CN101421336B - High-fluidity polyamide - Google Patents
High-fluidity polyamide Download PDFInfo
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- CN101421336B CN101421336B CN2007800110315A CN200780011031A CN101421336B CN 101421336 B CN101421336 B CN 101421336B CN 2007800110315 A CN2007800110315 A CN 2007800110315A CN 200780011031 A CN200780011031 A CN 200780011031A CN 101421336 B CN101421336 B CN 101421336B
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
Abstract
The present invention relates to a polyamide and a process for the preparation thereof, and to compositions containing it. It relates more particularly to a polyamide obtained by polymerization of diacid and diamine monomers in the presence of multifunctional and monofunctional compounds capable of forming an amide function by reaction with either an aminated function or an acid function. This polyamide can in particular be used for the preparation of compositions intended, for example, to be moulded.
Description
The present invention relates to the method for a kind of polymeric amide and this polymeric amide of preparation and relate to the compsn that comprises it.Be particularly related to through diacid and diamine monomer at multifunctional and the monofunctional compound polymeric amide that obtains of polymerization down, saidly multifunctionally can form amide functional group through perhaps reacting with amine functional group or acid functional group with monofunctional compound.This polymeric amide is particularly useful for preparing for example will be by the compsn of moulding.
The polyamide based thermoplastic compsn can be transformed the parent material that is used to prepare plastic assembly through moulding, particularly injection moulding.
For these polyamide-based compsns, at least three salient featuress are that expectation obtains, and especially work as them and are used for these method for transformation.
First of these performances be based on the following fact, and promptly employed these thermoplastic compounds have to have in molten state and interested moulding process such as injection moulding, compatible flowability or rheological behaviour.This be because these thermoplastic compounds when their fusions, to have to be abundant mobile so that in some shaped devices, can be transmitted and handle for example injection moulding easily and apace.
Also having a purpose is the mechanical property that strengthens these compsns.These mechanical propertys are resistance to impact shock especially, deflection or tensile modulus, deflection or tensile break strength etc.Usually use reinforcing filler for this reason, like spun glass.
At last, under the situation of the assembly that forms by these thermoplastic compounds mouldings, expectation cleaning and uniform appearance.This is constrained to and is insoluble problem, particularly uses when having the thermoplastic compounds of high capacity spun glass, and these spun glass influence the appearance of molding assembly unfriendly.In order to obtain acceptable appearance, known use has the thermoplastic compounds of high workability.Yet the mechanical property of the goods that the increase of this flowability causes being obtained worsens.
Therefore, conclusion is for identical thermoplastic compounds, is difficult to obtain these different performances.
The applicant's company has developed a kind of by the multifunctional and polymeric amide monofunctional compound modification; It is compared with the conventional linear polymeric amide; Flowability and equal or better mechanical property with increase; And it can prepare the goods with good surface outward appearance, particularly when they comprise high-load filler.
Such polymeric amide obtains through the polymerization of dicarboxylicacid and diamine monomer, polyfunctional compound and monofunctional compound; Said polyfunctional compound has at least 3 acid or the amine functional groups that can form amido linkage with the functional group of said dicarboxylicacid and diamine monomer, and said simple function group compound has acid or the amine functional group functional group's same nature, that can form amido linkage with the functional group of said dicarboxylicacid and diamine monomer with said polyfunctional compound.Polymerization technique is traditional and is generally used for the polymeric amide based on diacid and diamine monomer, like the polymerization method of polyamide 66
First theme of the present invention be can be in the presence of following at least material polymerization and the polymeric amide that obtains:
(i) dicarboxylicacid and diamine monomer, or its salt;
(ii) 0.05 to 0.5mol% the polyfunctional compound who comprises at least 3 X1 of functional group is with respect to the total mole number of the compositing monomer of polymeric amide;
(iii) 0.2 to 2mol% the monofunctional compound that comprises the X2 of functional group is with respect to the total mole number of the compositing monomer of polymeric amide;
X1 of functional group and X2 are the carboxylic acid functional or the amine functional groups that can react and can form amido linkage with dicarboxylicacid and diamine monomer (i);
When if-polyfunctional compound (ii) comprises the X1 of functional group of carboxylic acid type, then monofunctional compound (iii) comprises the X2 of functional group of carboxylic acid type; With
When if-polyfunctional compound (ii) comprises the X1 of functional group of amine type, then monofunctional compound (iii) comprises the X2 of functional group of amine type.
