium, diethyl phosphinic acids magnesium, aluminum diethylphosphinate, diethyl phosphinic acids zinc, methyl
N-propyl phosphinic acids calcium, methyl-n-propylphosphinic acid magnesium, methyl-n-propylphosphinic acid aluminium, methyl-n-propylphosphinic acid zinc, first are burnt
Two (methyl-phosphinic acid) calcium, methane two (methyl-phosphinic acid) magnesium, methane two (methyl-phosphinic acid) aluminium, methane two (methyl-phosphinic acid)
Zinc, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) calcium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) magnesium, benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) aluminium,
Benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid) zinc, methylphenylphosphinic acid calcium, methylphenylphosphinic acid magnesium, methylphenylphosphinic acid aluminium, first
Base phenyl phosphinic acid zinc, diphenyl phosphonic acid calcium, diphenyl phosphonic acid magnesium, diphenyl phosphonic acid aluminium, diphenyl phosphonic acid zinc etc.,
It is preferred that dimethylphosphinic acid calcium, dimethylphosphinic acid aluminium, dimethylphosphinic acid zinc, ethylimethyphosphinic acid calcium, ethyl-methyl time
Phosphonic acids aluminium, ethylimethyphosphinic acid zinc, diethyl phosphinic acids calcium, aluminum diethylphosphinate, diethyl phosphinic acids zinc, more preferable two
Ethylphosphinic acid aluminium.
Phosphinate salt compound as fire retardant can be obtained easily from market.The phosphinic acids salinization that can be obtained from market
Close object example include Clariant Corporation (Clariant) manufacture EXOLIT OP1230, OP1311, OP1312, OP930,
OP935 etc..
Moulding compound comprising above-mentioned Semi-aromatic polyamide resin of the invention, the additive component can also wrap
One or more of impact modifying agents containing at most 45wt%；Preferably 5~30wt%.
Wherein, the impact modifying agent can be natural rubber, polybutadiene, polyisoprene, polyisobutene, butadiene
And/or isoprene and styrene or with styrene derivative and with the copolymer of other comonomers, hydrogenated copolymer and/
By grafting or with acid anhydrides, (methyl) acrylic acid or its ester copolymerization prepared by copolymer；The impact modifying agent can be with
It is the graft rubber with cross-linked elastomer core, the cross-linked elastomer core is by butadiene, isoprene or alkyl acrylate
It constitutes, and there is the graft shell being made of polystyrene or can be nonpolarity or polar olefin homopolymer or copolymer,
Such as EP rubbers, ethylene/propylene/diene rubber or Ethylene-octene rubber or ethylene-vinyl acetate rubber, or it is logical
Nonpolarity or polar olefin homopolymer or copolymer obtained from crossing grafting or being copolymerized with acid anhydrides, (methyl) acrylic acid or its ester；
The impact modifying agent can also be carboxylic acid functionalized copolymer, such as poly- (ethylene -co- (methyl) acrylic acid) or poly- (second
Alkene -1- alkene -co- (methyl) acrylic acid), wherein 1- alkene be olefine or be more than 4 atoms unsaturation (first
Base) acrylate, including acid groups neutralize those of to a certain extent copolymer by metal ion.
The impact modifying agent of styrene-based monomer (styrene and styrene derivative) and other vi-ny l aromatic monomers,
It is the block copolymer being made of alkenyl aromatic compounds and conjugated diene, and by alkenyl aromatic compounds and conjugation two
The combination of hydrogenated block copolymer and these type impact modifying agents that alkene is constituted.The block copolymer includes at least one
Kind is derived from the block a and at least one block b derived from conjugated diene of alkenyl aromatic compounds.It is total in hydrogenated diblock
In the case where polymers, the ratio of aliphatic unsaturation carbon-to-carbon double bond is reduced by hydrogenation.Suitable block copolymer is that have
Two, three, the four of linear chain structure and segmented copolymer.But branching and star structure also can be used according to the present invention.With
Know that mode obtains branched block copolymer, such as is grafted some collateral chains on the main chain of polymer.
