CN104211956B - Polyesteramide, its preparation method and comprise its mechanograph - Google Patents
Polyesteramide, its preparation method and comprise its mechanograph Download PDFInfo
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- CN104211956B CN104211956B CN201310647003.XA CN201310647003A CN104211956B CN 104211956 B CN104211956 B CN 104211956B CN 201310647003 A CN201310647003 A CN 201310647003A CN 104211956 B CN104211956 B CN 104211956B
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Abstract
The present invention relates to polyesteramide, its preparation method and the mechanograph comprising it.Polyesteramide is: dicarboxylic acids；Diamidogen；Polymer with straight chain aliphatic diols, wherein, based on diamidogen and the total amount of the aliphatic diol of straight chain, diamidogen exists with the amount of 75mol% to 99mol% and straight chain aliphatic diols exists with the amount of 1mol% to 25mol%, and wherein, polyesteramide has the fusing point (Tm) from 280 DEG C to 320 DEG C and the crystallization temperature (Tc) from 260 DEG C to 290 DEG C.Polyesteramide shows the performance of excellence in terms of thermostability, discoloration-resistant and mouldability.
Description
Technical field
The present invention relates to polyesteramide, its preparation method and the mechanograph comprising it, and more
Body ground, relates to the polyamide showing excellent properties in terms of thermostability, discoloration-resistant and mouldability
Ester resin, its preparation method and comprise its mechanograph.
Background technology
High-fire resistance nylon can be obtained by the polycondensation reaction of aromatic dicarboxylic acid or aromatic diamine.High resistance to
Hot nylon can have anti-aromaticity structure (antiaromatic structure) and hypocrystalline texture,
And compared with common nylon, due to the thermostability that it is significantly higher, can be applied to need height
The various fields of thermostability.
The example of typical high-fire resistance nylon include PA4T, PA6T, PA9T, PA10T, PA11T,
PA12T etc..High-fire resistance nylon uses C9Or the diamidogen of more long-chain can directly with homopolymer,
Maybe can utilize the copolymerized polymer using comonomer (dicarboxylic acids or diamidogen).Normally, because
PA4T and PA6T can not be processed, by introducing substantial amounts of (number due to the high fusing point of homopolymer
Ten %) comonomer improves their melted machinability.For PA6T, adipic acid, isophthalic two
Formic acid etc. are widely used as comonomer, and can use short chain or long-chain aliphatic two
Amine, alicyclic diamine, the aliphatic diamine of side chain, short chain or the aliphatic dicarboxylic acid of long-chain, fat
Ring race dicarboxylic acids, the aliphatic dicarboxylic acid etc. of side chain.
High-fire resistance Buddhist nun at the LED reflection device of optical characteristics and discoloration-resistant for requiring excellence
In dragon product, it is possible to use alicyclic dicarboxylic acid replaces aromatic dicarboxylic acid to produce the light showing excellence
The product of/thermal property, or the list of glass transition temperature (Tg) can be improved with copolymerization
Body is to suppress the deterioration of the performance of nylon product under high temperature.But, when nylon exposes at high temperature
Time in air, this copolymerisation can not prevent nylon from suffering intrinsic variable color.
Due to these shortcomings, in the product requiring discoloration-resistant, it is possible to use high-heat-resistance polyester produces
Product replace high-fire resistance nylon.But, high-heat-resistance polyester product typically exhibit be worse than high heat-resisting
Property nylon thermostability, although and have excellence discoloration-resistant, but have under humid conditions
The shortcoming having weak hydrolyzable and mouldability.
Accordingly, there exist the needs to novel polyamide ester resin (amide-ester hybrid resin), this is new
Type polyesteramide shows at the aspect such as thermostability, discoloration-resistant and is better than existing high-fire resistance Buddhist nun
The performance of dragon product, and it has the mouldability of improvement.
Summary of the invention
It is an aspect of the invention to provide and show in terms of thermostability, discoloration-resistant and mouldability
Excellent performance guarantees the polyesteramide of the balance of excellence, its preparation method between performance simultaneously
With comprise its mechanograph.