Term " mole number of polymeric amide compositing monomer " is meant that the mole number of dicarboxylicacid adds the mole number of diamines, can choose the latter wantonly and appoint with the shape of salt and combined the optional mole number that adds upper amino acid or lactan.
Therefore, the polyfunctional compound (ii) (iii) relates to the carboxylic acid type of same nature or the X1 of functional group and the X2 of amine type with monofunctional compound.Preferably, the polyfunctional compound X1 of functional group (ii) is identical with the monofunctional compound X2 of functional group (iii).
Preferably, the polyfunctional compound of polymeric amide according to the present invention through dicarboxylicacid and diamine monomer or its salt, single type (ii) with the monofunctional compound of single type (iii) polymerization and obtain.
Dicarboxylicacid and diamine monomer particularly are generally used for preparing those monomers of following material:
The fatty polyamide of-PA6.6, PA6.10, PA6.12, PA12.12 or PA4.6 type,
-semiaromatic polyamide composition, as gather (m xylylene adipamide) (MXD6), gather terephthaloyl amine, like polyamide 6 .T and 6.6.6T, gather different benzene diamide, like polyamide 6 .I and 6.6.6I,
-polyaramide,
-or their multipolymer.
These dicarboxylicacid and/or diamine monomer can be aliphatic, particularly comprise linearity, branching or closed chain, perhaps aromatic.
As diacid monomer; What can mention especially is aliphatics or the aromatic dicarboxylic acid with 4 to 12 carbon atoms, like hexanodioic acid, terephthalic acid, iso-phthalic acid, oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, pimelic acid, sebacic acid or dodecanedioic acid.
As diamine monomer, what can mention especially is the aliphatics with 4 to 12 carbon atoms, optional cyclic aliphatic; Perhaps aromatic diamine; Like hexamethylene-diamine, tetramethylenediamine, m-xylene diamine, isophorone diamine, 3,3 ', 5-trimethylhexamethylenediamine and methyl pentamethylene diamine.
Especially preferably use the compositing monomer of polyamide 66 according to the present invention, it is a hexanodioic acid, hexamethylene-diamine, or its salt, and like hexanodioic acid hexa-methylene two ammoniums, optional known nylon salt or N salt.
In the method according to the invention, preferably can use the dicarboxylicacid and the diamines of equimolar amount, a kind of excessive in the perhaps said compound, to obtain carboxylic or amine-terminated unbalanced, this knows to those skilled in the art.
Can comprise one or more dissimilar dicarboxylicacid and one or more diamines according to modified polyamide of the present invention.Therefore, for example in polymerization, can add the dicarboxylicacid of equimolar amount and the another kind of dicarboxylicacid of diamines and a certain proportion of another kind of form.
Amino acid or its lactan can also in dicarboxylicacid and diamine monomer, be added, like hexanolactam.Especially can in reaction medium, add 1 to 15mol% amino acid or lactan, preferred 2 to 10mol%, with respect to the mole number of the compositing monomer of polymeric amide.
(ii) comprise at least 3 according to polyfunctional compound of the present invention, preferred 3 to 10, more preferably 3 or 4 X1 of functional group; X1 is the carboxylic acid functional or the amine functional group that can also can form amido linkage with the compositing monomer reaction of polymeric amide.
The X1 of functional group is carboxylic acid functional or primary amine or secondary amine functional groups preferably, perhaps their salt.
The polyfunctional compound's who is suitable for using example is especially at US5346984, and US5959069 is mentioned among WO9635739 and the EP672703.
The polyfunctional compound of preferred formula (1) is (ii) especially:
R-[A-X1]n(1)
Wherein:
-R is aliphatics (linearity or a branching), and cyclic aliphatic or aromatic hydrocarbons group comprise at least 2 carbon atoms and can comprise one or more heteroatomss;
-A is covalent linkage or aliphatic hydrocarbon groups, and said aliphatic hydrocarbon groups can comprise one or more heteroatomss, and comprises 1 to 20 carbon atom, preferred 1 to 6 carbon atom;
-X1 is carboxylic acid functional or primary amine or secondary amine functional groups, perhaps their salt; And
-n is 3 to 10 integer, preferably equals 3 or 4.
This polyfunctional compound (ii) preferably comprises at least 4 carbon atoms, preferably at least 5 carbon atoms, the particularly aliphatics of 10 to 100 carbon atoms (linearity or branching), and cyclic aliphatic or aromatic hydrocarbon compound, it can comprise one or many and heteroatoms.