The other alkenyl aromatic chemical combination that can be used together with styrene or be used with the form of mixtures with styrene
Object be aromatic ring and/or in C=C double bond by the alkyl of C1~20 or the vi-ny l aromatic monomers replaced by halogen atom.
The example of vi-ny l aromatic monomers is styrene, p-methylstyrene, α-methylstyrene, ethyl styrene, uncle
Butylstyrene, vinyltoluene, 1,2- diphenylethlene, 1,1- diphenylethlene, vinyl-dimethyl benzene, vinyltoluene,
One or more of combination in vinyl naphthalene, divinylbenzene, bromostyrene or chlorostyrene, optimization styrene, to first
Base styrene, α-methylstyrene and vinyl naphthalene.
It is preferable to use styrene, α-methylstyrene, p-methylstyrene, ethyl styrene, t-butyl styrene, ethylene
Base toluene, 1,2- diphenylethlene or 1, the combination of one or more of 1- diphenylethlene.Particularly preferably use benzene
Ethylene.But it is also possible to use alkenyl naphthalene.
The example for the diolefinic monomer that can be used is 1,3-butadiene, 2- methyl-1,3- butadiene, 2,3- dimethyl-
1,3-butadiene, 1,3-pentadiene, 1,3- hexadiene, isoprene, chlorobutadiene and pentadiene.It is preferred that 1,3-butadiene and
Isoprene, more preferably 1,3-butadiene (are hereinafter indicated with abbreviated form butadiene).
Used alkenyl aromatic monomer preferably includes styrene, and used diolefinic monomer preferably includes fourth two
Alkene, it means that optimization styrene-butadiene block copolymer.The block copolymer passes through anionic polymerisation usually with it
It is prepared by mode known to body.
Other than styrene monomer and diolefinic monomer, other other monomers can also be used simultaneously.Based on being made
With the total amount of monomer, the ratio of comonomer is preferably 0~50wt%, particularly preferably 0~30wt%, particularly preferably 0~
15wt%.The example of suitable comonomer is acrylate respectively, especially acrylic acid C1~C12 Arrcostab, such as propylene
Sour N-butyl or 2-EHA and methacrylate, especially methacrylic acid C1~C12 Arrcostab, such as
Methyl methacrylate (MMA).Other possible comonomers be (methyl) acrylonitrile, (methyl) glycidyl acrylate,
Vinyl methyl ether, the diallyl of dihydric alcohol and divinyl ether, divinylbenzene and vinyl acetate.
Other than conjugated diene, if applicable, hydrogenated block copolymer also includes lower hydrocarbon part, such as second
Alkene, propylene, 1- butylene, bicyclopentadiene or non-conjugated diene hydrocarbon.Unreduced aliphatic unsaturated bond derived from block b is in hydrogen
Ratio in change block copolymer is less than 50%, and preferably smaller than 25%, especially less than 10%.Aromatics portion derived from block a
Point revert at most 25% degree.It is total by the hydrogenation of styrene-butadiene copolymer and s-B-S
The hydrogenation of polymers obtains hydrogenated block copolymer, i.e. styrene-(Ethylene/Butylene) diblock copolymer and styrene-(ethylene-
Butylene)-styrene triblock copolymer.
Block copolymer preferably comprises the block a of the block a, especially 50~85wt% of 20~90wt%.Alkadienes can
To be introduced into block b with 1,2- orientation or Isosorbide-5-Nitrae-orientation.
The molal weight of block copolymer be 5000~500000g/mol, preferably 20000~300000g/mol, more preferably
40000~200000g/mol.
Suitable hydrogenated block copolymer is the product being available on the market, such as (Kraton polymer) G1650,
G1651 and G1652, and (Asahi Chemicals) H1041, H1043, H1052, H1062, H1141 and H1272.
The example of non-hydrogenated block copolymer is polystyrene-polybutadiene, polystyrene-poly (ethylene-propylene), polyphenyl
Ethylene-polyisoprene, polystyrene-polybutadiene-polystyrene (SBS), gathers poly- (α-methylstyrene)-polybutadiene
Poly- (the ethylene-propylene)-polystyrene of styrene-, polystyrene-polyisoprene-polystyrene or poly- (α-methylstyrene)
The combination of one or more of polybutadiene-poly- (α-methylstyrene).