One aspect of the present invention relates to polyesteramide.This polyesteramide is: dicarboxylic acids；
Diamidogen；With the polymer of straight chain aliphatic diols, wherein, based on diamidogen and straight chain aliphatic diols
Total amount, diamidogen exists with the amount of 75mol% to 99mol% and straight chain aliphatic diols is with 1mol%
Amount to 25mol% exists, and wherein this polyesteramide has from 280 DEG C to 320 DEG C
Fusing point (Tm) and the crystallization temperature (Tc) from 260 DEG C to 290 DEG C.
In one embodiment, dicarboxylic acids can include C8To C20Aromatic dicarboxylic acid and C8To C20
At least one in alicyclic dicarboxylic acid.
In one embodiment, diamidogen can include C4To C20In aliphatic diamine at least one
Kind.
In one embodiment, straight chain aliphatic diols can include C2To C20Straight-chain aliphatic
At least one in glycol.
In one embodiment, polyesteramide can have the glass from 80 DEG C to 120 DEG C
Change transition temperature (Tg).
In one embodiment, polyesteramide can have from 0.5dL/g's to 1.0dL/g
Intrinsic viscosity.
In one embodiment, polyesteramide can have by equation 1 calculate from 5
Color to 10 changes (Δ E):
Wherein Δ L*It is the L before and after scorch test (scorch testing)*Difference between value
(difference), Δ a*It is a before and after scorch test*Difference between value, and Δ b*It is Jiao
Burn the b before and after test*Difference between value, wherein by the polyesteramide indwelling of 1g to 3g in right
Stream baking oven continues 1 hour at 200 DEG C.
In one embodiment, polyesteramide can have to comprise aliphatic carboxylic acid and aromatics
The end-capping reagent of at least one in carboxylic acid is closed the end group of (encapsulated).
End-capping reagent can include acetic acid, propanoic acid, butanoic acid, valeric acid, caproic acid, octanoic acid, lauric acid, ten
Three alkanoic acids, myristic acid, Palmic acid, stearic acid, neopentanoic acid, isopropylformic acid., benzoic acid, toluene first
At least one in acid, α-naphthoicacid, β-naphthoic acid and methyl naphthalene formic acid.
The method that another aspect of the present invention relates to preparing polyesteramide.The method includes: make two
Carboxylic acid, diamidogen and straight chain aliphatic diols polymerization, wherein, based on diamidogen and straight chain aliphatic diols
Total amount, diamidogen exists with the amount of 75mol% to 99mol% and straight chain aliphatic diols is with 1mol%
Amount to 25mol% exists, and wherein this polyesteramide has from 280 DEG C to 320 DEG C
Fusing point (Tm) and the crystallization temperature (Tc) from 260 DEG C to 290 DEG C.
The further aspect of the present invention relates to the mechanograph comprising polyesteramide.
In one embodiment, mechanograph can be LED reflection device.
Detailed description of the invention
Hereinafter, will be described in detail embodiments of the present invention.
According to the present invention, polyesteramide is: (A) dicarboxylic acids；(B) diamidogen；(C)
The polymer of straight chain aliphatic diols.Polyesteramide has wherein derived from (A) dicarboxylic acids
Dicarboxylic acid moiety, derived from the diamine portion of (B) diamidogen with derived from (C) straight-chain aliphatic two
The structure of the straight chain aliphatic diols part of alcohol, wherein, based on (B) diamidogen and (C) straight chain fat
The total amount of fat race glycol, (B) diamidogen exists and (C) straight chain with the amount of 75mol% to 99mol%
Aliphatic diol exists with the amount of 1mol% to 25mol%, and wherein polyesteramide have from
The fusing point (Tm) of 280 DEG C to 320 DEG C and the crystallization temperature (Tc) from 260 DEG C to 290 DEG C.