Heteroatoms can be O, S, N or P.
A can be methylene radical or polymethylene group, and like ethyl, propyl group or butyl, perhaps polyoxy alkylidene group is like polyoxy ethylidene group.
R can be the aliphatics hydrocarbon chain that comprises saturated or undersaturated and linear or the branching of 2 to 10 carbon atoms; It can comprise cyclohexyl, hexamethylene acyl group, benzyl, naphthyl, anthryl, xenyl, triphenyl, pyridine, dipyridyl, pyrroles, indoles, furans, thiophene, purine, quinoline, phenanthrene, porphyrin, phthalocyanine, naphthalene phthalocyanine, 1,3,5-triazines, 1; 4-diazine, 2; 3,5,6-tetraethyl-piperazine, piperazine or tetrathiafulvalene.
As the polyfunctional compound who has carboxylic acid functional X1 example (ii), can mention 2,2,6 especially, 6-four (β-propyloic) pimelinketone, diaminopropanes-N, N, N '; N '-tetraacethyl, 3,5,3 ', 5 '-xenyl tetracarboxylic acid, from the acid, 3,5 of phthalocyanine and naphthalene phthalocyanine, 3 ', 5 '-xenyl tetracarboxylic acid, 1; 3,5,7-naphthalene tetracarboxylic acid, 2,4,6-pyridinetricarboxylic acid, 3,5,3 '; 5 '-dipyridyl tetracarboxylic acid, 3,5,3 ', 5 '-UVNUL MS-40 tetracarboxylic acid, 1,3,6,8-acridine tetracarboxylic acid, trimesic acid, 1; 2,4,5-benzene tertacarbonic acid and 2,4,6-three (hexosamine)-1,3,5-triazines (TACT).
As the polyfunctional compound who has amine functional group X1 example (ii); Can mention particularly nitrilo triethylamine of nitrilo trialkylamine; Two alkylene triamine are NSC 446, bis hexamethylene triamine, three alkylidene group tetramines and four alkylidene groups, five amine particularly; Alkylidene group is ethylidene preferably; 4-amino-ethyl-1,8, octamethylenediamine; Trimeric cyanamide, carry out the compound (from the Jeffamine
of Hunt sman) that amination obtains by TriMethylolPropane(TMP) or glycerine and propylene oxide reaction and to terminal hydroxy group shown in the following general formula:
Wherein: R
1Expression propane-1,1,1-three base or propane-1,2,3-three groups and A represent polyoxy ethylidene group.
For example can use the Jeffamine
(polyoxyethylene triamine) that makes by Huntsman as according to polyfunctional compound of the present invention.
Monofunctional compound (iii) preferably comprises aliphatics, cyclic aliphatic or the aromatic hydrocarbon compound of at least 2 carbon atoms, and can comprise heteroatoms (O, S, N or P).
Monofunctional compound (iii) is preferably selected from n-hexadecyl amine, Octadecane base amine and dodecyl amine, acetate, LAURIC ACID 99 MIN, benzylamine, phenylformic acid, propionic acid and 4-amino-2,2,6,6-tetramethyl piperidine.
The polymerization of the inventive method is particularly carried out according to the polymeric routine operation condition of dicarboxylicacid and diamines, when when not having multifunctional and monofunctional compound, carrying out polymerization.
Such polymerization method can comprise, briefly:
-stir with pressure under heat monomer, polyfunctional compound (ii) and the mixture of monofunctional compound (i),
-mixture is being kept the scheduled time under the pressure He under the temperature, relief pressure and under the temperature greater than the mixture fusing point, keep the scheduled time then particularly under nitrogen or vacuum, thereby continues polymerization through the water of removing formation.
The polyfunctional compound (ii) and monofunctional compound (i) preferably when polymerization begins, add.In the case, (ii) and the polymerization of mixtures of monofunctional compound (i) to dicarboxylicacid and diamine monomer and polyfunctional compound.
In case from polymerization, withdraw from, polymkeric substance can be cooled, advantageously use water cooling and extrude and cut with the preparation particle.
Certainly carry out continuously or intermittently according to polymerization method of the present invention.
In polymerization method of the present invention; Use 0.05 to 0.5mol%, preferred 0.2 to 0.5mol%, more preferably 0.25 to 0.4mol% polyfunctional compound are (ii); With respect to the total mole number of the compositing monomer of polymeric amide, particularly 0.25,0.5,0.1,0.15,0.2,0.25,0.3,0.35 and 0.4mol%.