The suitable non-hydrogenated block copolymer being available on the market have trade mark be (Phillips), (Shell),
(Dexco) and the multiple product of (Kuraray).
It can also be modified by being grafted with unsaturated silane compound based on the impact modifying agent of olefin polymer, it is described
Unsaturated silane compound is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl triacetyl silicon
Alkane, methacryloxypropyl trimethoxy silane or acrylic trimethoxy silane.
Elastomeric polyolefin is have straight chain, branch or core-shell structure random, alternately or block copolymer, and containing can
With the functional group reacted with the end group of polyamide, enough tolerabilities are thus provided between polyamide and impact modifying agent.
Therefore, impact modifying agent of the invention includes homopolymer or the copolymerization of alkene (such as ethylene, propylene, 1- butylene)
The copolymer of object or alkene and copolymerisable monomer (such as vinyl acetate, (methyl) acrylate and methyl hexadiene).
The commercially available impact modifying agent example that can be used for the additive component has:
TAFMER MC201:g-MA (- 0.6%) 67%EP copolymer (20mol% propylene)+33%EB copolymer
(15mol%1- butylene)) blend: Mitsui Chemicals, Japan.
TAFMER MH5010:g-MA (- 0.6%) ethylene-butene copolymer；Mitsui.
TAFMER MH7010:g-MA (- 0.7%) ethylene-butene copolymer；Mitsui.
TAFMER MH7020:g-MA (- 0.7%) EP copolymer；Mitsui.
EXXELOR VA1801:g-MA (- 0.7%) EP copolymer；Exxon Mobile Chemicals, US.
EXXELOR VA1803:g-MA (0.5-0.9%) EP copolymer, amorphous, Exxon.
EXXELOR VA1810:g-MA (- 0.5%) EP copolymer, Exxon.
EXXELOR MDEX 941l:g-MA (0.7%) EPDM, Exxon.
FUSABOND MN493D:g-MA (- 0.5%) ethylene-octene copolymer, DuPont, US.
FUSABOND A EB560D:(g-MA) ethylene/n-butyl acrylate copolymer, DuPont ELVALOY,
DuPont。
Daiamid composition comprising above-mentioned polyamide of the invention, the additive component can also include other
Polymer, other polymer are selected from fatty polyamide, polyolefin homopolymer or ethene-alpha-olefin copolymer, ethylene-the third
Olefin(e) acid ester copolymer.
The fatty polyamide includes but are not limited to aliphatic diacid and aliphatic two from 4~20 carbon atoms
Amine perhaps aliphatic diacid, aliphatic diamine and the lactams of the lactams of 4~20 carbon atoms or 4~20 carbon atoms
One of polymer or a variety of.It includes but are not limited to, polyhexamethylene adipamide (PA66), gathers polycaprolactam (PA6)
Hexamethylene sebacamide (PA610), nylon 1010 (PA1010), adipic acid-hexamethylene diamine-caprolactam copolymer
(PA66/6), poly- 11 lactams (PA11), nylon 12 (PA12) and its two or more of mixtures.
The preferred EP elastomer of the ethene-alpha-olefin copolymer and/or EPDM elastomer (are ethylene-propylene rubber respectively
With ethylene/propylene/diene rubber).For example, elastomer may include being based on containing 20~96wt%, preferably 25~85wt%
Ethylene-the C3 of ethylene~C12- alpha olefin copolymer elastomer, wherein being particularly preferably C3~C12- alpha-olefin packet herein
The alkene selected from propylene, 1- butylene, 1- amylene, 1- hexene, 1- octene, 1- decene and/or 1- laurylene is included, it is particularly preferably other
Polymer includes the one or more of ethylene-propylene rubber, LLDPE, VLDPE.
Alternatively or additionally (such as in the mixture), other polymer can also be comprising being based on ethylene-
The terpolymer of C3~C12- alpha-olefin and non-conjugated diene hydrocarbon, preferably it contains 25~85wt% ethylene and extremely herein
The non-conjugated diene hydrocarbon of mostly 10wt%, particularly preferred C3~C12- alpha-olefin includes being selected from propylene, 1- butylene, 1- penta herein
Alkene, 1- hexene, 1- octene, 1- decene and/or 1- laurylene alkene, and/or wherein non-conjugated diene hydrocarbon is preferably two rings
[2.2.1] heptadiene, Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene and/or especially 5- ethylidene norbornene.