As it is used in the present context, " dicarboxylic acids " includes dicarboxylic acids, its ester (C1To C4Lower alkyl
Base ester such as monomethyl ester, single ethyl ester, dimethyl esters, diethyl ester, dibutyl ester etc.), its acid
Acid anhydride etc., and form the dicarboxylic acid moiety formed via the reaction with diamidogen and straight chain aliphatic diols.
Additionally, as it is used in the present context, dicarboxylic acids, diamidogen and straight chain aliphatic diols part refer to when two
When carboxylic acid, diamidogen and straight chain aliphatic diols are polymerized after removing hydrogen atom, hydroxyl or alkoxyl
Remaining residue.
(A) dicarboxylic acids
According to the present invention, (A) dicarboxylic acids can be included in typical polyamide two used
Carboxylic acid, such as C8To C20Aromatic dicarboxylic acid, C8To C20Ring-type (aliphatic) dicarboxylic acids and they
Mixture.
Aromatic dicarboxylic acid is comprised in polyesteramide to give high-fire resistance, and can include
P-phthalic acid, M-phthalic acid, 2,6 naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids,
1,4-phenylene two epoxide diphenolic acid (1,4-phenylene dioxydiphenolic acid), 1,3-phenylene
Two epoxide oxalic acid, diphenic acid, 4,4'-oxo double (benzoic acid), diphenyl methane-4,4'-dicarboxylic acids,
Diphenyl sulphone (DPS)-4,4'-dicarboxylic acids, 4,4'-diphenyldicarboxylic acid or their mixture, but it is not limited to this.Example
As, aromatic dicarboxylic acid can be p-phthalic acid, M-phthalic acid or their mixture.Specifically,
Aromatic dicarboxylic acid can be p-phthalic acid or p-phthalic acid and the mixture of M-phthalic acid.
The example of cyclic dicarboxylic acid includes 2-cyclohexene-1,4-dicarboxylic acids, hexamethylene-1,1-dicarboxylic acids, anti-
Formula-1,2-hexamethylene-dicarboxylic acids, 1,4-hexamethylene-dicarboxylic acids, 1,3-hexamethylene-dicarboxylic acids and diformazan basic ring
Hexane-Isosorbide-5-Nitrae-dicarboxylic acids, but it is not limited to this.These can be used alone or use with a combination thereof.
In one embodiment, when being used together aromatic dicarboxylic acid and cyclic dicarboxylic acid, based on pressing
Mole meter aromatic dicarboxylic acid of 100 parts, cyclic dicarboxylic acid can with by mol 0.01 part to by mole
Count 50 parts, such as, by mol 5 parts to by mol 30 parts amount exist.In this range,
Polyesteramide can show the machinability of excellence.
(B) diamidogen
According to the present invention, polyesteramide comprises (B) diamidogen to improve chemical resistance and can
Mouldability.(B) diamidogen used during diamidogen can be included in typical polyesteramide, such as,
C4To C20Aliphatic diamine.(B) example of diamidogen includes: straight-chain aliphatic diamidogen, such as Isosorbide-5-Nitrae-fourth
Diamidogen, 1,5-pentanediamine, 1,6-hexamethylene diamine (hexamethylene diamine), 1,7-heptamethylene diamine, 1,8-octamethylenediamine,
1,9-nonamethylene diamine, 1,10-decamethylene diamine, 1,12-dodecamethylene diamine, 2-methyl isophthalic acid, 5-pentanediamine, 2,2,4-tri-
Methyl isophthalic acid, 6-hexamethylene diamine, 2,4,4-trimethyl-1,6-hexamethylene diamine, 5-methyl isophthalic acid, 9-nonamethylene diamine, 2,2-oxo
Double (ethamine), double (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether (EGBA), 1,7-bis-
Amino-3,5-dioxo heptane and their mixture, but it is not limited to this.Such as, (B) diamidogen is permissible
It is C4To C12Aliphatic diamine, as Putriscine, 1,6-hexamethylene diamine, 1，10-diaminodecane, 1,12-
Dodecamethylene diamine or their mixture.Specifically, (B) diamidogen can be 1,6-hexamethylene diamine, 1,10-
Heptamethylene diamine, 1,12-dodecamethylene diamine or their mixture.