In polymerization method of the present invention; Use 0.2 to 2mol%, preferred 0.5 to 2mol%; More preferably 0.5 to 1mol% monofunctional compound (iii), with respect to the total mole number of the compositing monomer of polymeric amide, particularly 0.4,0.5,0.6,0.7,0.8 and 0.9mol%.
The preferred polyfunctional compound who uses (ii) follows following relational expression with monofunctional compound ratio (iii):
(nCpo * FX1)/nCmo between 0.1 to 4,
Wherein:
NCpo polyfunctional compound mole number (ii),
The nCmo monofunctional compound (iii) mole number and
The number of the FX1 polyfunctional compound X1 of functional group (ii).
According to the present invention, according to standard ISO 307 (0.5% polymers soln in 90% formic acid, temperature are 25 ℃), the viscosity index that preferred modified polyamide has in solution is 80 to 120, particularly 85 to 110.
Another theme of the present invention is the compsn that comprises above-mentioned at least polymeric amide.
Preferably, polymeric amide of the present invention is used as matrix in said composition, particularly in order to prepare moulded parts.
In order to improve the mechanical property of said composition; Add at least a enhancing and/or loose filler is favourable to it; Said filler is preferably selected from fibrous packing such as spun glass, the filler such as the mica of mineral filler such as clay, kaolin or enhancing or thermoset nano particle and powder type.Strengthen and/or the degree of mixing of filler according to the standard of field of compound material, it can be, for example 1 to 80%, preferred 10 to 70%, the degree of 30 to 60% filler particularly.
Except modified polyamide of the present invention, said composition can comprise one or more other polymkeric substance, preferred polyamide or copolyamides.
Can be additionally contained in preparation according to compsn of the present invention and plan normally used additive in the preparation of daiamid composition of moulding.Therefore, the reagent that can mention lubricant, fire retardant, softening agent, nucleator, catalyzer, enhance mechanical properties is like optional grafted elastomerics, light and/or thermo-stabilizer, oxidation inhibitor, static inhibitor, tinting material, matting agent, moulding auxiliary agent or other common additive.
These fillers and additive can for example join in the modified polyamide in melting mixing or polymerization process through being suitable for the standard manner of various fillers or additive.
According to polymeric amide of the present invention can also the masterbatch type compsn of additive be used as matrix being used for comprising at high proportion with other thermoplastic compounds blended.
Particularly in order to give certain performance, particularly rheological property, can also comprise thermoplastic polymer, particularly (be total to) in the compsn of polymeric amide as matrix and be used as additive or mixture according to polymeric amide of the present invention.Common and the thermoplastic polymer melting mixing according to polymeric amide of the present invention.Can use (being total to) polymeric amide of 10 to 90 weight % especially, like linear (being total to) polymeric amide, preferred 30 to 80 weight % are with respect to the total amount of (being total to) polymeric amide and polymeric amide of the present invention.
Can be according to compsn of the present invention as the parent material in engineering plastics field, as through in through injection moulding, through injection moulding/blowing, preparation through the goods extruding or obtain through extrusion molding/blowing.
According to the embodiment of standard, modified polyamide is extruded with the form of rod for example in double screw extruder, is cut into pellet subsequently.Prepare molding assembly through the above-mentioned pellet of fusion with molten state to the injection moulding apparatus feed composition subsequently.
The concrete term that uses in the specification sheets is to understand principle of the present invention for ease.Yet, be to be understood that the use of these concrete terms is not regarded as limiting scope of invention.Term " and/or " comprise implication with, or and all of this term coherent element possibly make up.
By the following example other details of the present invention or advantage are described more clearly, said embodiment is only used for explaining the present invention.
Experimental section
Embodiment 1: the preparation polymeric amide
In the autoclave that comprises whipping appts of heating, carry out polymerization.
In autoclave, add 11.111kg N salt (waiting mole hexanodioic acid and hexamethylene-diamine) at 90 ℃ with 5 liters of zero(ppm) water; 81g2,2,6; 6-four-(β-propyloic) pimelinketone (0.25mol%), 80g phenylformic acid (0.78mol%) and 40g skimmer (Silcolapse).
Mixture is heated to 280 ℃ temperature under the whipped state under 7.5 normal atmosphere.Under this temperature and pressure, kept 2 hours.