Other possible forms of other polymer are ethylene-butene copolymers.
Preferably, other polymer include the ingredient with anhydride group, these pass through trunk polymer and insatiable hunger
With dicarboxylic anhydride, with unsaturated dicarboxylic or with the thermal response or radical reaction of the monoalkyl ester of unsaturated dicarboxylic, to be enough
It is introduced with the concentration of polyamide good combination, and herein preferably with reagent selected from the following:
Maleic acid, maleic anhydride, butyl maleate, fumaric acid, aconitic acid and/or itaconic anhydride.It is preferred that 0.1~
The unsaturated acid anhydride of 4.0wt% is grafted to as in impact modifying agent component, or unsaturated dicarboxylic anhydride or its precursor by with
Other unsaturated monomers are grafted together to apply.Generally preferable grafting degree is 0.1~1.0%, particularly preferably 0.3~0.7%.
Another possible ingredient of other polymer is the mixture being made of ethylene-propylene copolymer and ethylene-butene copolymer.
Above-mentioned possible system for other polymer can also use as a mixture.
In addition, in the range of not destroying effect of the present invention, it can be at any time in polyamide of the invention
Add various processing aids, for example, antioxidant and/or heat-resisting stabilizing agent (hindered phenolic, quinhydrones system, phosphite ester system and it
Substitution body, copper halide, iodine compound etc.), weather resisting agent (resorcinol system, salicylate system, enumerate BTA system, hexichol first
Ketone system, amine system of being obstructed etc.), release agent and lubricant (aliphatic alcohol, aliphatic amide, aliphatic bisamide, two ureas and polyethylene
Wax etc.), pigment (cadmium sulfide, phthalocyanine, carbon black etc.), dyestuff (nigrosine, nigrosine etc.), (P-hydroxybenzoic acid is pungent for plasticizer
Ester, N-butylbenzenesulfonamide etc.), (alkyl sulphate type anionic system antistatic agent, quaternary ammonium salt cationic system are anti-for antistatic agent
The nonionic systems antistatic agents such as electrostatic agent, polyoxyethylene sorbitan monostearate, glycine betaine system both sexes antistatic agent
Deng).
In order to obtain molded product of the invention, polyamide or Amilan polyamide resin composition of the invention can be passed through
The random moldings methods such as injection moulding, extrusion molding, blow molding, vacuum forming, melt spinning, film molding form.It can be with
These molded products are molded into required shape, and can be used in synthetic resin of automobile component, mechanical part etc. etc..Make
It is useful in following use on the way: the top of automobile engine cooling water component, particularly radiator tank for specific purposes
Pump parts such as the radiator waters box part such as portion and bottom, coolant liquid reserve tank, water pipe, water pump shell, water pump vane, valve etc. are in vapour
The component used is contacted down in car engine room with cooling water, with Switch, microminiature slide switch, DIP switch, switch it is outer
Shell, lamp holder, strapping, connector, the shell of connector, the shell of connector, IC socket class, roll, bobbin cover, relay,
Electrical relaybox, capacitor casing, the internal part of motor, small size motor shell, gear cam, dancing pulley, gasket, insulator,
Fastener is buckled, the insulation division of the shell of wire clamp, cycle wheel, Caster, safety cap, terminal board, electric tool, starter
Divide, spoiler, tank, radiator tank, chamber tank (Chamber tank), receiver, fuse box, shell of air purifier, sky
Adjust fan, the shell of terminal, wheel cover, suction tracheae, bearing retainer, cylinder head cover, inlet manifold, water pipe impeller (waterpipe
Impeller), clutch lever, speaker diaphragm, heatproof container, microwave oven component, electric cooker component, printer color tape
Guider etc. is the electrical/electronic associated components of representative, automobile/vehicle associated components, household electrical appliances/office electric component, computer
Associated components, facsimile machine/duplicator associated components, mechanical associated components, various other purposes.The present invention and prior art phase
Than having the following beneficial effects:
By the present invention in that with Long carbon chain diamines, and by the content of control biology base carbon, the semi-aromatic being prepared
Low environmental impact can not only drop in polyamide, and GanzWhiteness value can reach 50 or more, have good color level, by this
The moulding compound of Semi-aromatic polyamide resin composition also has a clear superiority in terms of color characteristics.