(C) straight chain aliphatic diols
According to the present invention, the aliphatic diol comprising (C) straight chain in polyesteramide gives resistance to
Discolouration.(C) straight chain aliphatic diols can include C2To C20, such as, C4To C12Straight chain fat
Fat race glycol.(C) example of straight chain aliphatic diols includes 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-HD (hexamethylene glycol), 1,7-heptandiol, 1,8-are pungent
Glycol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl isophthalic acid, 5-pentanediol, 2,2,4-trimethyl-1,6-
Hexanediol, 2,4,4-trimethyl-1,6-hexanediol, 5-methyl isophthalic acid, 9-nonanediol and their mixture, but
It is not limited to this.Such as, (C) straight chain aliphatic diols can include BDO, 1,6-hexanediol,
1,10-decanediol, 1,12-dodecanediol or their mixture.Specifically, (C) straight chain fatty
Race's glycol can be 1,6-HD, 1,10-decanediol, 1,12-dodecanediol or their mixture.
According to the present invention, in (B) diamidogen and (C) straight chain aliphatic diols of polyesteramide
In, (B) diamidogen can be with 75mol% to 99mol%, such as, 80mol% to 95mol%, more
Specifically, the amount of 82mol% to 95mol% exists, and (C) straight chain aliphatic diols can be with
1mol% to 25mol%, such as, 5mol% to 20mol% are more specifically, 5mol% to 18mol%
Amount exist.If (B) amount of diamidogen is more than 99mol% or the amount of (C) straight chain aliphatic diols
Less than 1mol%, polyesteramide can be deteriorated in terms of discoloration-resistant, and if (B)
The amount of diamidogen less than the amount of the aliphatic diol of 75mol% or (C) straight chain more than 25mol%, due to
Polyesteramide significantly reducing in terms of melt temperature and crystallization temperature, polyesteramide is permissible
Deteriorated by such as the performances such as chemical resistance, machinability, thermostability.
Additionally, (B) diamidogen and (C) straight chain aliphatic diols and (A) aromatic dicarboxylic acid mole
Can be in the range of 0.9 to 1.3 than (((B)+(C))/(A)), such as, from 0.95
In the range of 1.25.In this range, due to this polyesteramide of unreacted monomer can in case
Stop the deterioration of performance and excellence can be shown in terms of thermostability, discoloration-resistant and mouldability
Performance.
According to the present invention, polyesteramide can have to comprise aliphatic carboxylic acid, aromatic carboxylic acid
Or the end group that the end-capping reagent of their mixture is closed.The example of end-capping reagent can include second
Acid, propanoic acid, butanoic acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, myristic acid, palm fibre
Palmitic acid acid, stearic acid, neopentanoic acid, isopropylformic acid., benzoic acid, toluic acid, α-naphthoicacid, β-naphthalene first
Acid, methyl naphthalene formic acid and their mixture, but it is not limited to this.Institutes based on by mol 100 parts
Having monomer ((A)+(B)+(C)), end-capping reagent is alternatively with less than by mol 5 parts, such as,
The amount of 0.01 part to by mol 3 parts exists by mol.
According to the present invention, polyesteramide have from 280 DEG C to 320 DEG C, such as, from 290 DEG C
To the fusing points of 310 DEG C (Tm).If the fusing point of polyesteramide is less than 280 DEG C, this polyamide
Ester resin can show the thermostability of deterioration, and if the fusing point of polyesteramide exceed
320 DEG C, this polyesteramide has poor mouldability (machinability).
Additionally, polyesteramide have from 260 DEG C to 290 DEG C, such as, from 270 DEG C to 280 DEG C
Crystallization temperature (Tc).If the crystallization temperature of polyesteramide is less than 260 DEG C, this resin is permissible
Reduced and can be had the mouldability of deterioration by crystallization rate aspect.If polyesteramide tree
The crystallization temperature of fat is more than 290 DEG C, and the mouldability of this polyesteramide can be deteriorated so that note
Molded condition becomes complicated and widget injection mo(u)lding and becomes difficulty.