Reduce pressure subsequently, used the nitrogen purging autoclave then one and a half hours, keeping temperature simultaneously is 280 ℃.Subsequently system was placed 0.5 atmospheric pressure vacuum condition following 1 hour.
The fused polymkeric substance is extruded with bar-shaped subsequently, and water cools off fast and cuts into particle then.
Through the synthetic by this way various polymkeric substance of the ratio that changes polyfunctional compound and monofunctional compound.
Embodiment C 1 is corresponding to there not being the linear polyamidoamine 66 for preparing under multifunctional and the monofunctional compound.
Embodiment 2: the polymeric amide performance
The characteristic of these polymkeric substance, rheological property and mechanical property are collected in the following table 1.In order to test some performances, the specimen that preparation is produced through injection moulding.
Table 1
| C1 | 1 | 2 | 3 | 4 | |
| Polyfunctional compound's content (mol%) | 0 | 0.25 | 0.3 | 0.25 | 0.4 |
| The content of monofunctional compound (mol%) | 0 | 0.78 | 0.8 | 0.6 | 0.8 |
| NH 2(meq/kg) | 50 | 13 | 14 | 15 | 14 |
| COOH(meq/kg) | 70 | 190 | 205 | 180 | 222 |
| IV(1) | 142 | 92 | 87 | 102 | 100 |
| Melt flow index (2) (g/10min) | 8 | 43.2 | 42.5 | 32 | 39 |
| Notched Izod impact strength (kJ/m 2) | 5.7 | 3.7 | 3.5 | 3.9 | 3.6 |
| Notched Izod impact strength (kJ/m not 2) | - | 72 | 60 | 63 | 78 |
| Tensile strength (N/mm 2) | 55 | 75 | 67 | 75 | 70 |
| Elongation (%) | 30 | 2.7 | 2.7 | 3.2 | 2.7 |
| Tensile modulus (N/mm 2) | 3100 | 3410 | 3110 | 3080 | 3010 |
(1) viscosity index is measured by 0.5% solution that polymkeric substance is dissolved in 90% formic acid according to standard ISO 307.
(2) melt flow index (MFI) according to standard A STM D1238, is measured with g/10min under load 325g in 275 ℃.
Sour and amine-terminated content is through the potentiometric analysis method quantitative measurement, and notch shock is measured according to standard ISO 179/1eU and ISO179/1eA, and tensile strength, elongation and tensile modulus are measured under 23 ℃ temperature according to standard ISO 527.
Embodiment 3: the compsn that contains filler
Add 50 weight % spun glass to the polymeric amide that comprises above-mentioned preparation in as the compsn of polyamide matrix through have in venting port (venting) twin screw extruder (L/D=36) melting mixing in Werner-Pfleiderer ZSK40 type.Said spun glass is Vetrotex99B.It is following to extrude parameter: extrusion temperature has distribution 235-280 ℃ of increase; The screw rod speed of rotation: PM 260 changes; Compsn output: 40kg/h; Motor torque (motortorque) and the motor output (motor output absorbed) that absorbs change according to polymeric amide.
The performance that contains the compsn of filler is collected in the following table 2.In order to measure some performances, the specimen that preparation is produced through injection moulding.
Table 2
| C1 | 1 | 2 | 3 | 4 | |
| Melt flow index (3) (g/10min) | 2.8 | 16.5 | 18 | 11 | 13 |
| Notched Izod impact strength (kJ/m 2) | 17.8 | 18.4 | 18.8 | 17 | 18 |
| Notched Izod impact strength (kJ/m not 2) | 92 | 86 | 90 | 81 | 82 |
| Tensile stress (N/mm 2) | 224 | 244 | 251 | 233 | 247 |
| Elongation (%) | 2.7 | 2.3 | 2.5 | 2.2 | 2.3 |
| Tensile modulus (N/mm 2) | 15300 | 15100 | 16300 | 15400 | 16300 |
| Spiral test (spiral test) (cm) | 33 | 45 | 48 | 40 | 45 |
| Appearance | Difference | Fine | Fine | Fine | Fine |
| Motor torque (N/mm) | 50-55 | 30-35 | 30-35 | 30-35 | 30-35 |
| The motor output (A) that absorbs | 26 | 16 | 16 | 17 | 16 |
(3) melt flow index (MFI) according to standard A STM D1238, is measured with g/10min under load 2160g in 275 ℃.