Specific embodiment
Further illustrate that the present invention, following embodiment are the preferable embodiment party of the present invention below by specific embodiment
Formula, but embodiments of the present invention are not limited by following embodiments.
Raw material of the present invention derives from commercial products.
Performance test methods:
The content of the biology base carbon is measured according to ASTM standard D6866-12/Method-B, and the biology base carbon rubs
You are calculated content as the following formula:
The content of biology base carbon=(biology base carbon mole/total organic carbon mole) × 100%.
The test method of the relative viscosity of gained Semi-aromatic polyamide resin: specific to test referring to GB12006.1-89
Method are as follows: in 25 ± 0.01 DEG C, 98% concentrated sulfuric acid, measurement concentration tests relative viscosity η under conditions of being 10mg/mlr；
The test method of the fusing point of Semi-aromatic polyamide resin: referring to ASTM D3418-2003；Specific test method
It is: using the fusing point of Perkin Elmer Diamond dsc analysis instrument test sample；Nitrogen atmosphere, flow velocity 40mL/min；
340 DEG C first are warming up to 10 DEG C/min when test, in 340 DEG C of holding 2min, is then cooled to 50 DEG C with 10 DEG C/min, then with 10
DEG C/min is warming up to 340 DEG C, endotherm peak temperature at this time is set as fusing point Tm；
The characterization (GanzWhiteness) of Semi-aromatic polyamide resin and moulding compound:
Polyamide or moulding compound are being projected into pressure 2000kg/cm first2, injection temperature is higher than melting point resin
In the case where 20 DEG C, by resin injection molding growth 5cm, wide 3cm, the colour table of thick 2mm, then in X-Rite after solid-phase tack producing
GanzWhiteness option is directly selected on ColorEye7000A colour photometer obtains the GanzWhiteness value WI of resin.WI value is bigger, color
It is whiter；WI value is smaller, and color of resin is poorer.
Examples 1 to 10 and comparative example 1~5
Equipped with magnetic coupling stirring, condenser pipe, gas phase mouth, feed opening, pressure explosion-proof mouth autoclave pressure in by table 1 ratio
Reaction raw materials are added in example, add benzoic acid, sodium hypophosphite and deionized water, and the amount of benzoic acid species is diamines, diacid, interior acyl
The 2.5% of the amount of amine and amino acid total material, sodium hypophosphite weight are 0.1% of other charged material weights in addition to deionized water, are gone
Ionized water weight is the 30% of total charged material weight；It vacuumizes and is filled with high-purity argon gas as protection gas, start to react.Reaction is mixed
Object is warming up to 220 DEG C of -230 DEG C of stirrings 3-5 hours, and then opening valve, slowly pressure release drains, while keeping temperature and pressure not
Become.It drains always to displacement and reaches the 70% of investment amount of deionized water.It starts to warm up at this time, is warming up to 250 in 3 hours
DEG C -270 DEG C, constant temperature 2 hours.Valve discharging is opened after the reaction was completed, obtains prepolymer.
According to the fusing point of the method test prepolymer of test Semi-aromatic polyamide resin fusing point, it is set as T DEG C.
After prepolymer is dried in vacuo 24 hours at 80 DEG C, use carbon dioxide/vapor mixed gas as protection
Gas carries out solid-phase tack producing.It is warming up to first (T-70) DEG C, constant temperature 1-5 hours.It is continuously heating to (T-50) DEG C, constant temperature 1-3 hours.
Then it is cooled to again (T-60) DEG C, constant temperature 1-5 hours.It is finally warming up to (T-40) DEG C, constant temperature is until discharging.Last thermostatic process
In constantly sample, pass through sampling and testing viscosity and determine final polymerization terminal.