Additionally, polyesteramide can have from 1.07 to 1.25, such as, from 1.10 to 1.15
The ratio (Tm/Tc) of fusing point (Tm) and crystallization temperature (Tc).In this range, polyesteramide
Resin can show the mouldability of excellence.
Polyesteramide can have from 80 DEG C to 120 DEG C, such as, from 85 DEG C to 110 DEG C
Glass transition temperature (Tg).In this range, polyesteramide can show the resistance to of excellence
Hot.
Polyesteramide can have use Ubbelohde viscometer in the m-cresol solution at 25 DEG C and survey
Fixed from 0.5dL/g to 1.0dL/g, such as, from the intrinsic viscosity of 0.8dL/g to 1.0dL/g.?
In the range of this, polyesteramide shows excellent at aspects such as thermostability, discoloration-resistant, mouldabilities
Different performance.
Color space value according to polyesteramide prepared by ASTM D1209 initial measurement
(color space values) (L*, a*, b*), and wherein by the polyesteramide of 1g to 3g
Resin indwelling continues after the scorch test after 1 hour with equally in convection oven at 200 DEG C
Mode measures color space value again, thus changes (Δ E) by the color according to formula 1 and evaluate resistance to
Discolouration:
Wherein, Δ L*It is L before and after incipient scorch experiment*Difference between value, Δ a*Before and after being incipient scorch experiment
a*Difference between value, and Δ b*It is b before and after scorch test*Difference between value.
Polyesteramide can have from 5 to 10, such as, color change (Δ E) of 5 to 8.
In this range, polyesteramide can show the discoloration-resistant of excellence.
According to the present invention, the method preparing polyesteramide includes: make (A) dicarboxylic acids, (B)
Diamidogen and (C) straight chain aliphatic diols are polymerized, and the polyesteramide wherein prepared has from 280 DEG C
To the fusing points of 320 DEG C (Tm) and the crystallization temperature (Tc) from 260 DEG C to 290 DEG C.
In one embodiment, using typical polymerization, such as, melt polymerization can complete
(co) polymerization.
When polymerization, polymerization temperature can be with scope for from 80 DEG C to 300 DEG C, such as, from 80 DEG C
To 280 DEG C, and polymerization pressure can be with scope for from 10kgf/cm2To 40kgf/cm2, but be not limited to
This.
In one embodiment, polyesteramide can be obtained by procedure below, including: will
(A) dicarboxylic acids, (B) diamidogen, (C) straight chain aliphatic diols, catalyst and water are placed in reactor
In and at 80 DEG C to 150 DEG C stirring continue 0.5 hour to 2 hours, at 10kgf/cm2Extremely
40kgf/cm2Pressure under maintain at 200 DEG C to 280 DEG C this mixture continue 2 hours little to 4
Time, by pressure drop as little as 10kgf/cm2To 20kgf/cm2To carry out (A) dicarboxylic acids, (B) diamidogen
(C) (combined polymerization) reaction of straight chain aliphatic diols continues 1 hour to 3 hours, and
Temperature between the glass transition temperature (Tg) and its fusing point (Tm) of polyesteramide in vacuum
Under carry out obtained polyesteramide solid-state polymerization continue 10 minutes to 30 minutes.
Catalyst can be phosphorus catalyst, such as, phosphoric acid, phosphorous acid, hypophosphorous acid, they salt,
Their derivant etc..More specifically, catalyst can be phosphoric acid, phosphorous acid, hypophosphorous acid, even two
Sodium phosphate, sodium hypophosphite etc..
All monomers based on 100 weight portions ((A)+(B)+(C)), catalyst alternatively with
Such as 0.001 weight portion to 1 weight portion below 3 weight portions, more specifically 0.01 weight portion are to 0.5
The amount of weight portion exists, but is not limited to this.