The visual evaluation appearance; Spiral test can be through the flowability of following quantized sets compound, promptly through in the volution mould that under the injection pressure of 275 ℃ of barrel zone temperatures, 80 ℃ of die temperatures and 80bar, is injected into semi-circular cross-section, thickness 2mm and diameter 4cm with the pellet fusion with in BM-Biraghi85T press (press) (result is expressed as the length of the mould that is full of compsn suitably).
Embodiment 4:Comprise linear polyamidoamine and according to the compsn that contains filler of the mixture of polymeric amide of the present invention
Exist under the 30 weight % spun glass, preparing the compsn of the polyamide 66 (PA C1) of the polymeric amide that comprises embodiment 4 (PA4) and various ratios through melting mixing in the twin screw extruder that has venting port (L/D=36) in Werner-Pfleiderer ZSK40 type.It is following to extrude parameter: extrusion temperature has distribution 250-285 ℃ of increase; The screw rod speed of rotation: PM 260 changes; Compsn output: 40kg/h; The motor output of motor torque and absorption changes according to polymeric amide.
The performance that contains the compsn of filler is collected in the following table 3.In order to measure some performances, the specimen that preparation is produced through injection moulding.
Table 3
| 4 | 5 | 6 | 7 | |
| Daiamid composition | 100％PA4 | 80％PA4+20％PAC1 | 70％PA4+30％PAC1 | 50％PA4+50％PAC1 |
| Melt flow index (3) (g/10min) | 10 | 11.5 | 10 | 8.1 |
| Breach charpy impact (kJ/m 2) | 11 | 10 | 11 | 11 |
| Breach charpy impact (kJ/m not 2) | 45 | 50 | 54 | 67 |
(3) melt flow index (MFI) according to standard A STMD1238, is measured with g/10min under load 2160g in 275 ℃.
Charpy impact is measured according to standard ISO 179/leA.
Observe in polymeric amide according to the present invention and to add the mechanical property that linear polyamidoamine 66 can improve the compsn of generation, and its melt flow index of not negative impact.
Embodiment 5: the preparation of modified polyamide and performance
Record according to embodiment 1 prepares according to modified polyamide of the present invention with adding 5 or 10 weight % hexanolactams (therefore replacing 5 or 10 weight %N salt) according to the monomer ratio of testing 4.
The fused polymkeric substance is extruded with bar-shaped subsequently, in water, cools off fast then and is cut into particle.
The characteristic of these polymkeric substance, rheological property and mechanical property are collected in the following table.
Table 4
| C1 | 4 | 8 | 9 | |
| Hexanolactam (weight %) | 0 | 0 | 5 | 10 |
| Melt flow index (2) (g/10min) | 8 | 32 | 31 | 32 |
| Breach charpy impact (kJ/m 2) | 4.5 | 3.4 | 4.2 | 4.6 |
(2) melt flow index (MFI) according to standard A STM D1238, is measured with g/10min under the 325g load in 275 ℃.
Claims (23)
1. polymeric amide can obtain through polymerization in the presence of following at least material:
(i) dicarboxylicacid and diamine monomer, or their salt,
(ii) 0.05 to 0.5mol% the polyfunctional compound who comprises at least 3 X1 of functional group is with respect to the total mole number of the compositing monomer of polymeric amide;
(iii) 0.2 to 2mol% the monofunctional compound that comprises the X2 of functional group is with respect to the total mole number of the compositing monomer of polymeric amide;
X1 of functional group and X2 are the carboxylic acid functional or the amine functional groups that can react and can form amido linkage with dicarboxylicacid and diamine monomer (i);
If-polyfunctional compound (ii) comprises the X1 of functional group of carboxylic acid type, then monofunctional compound (iii) comprises the X2 of functional group of carboxylic acid type; With
If-polyfunctional compound (ii) comprises the X1 of functional group of amine type, then monofunctional compound (iii) comprises the X2 of functional group of amine type.
2. the described polymeric amide of claim 1, the compositing monomer that it is characterized in that the polymeric amide of dicarboxyl acid type are aliphatics or aromatic and comprise 4 to 12 carbon atoms.
3. claim 1 or 2 described polymeric amide, the compositing monomer that it is characterized in that the polymeric amide of diamines type are aliphatics or aromatic and comprise 4 to 12 carbon atoms.