The formula composition and the performance test results of the Semi-aromatic polyamide resin of 1 embodiment and comparative example of table
Relative to using decamethylene diamine or petroleum base diamines, the present invention to be greater than using carbon atom number it can be seen from 1 result of table
The GanzWhiteness of polymerizate obtained by 11 biology base diamines has a clear superiority.Comparative example 4 and 5 although biology base carbon content
It is higher, but that using diamines more than 11 carbon atoms, product GanzWhiteness is not lower, and color is bad.
Embodiment 11~16 and comparative example 6-9: the preparation of semiaromatic polyamide composition moulding compound
By the formula of table 2 by Semi-aromatic polyamide resin, additive after high-speed mixer and mixing is uniform, pass through main feeding
Mouth adds twin-screw extrude, and reinforcing filler is squeezed out by side feeding scale side feed, crosses water cooling, is granulated and obtains after drying
The semiaromatic polyamide composition moulding compound.
The formula and the performance test results of 2 semiaromatic polyamide composition moulding compound of table (formula is parts by weight in following table)
It include semiaromatic polyamide composition tree of the present invention it can be seen from 2 result of table under same molding combination composition formula
The GanzWhiteness of the moulding compound of rouge also has a clear superiority.
Claims (20)
1. a kind of Semi-aromatic polyamide resin, which is characterized in that by mole meter, by being derived from repetitive unit below
It constitutes:
(i) two acid unit；
(ii) diamine unit；
(iii) optional one or more amino carboxylic acids and/or lactams；
Wherein, the integral molar quantity based on component (i), terephthalic acid units account for the 50-100mol% of component (i)；
Wherein, the integral molar quantity based on component (ii), the aliphatic diamine with 11-20 carbon atom account for the 50- of component (ii)
100mol%；And component (iii) accounts for the 0-25mol% of the integral molar quantity of component (i)+(ii)+(iii)；
Wherein, in the Semi-aromatic polyamide resin, the content of biology base carbon is 56-100mol%；The biology base carbon contains
Amount is measured according to ASTM standard D6866-12/Method-B.
2. Semi-aromatic polyamide resin according to claim 1, which is characterized in that the Semi-aromatic polyamide resin
In, the content of biology base carbon is 65-100mol%；The content of the biology base carbon is according to ASTM standard D6866-12/Method-B
It measures.
3. Semi-aromatic polyamide resin according to claim 1 or 2, which is characterized in that the total moles based on component (i)
Amount, the content of terephthalic acid units are 100mol%.
4. Semi-aromatic polyamide resin according to claim 1 or 2, which is characterized in that always rubbing based on component (ii)
You measure, and the content of the aliphatic diamine with 11-20 carbon atom is 100mol%.
5. Semi-aromatic polyamide resin according to claim 1 or 2, which is characterized in that described to have 11-20 carbon former
The aliphatic diamine of son is selected from 1,11- hendecane diamines, 1,12- dodecamethylene diamine, 1,13- tridecane diamine, the 1,14- tetradecane
One or more of diamines or 1,16- hexadecane diamines.
6. Semi-aromatic polyamide resin according to claim 1 or 2, which is characterized in that the content of component (iii) is 0.
7. Semi-aromatic polyamide resin according to claim 1 or 2, which is characterized in that the semiaromatic polyamide composition
Resin is at 25 DEG C ± 0.01 DEG C, 98% concentrated sulfuric acid, under conditions of measurement concentration is 10mg/ml, relative viscosity 1.7-2.8.
8. Semi-aromatic polyamide resin according to claim 7, which is characterized in that the Semi-aromatic polyamide resin
At 25 DEG C ± 0.01 DEG C, 98% concentrated sulfuric acid, under conditions of measurement concentration is 10mg/ml, relative viscosity 1.85-2.45.
9. Semi-aromatic polyamide resin according to claim 8, which is characterized in that the Semi-aromatic polyamide resin
At 25 DEG C ± 0.01 DEG C, 98% concentrated sulfuric acid, under conditions of measurement concentration is 10mg/ml, relative viscosity 2.0-2.3.
10. Semi-aromatic polyamide resin according to claim 1 or 2, which is characterized in that the semiaromatic polyamide composition
The fusing point of resin is 260-340 DEG C, and wherein fusing point is tested to obtain referring to ASTM D3418-2003.