Additionally, in preparation method, end-capping reagent can be used with amount described above, and permissible
Viscosity by the polyesteramide of the amount regulation synthesis of regulation end-capping reagent.
According to the present invention it is possible to preparation comprises the mechanograph of polyesteramide.Such as, crystallization polyamides
Amine ester resin can be used for preparing and require thermostability, light resistance, discoloration-resistant and mouldability
LED reflection device etc., but it is not limited to this.Mechanograph can be readily formed by those skilled in the art.
It follows that the present invention will be illustrated in greater detail with reference to some embodiments.It is, however, to be understood that carry
These embodiments of confession are merely to illustrate and are construed to never in any form limit the present invention.
Embodiment
Embodiment 1
According to the component listed the most in Table 1, using 49.84g(0.300mol) as dicarboxylic acids
P-phthalic acid (TPA), 49.85g(0.289mol) the 1,10-decamethylene diamine (DDA) as diamidogen,
The 1,6-HD as glycol (HDO) 1.80g(0.015mol), 1.01g as end-capping reagent
Benzoic acid, 0.10g to be placed in 2L as the sodium hypophosphite of catalyst and the water of 38.5ml high
In pressure still, it is then used by nitrogen and fills.It follows that continue in these components of stirring at 130 DEG C
After 60 minutes, heat the mixture to 230 DEG C and continue 2 hours, and indwelling is in 25kgf/cm2
Pressure under continue 3 hours, subsequently by by pressure drop as little as 15kgf/cm2Produce with making reaction
Material reaction continues 1 hour thus prepares polyesteramide preformed copolymer.It is prepared at 230 DEG C
The solid-state polymerization of polyesteramide preformed copolymer continues 6 hours, thus obtains polyesteramide.
Example 2
According to the component listed the most in Table 1, except using 41.98g(0.244mol) 1,10-
Decamethylene diamine (DDA) as diamidogen replace 49.85g(0.289mol) 1,10-decamethylene diamine (DDA),
With use 7.20g(0.061mol) 1,6-HD (HDO) as glycol replace 1.80g
(0.015mol) 1,6-hexanediol (HDO) outward, obtains with the method as in embodiment 1
Obtain polyesteramide.
Embodiment 3
According to the combination listed the most in Table 1, except using 44.60g(0.259mol) 1,10-
Decamethylene diamine (DDA) as diamidogen replace 49.85g(0.289mol) 1,10-decamethylene diamine (DDA),
With use 5.40g(0.046mol) 1,6-HD (HDO) as glycol replace 1.80g
(0.015mol) 1,6-hexanediol (HDO) outward, obtains with the method as in embodiment 1
Obtain polyesteramide.
Embodiment 4
According to the combination listed the most in Table 1, except using 44.60g(0.259mol) 1,10-
Decamethylene diamine (DDA) as diamidogen replace 49.85g(0.289mol) 1,10-decamethylene diamine (DDA),
With use 7.96g(0.046mol) 1,10-decanediol (DDO) as glycol replace 1.80g
(0.015mol) 1,6-hexanediol (HDO) outward, obtains with the method as in embodiment 1
Obtain polyesteramide.
Comparative example 1
According to the combination listed the most in table 2, except using 52.21g(0.302mol) 1,10-
Decamethylene diamine (DDA) as diamidogen replace 49.85g(0.289mol) 1,10-decamethylene diamine (DDA),
With use 0.18g(0.002mol) 1,6-HD (HDO) as glycol replace 1.80g
(0.015mol) 1,6-hexanediol (HDO) outward, obtains with the method as in embodiment 1
Obtain polyesteramide.
Comparative example 2
According to the combination listed the most in table 2, except using 52.21g(0.303mol) 1,10-
Decamethylene diamine (DDA) as diamidogen replace 49.85g(0.289mol) 1,10-decamethylene diamine (DDA),
With use 0.27g(0.002mol) 1,10-decanediol (DDO) as glycol replace 1.80g
(0.015mol) 1,6-hexanediol (HDO) outward, obtains with the method as in embodiment 1
Obtain polyesteramide.