4. claim 1 or 2 described polymeric amide, the compositing monomer that it is characterized in that polymeric amide are hexanodioic acid and hexamethylene-diamine or their salt.
5. claim 1 or 2 described polymeric amide is characterized in that the polyfunctional compound is (ii) by shown in the general formula (1):
R-[A-X1]n (1)
Wherein:
-R is the aliphatics of linearity or branching, and cyclic aliphatic or aromatic hydrocarbons group comprise at least 2 carbon atoms and optional and comprise one or more heteroatomss;
-A is covalent linkage or aliphatic hydrocarbon groups, and said aliphatic hydrocarbon groups is optional to comprise one or more heteroatomss, and said aliphatic hydrocarbon groups comprises 1 to 20 carbon atom;
-X1 is carboxylic acid functional or primary amine or secondary amine functional groups, perhaps their salt; With
-n is 3 to 10 integer.
6. claim 1 or 2 described polymeric amide is characterized in that the polyfunctional compound (ii) is aliphatics, cyclic aliphatic or the aromatic hydrocarbon compound that comprises at least 4 carbon atoms, and it is chosen wantonly and comprises one or more heteroatomss.
7. claim 1 or 2 described polymeric amide is characterized in that the polyfunctional compound who has carboxylic acid functional X1 (ii) is selected from 2,2,6,6-four-(β-propyloic) pimelinketone, diaminopropanes-N, N, N '; N '-tetraacethyl, 3,5,3 ', 5 '-biphenyltetracarboxyacid acid, from the acid, 1,3,5 of phthalocyanine and naphthalene phthalocyanine, 7-naphthalene tetracarboxylic acid, 2; 4,6-pyridinetricarboxylic acid, 3,5,3 ', 5 '-dipyridyl tetracarboxylic acid, 3,5; 3 ', 5 '-UVNUL MS-40 tetracarboxylic acid, 1,3,6,8-acridine tetracarboxylic acid, trimesic acid, 1,2; 4,5-benzene tertacarbonic acid and 2,4,6-three (hexosamine)-1,3,5-triazines (TACT).
8. claim 1 or 2 described polymeric amide; It is characterized in that the polyfunctional compound who has amine functional group X2 (ii) is selected from the nitrilo trialkylamine, two alkylene triamine, three alkylidene group tetramines and four alkylidene groups, five amine; 4-amino-ethyl-1; The 8-octamethylenediamine, trimeric cyanamide, carry out the compound that amination obtains by TriMethylolPropane(TMP) or glycerine and propylene oxide reaction and to terminal hydroxy group shown in the following general formula:
Wherein: R
1Expression propane-1,1,1-three base or propane-1,2,3-three groups and A represent polyoxy ethylidene group.
9. claim 1 or 2 described polymeric amide is characterized in that monofunctional compound (iii) is aliphatics, cyclic aliphatic or the aromatic hydrocarbon compound that comprises at least 2 carbon atoms, its optional heteroatoms that comprises.
10. claim 1 or 2 described polymeric amide; It is characterized in that monofunctional compound (iii) is selected from n-hexadecyl amine, Octadecane base amine and dodecyl amine, acetate, LAURIC ACID 99 MIN, benzylamine, phenylformic acid, propionic acid and 4-amino-2; 2,6, the 6-tetramethyl piperidine.
11. claim 1 or 2 described polymeric amide is characterized in that the polyfunctional compound X1 of functional group (ii) is identical with the monofunctional compound X2 of functional group (iii).
12. claim 1 or 2 described polymeric amide, the polyfunctional compound who it is characterized in that using 0.2 to 0.5mo % (ii), with respect to the total mole number of the compositing monomer of polymeric amide.
13. claim 1 or 2 described polymeric amide is characterized in that using 0.5 to 1mol% monofunctional compound (iii), with respect to the total mole number of the compositing monomer of polymeric amide.
14. claim 1 or 2 described polymeric amide is characterized in that the polyfunctional compound who uses (ii) follows following relation with monofunctional compound ratio (iii):
(nCpo * FX1)/nCmo between 0.1 to 4,
Wherein:
NCpo polyfunctional compound mole number (ii),
The nCmo monofunctional compound (iii) mole number and
The number of the FX1 polyfunctional compound X1 of functional group (ii).
15. claim 1 or 2 described polymeric amide is characterized in that being aggregated under the condition that has amino acid or lactan and carry out.