11. Semi-aromatic polyamide resin according to claim 10, which is characterized in that the semiaromatic polyamide composition tree
The fusing point of rouge is 280-330 DEG C, and wherein fusing point is tested to obtain referring to ASTM D3418-2003.
12. Semi-aromatic polyamide resin according to claim 11, which is characterized in that the semiaromatic polyamide composition tree
The fusing point of rouge is 295-325 DEG C, and wherein fusing point is tested to obtain referring to ASTM D3418-2003.
13. Semi-aromatic polyamide resin according to claim 1 or 2, which is characterized in that the semiaromatic polyamide composition
Only one fusing point of resin.
14. a kind of moulding compound comprising the described in any item Semi-aromatic polyamide resins of claim 1-13, by weight
Number meter, including following component:
30-99 parts of Semi-aromatic polyamide resin；
0-70 parts of reinforcing filler；
0-50 parts of additive.
15. the moulding compound of Semi-aromatic polyamide resin according to claim 14, which is characterized in that the enhancing
The shape of filler is threadiness, average length 0.01mm-20mm；Its draw ratio is 5:1-2000:1；Based on polyamide mould
The total weight of molding composition, the content of the reinforcing filler are 10-50 parts；The reinforcing filler is inorganic reinforcing filler or organic
Reinforcing filler, the inorganic reinforcing filler be selected from glass fibre, potassium titanate fibre, the glass fibre of clad, ceramic fibre,
The one or more of wollastonite fibre, asbestos fibre, alumina fibre, silicon carbide fibre, gypsum fiber or boron fibre；It is described to have
Machine reinforcing filler is selected from aramid fibre and/or carbon fiber.
16. the moulding compound of Semi-aromatic polyamide resin according to claim 15, which is characterized in that the enhancing
The average length of filler is 0.1mm-6mm；Its draw ratio is 30:1-600:1；Total weight based on polyamide moulding composition,
The content of the reinforcing filler is 15 parts -40 parts；The inorganic reinforcing filler is glass fibre.
17. the moulding compound of Semi-aromatic polyamide resin according to claim 14, which is characterized in that the enhancing
The shape of filler is Non-fibrous, and average grain diameter is 0.001 μm -100 μm, is selected from potassium titanate crystal whisker, ZnOw, boric acid
Al whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophillite, bentonite, montmorillonite, lithium, which cover, to be taken off
Soil, synthetic mica, asbestos, alumino-silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, carbon
Sour magnesium, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, bead, ceramic bead, boron nitride, carbon
The one or more of SiClx or silica.
18. the moulding compound of Semi-aromatic polyamide resin according to claim 17, which is characterized in that the enhancing
The average grain diameter of filler is 0.01 μm -50 μm.
19. the moulding compound of Semi-aromatic polyamide resin according to claim 14, which is characterized in that the addition
Agent is selected from one or more of fire retardant, impact modifying agent, other polymer, processing aid；The fire retardant is halogen system resistance
Fire agent or halogen-free flame retardants；Other polymer are fatty polyamide, polyolefin homopolymer, ethene-alpha-olefin copolymer
Or the one or more of vinyl-acrylate copolymer；The processing aid is antioxidant, heat-resisting stabilizing agent, weather resisting agent, demoulding
Agent, lubricant, pigment, dyestuff, plasticizer or antistatic agent.
20. the moulding compound of Semi-aromatic polyamide resin according to claim 19, which is characterized in that described fire-retardant
Agent is halogen-free flame retardants.
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| CN108559076A (en) * | 2018-04-08 | 2018-09-21 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it |
| CN108517113A (en) * | 2018-05-07 | 2018-09-11 | 安徽悦尔伟塑料机械有限公司 | High rigidity plastics machinery hand and preparation method thereof |
| CN108659522A (en) * | 2018-05-07 | 2018-10-16 | 安徽悦尔伟塑料机械有限公司 | High rigidity engineering plastics and preparation method thereof |
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| CN110790920B (en) * | 2019-10-28 | 2022-06-10 | 金发科技股份有限公司 | Semi-aromatic polyamide and polyamide molding composition composed of same |
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