Comparative example 3
According to the combination listed the most in table 2, except using 36.73g(0.213mol) 1,10-
Decamethylene diamine (DDA) as diamidogen replace 49.85g(0.289mol) 1,10-decamethylene diamine (DDA),
With use 10.80g(0.091mol) 1,6-HD (HDO) as glycol replace 1.80g
(0.015mol) 1,6-hexanediol (HDO) outward, obtains with the method as in embodiment 1
Obtain polyesteramide.
Comparative example 4
According to the combination listed the most in table 2, except using 36.73g(0.213mol) 1,10-
Decamethylene diamine (DDA) as diamidogen replace 49.85g(0.289mol) 1,10-decamethylene diamine (DDA),
With use 15.92g(0.091mol) 1,10-decanediol (DDO) as glycol replace 1.80g
(0.015mol) 1,6-hexanediol (HDO) outward, obtains with the method as in embodiment 1
Obtain polyesteramide.
Comparative example 5
According to the combination listed the most in table 2, except using 52.47g(0.305mol) 1,10-
Decamethylene diamine (DDA) as diamidogen replace 49.85g(0.289mol) 1,10-decamethylene diamine (DDA),
And do not use outside glycol, obtain polyesteramide with the method as in embodiment 1.
Table 1
Table 2
EXPERIMENTAL EXAMPLESThe
By the following method for the fusing point between before and after scorch test, crystallization temperature, glass transition
Temperature, intrinsic viscosity and color (Δ E) have rated the polyamide of preparation in embodiment and comparative example
Ester resin.Result is shown in table 3.
Performance evaluation
(1) fusing point, crystallization temperature and glass transition temperature (unit: DEG C): use differential to sweep
Retouch calorimeter (DCS) and measure the fusing point of every kind of polyesteramide, crystallization temperature and glass transition
Temperature.By Q20 tester (TA Instrument Inc.) be used as DSC, and from 30 DEG C to
With the rate of heat addition of 10 DEG C/min and exist with the cooldown rate of 10 DEG C/min within the temperature range of 400 DEG C
Measure under nitrogen.Here, crystallization temperature is determined to be in the peak of exothermic peak when cooling,
And fusing point is determined to be in the peak of endothermic peak when second time heats.Additionally, based on second time
The temperature measured when heating determines glass transition temperature.
(2) intrinsic viscosity (unit: dL/g): use Ubbelohde viscometer in m-cresol solution
Intrinsic viscosity at 25 DEG C.
(3) discoloration-resistant: evaluate resistance to by color change (Δ E) between before and after scorch test
Discolouration.According to ASTM D1209 use colorimeter (CM-2600d, Konica Minolta Co.,
Ltd.) color space value (L of the polyesteramide of preparation is measured*, a*, b*), and carry out
Wherein the polyesteramide of 1g to 3g is stayed in convective oven and continue 1 hour at 200 DEG C
Scorch test after the most again measure color space value, from there through according to equation 1
Color change (Δ E) evaluate its discoloration-resistant:
Wherein, Δ L*It is L before and after incipient scorch experiment*Difference between value, Δ a*Before and after being incipient scorch experiment
a*Difference between value, and Δ b*It is b before and after scorch test*Difference between value.
Table 3
In table 3 it can be seen that owing to these resins have the glass transition temperature of more than 90 DEG C,
Polyesteramide according to the present invention (embodiment 1 to 4) shows the thermostability of excellence, and
The mouldability of excellence is shown by the result of fusing point, crystallization temperature etc..Additionally, due to scorch test
It is excellent that the result of color change (Δ E) between front and back can be seen that these polyesteramide show
Different discoloration-resistant.I.e., it is possible to find out that these polyesteramide are at thermostability, discoloration-resistant and can
There is between mouldability the balance of excellence.
On the contrary, when not using (C) straight chain aliphatic diols (comparative example 5) or using a small amount of
(C) during straight chain aliphatic diols (comparative example 1 and 2), it can be seen that due to before scorch test
High color changing value (Δ E) between Hou, these polyesteramide show the discoloration-resistant of deterioration,
Thus be unsuitable for LED etc..Additionally, when (C) straight chain aliphatic diols using excess
Time (comparative example 3 and 4), it can be seen that although color change low between before and after scorch test
(Δ E), these polyesteramide have low fusing point and low crystallization temperature, thus performance is gone on business
Machinability and thermostability.
Should be appreciated that those skilled in the art can carry out various amendment, change, replace, Yi Jitong
Deng embodiment without departing from spirit and scope of the invention.
Claims (12)
1. a polyesteramide, comprises following polymer:
Dicarboxylic acids；
Diamidogen；With
Straight chain aliphatic diols,
Wherein, based on described diamidogen and the total amount of described straight chain aliphatic diols, described diamidogen
Exist with the amount of 85mol% to 99mol% and described straight chain aliphatic diols with 1mol% extremely
The amount of 15mol% exists, and wherein, described polyesteramide have from 280 DEG C to
The fusing point Tm of 320 DEG C and crystallization temperature Tc from 260 DEG C to 290 DEG C.
Polyesteramide the most according to claim 1, wherein, described dicarboxylic acids includes C8Extremely
C20Aromatic dicarboxylic acid and C8To C20At least one in alicyclic dicarboxylic acid.
Polyesteramide the most according to claim 1, wherein, described diamidogen includes C4Extremely
C20At least one in aliphatic diamine.
Polyesteramide the most according to claim 1, wherein, described straight chain aliphatic diols
Including C2To C20At least one in straight chain aliphatic diols.
Polyesteramide the most according to claim 1, wherein, described polyesteramide has
There is the glass transition temperature Tg from 80 DEG C to 120 DEG C.
Polyesteramide the most according to claim 1, wherein, described polyesteramide has
There is the intrinsic viscosity from 0.5dL/g to 1.0dL/g.
Polyesteramide the most according to claim 1, wherein, described polyesteramide has
Have by equation 1 below calculate from 5 to 10 color changes delta E:
Wherein Δ L* is the difference between the L* value before and after scorch test, and Δ a* is at incipient scorch
The difference between a* value before and after test, and Δ b* be the b* value before and after scorch test it
Between difference, wherein by the described polyesteramide indwelling of 1g to 3g in convection oven
1 hour is continued at 200 DEG C.
Polyesteramide the most according to claim 1, wherein, described polyesteramide has
Have and use the end-capping reagent of at least one comprising in aliphatic carboxylic acid and aromatic carboxylic acid to be closed
End group.
Polyesteramide the most according to claim 8, wherein, described end-capping reagent include acetic acid,
Propanoic acid, butanoic acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, myristic acid,
Palmic acid, stearic acid, neopentanoic acid, isopropylformic acid., benzoic acid, toluic acid, α-naphthoicacid,
At least one in β-naphthoic acid and methyl naphthalene formic acid.
10. the method preparing polyesteramide, including: make the fat of dicarboxylic acids, diamidogen and straight chain
The glycol polymerization of fat race,
Wherein, based on described diamidogen and the total amount of described straight chain aliphatic diols, described diamidogen
Exist with the amount of 85mol% to 99mol% and described straight chain aliphatic diols with 1mol% extremely
The amount of 15mol% exists, and
Wherein, described polyesteramide have from the fusing point Tm of 280 DEG C to 320 DEG C and
From crystallization temperature Tc of 260 DEG C to 290 DEG C.
11. 1 kinds of mechanographs, comprise polyesteramide tree according to any one of claim 1 to 9
Fat.
12. mechanographs according to claim 11, wherein, described mechanograph is LED reflection device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130062737A KR101593745B1 (en) | 2013-05-31 | 2013-05-31 | Polyamide ester resin, method for preparing the same, and article comprising the same |
| KR10-2013-0062737 | 2013-05-31 |
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