16. claim 1 or 2 described polymeric amide is characterized in that according to standard ISO 307 viscosity that this modified polyamide has is 80 to 120 in solution, said solution be 0.5% polymkeric substance in 90% formic acid, under 25 ℃ of temperature, measure.
17. a compsn comprises each described polymeric amide of claim 1 to 16 at least.
18. the described compsn of claim 17 comprises each described polymeric amide of claim 1 to 16 as matrix.
19. the described compsn of claim 17 comprises the mixture of each said polymeric amide of thermoplastic polymer and claim 1 to 16.
20. the described compsn of claim 19 comprises the mixture of each said polymeric amide of polymeric amide and claim 1 to 16.
21. the described compsn of claim 19 comprises the mixture of each said polymeric amide of copolyamide and claim 1 to 16.
22. each described compsn of claim 17 to 21 comprises at least a reinforcing filler and/or loose filler.
23. goods, it is through carrying out injection moulding to each said compsn of claim 17 to 22 or blowing obtains.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0602784A FR2899232B1 (en) | 2006-03-31 | 2006-03-31 | POLYAMIDE OF HIGH FLUIDITY |
| FR0602784 | 2006-03-31 | ||
| FR0610513A FR2909384A1 (en) | 2006-12-01 | 2006-12-01 | New polyamide formed by polymerization of carboxylic diacid/diamine monomer in presence of multifunctional compounds e.g. 2,2,6,6-tetra-(beta-carboxyethyl)cyclohexanone and benzoic acid useful to make molded articles e.g. plastic articles |
| FR0610513 | 2006-12-01 | ||
| PCT/EP2007/053119 WO2007113262A1 (en) | 2006-03-31 | 2007-03-30 | High-fluidity polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101421336A CN101421336A (en) | 2009-04-29 |
| CN101421336B true CN101421336B (en) | 2012-06-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800110315A Active CN101421336B (en) | 2006-03-31 | 2007-03-30 | High-fluidity polyamide |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101421336B (en) |
| FR (1) | FR2899232B1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2950626B1 (en) * | 2009-09-30 | 2013-11-08 | Rhodia Operations | POLYAMIDES WITH HIGH FLUIDITY |
| CN102153857B (en) * | 2011-03-16 | 2014-03-26 | 金发科技股份有限公司 | High-filled modified-surface strengthened polyamide composition |
| CN103589138A (en) * | 2012-08-15 | 2014-02-19 | 上海杰事杰新材料(集团)股份有限公司 | Continuous-fiber-reinforced polyamide composite material prepreg tape and preparation method thereof |
| CN102911355B (en) * | 2012-11-20 | 2016-01-13 | 中国石油化工股份有限公司 | The preparation method of a kind of high gloss high workability PA6 |
| CN103642037A (en) * | 2013-11-12 | 2014-03-19 | 金发科技股份有限公司 | Polyamide resin and polyamide composition composed of same |
| EP3077088B1 (en) * | 2013-12-02 | 2017-12-27 | Dow Global Technologies LLC | Method for forming a composite polyamide membrane post treated with nitrious acid |
| CN105885055A (en) * | 2016-01-22 | 2016-08-24 | 东华大学 | High-flow polyamide resin and preparing method thereof |
| CN108239281A (en) * | 2016-12-27 | 2018-07-03 | 上海杰事杰新材料(集团)股份有限公司 | A kind of branched high-temperature nylon and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0345648A2 (en) * | 1988-06-07 | 1989-12-13 | Ems-Inventa Ag | Thermoplastically processable polyamides |
| EP0774480A1 (en) * | 1995-11-18 | 1997-05-21 | Basf Aktiengesellschaft | Preparation method for branched polyamides |
| CN1264397A (en) * | 1997-07-17 | 2000-08-23 | 罗狄亚工程塑料有限责任公司 | Thermoplastic copolyamide and its composition |
| US20040030057A1 (en) * | 2000-06-16 | 2004-02-12 | Nicolangelo Peduto | Modified polyamides, polyamide compositions, and method for making same |
-
2006
- 2006-03-31 FR FR0602784A patent/FR2899232B1/en not_active Expired - Fee Related
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- 2007-03-30 CN CN2007800110315A patent/CN101421336B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0345648A2 (en) * | 1988-06-07 | 1989-12-13 | Ems-Inventa Ag | Thermoplastically processable polyamides |
| EP0774480A1 (en) * | 1995-11-18 | 1997-05-21 | Basf Aktiengesellschaft | Preparation method for branched polyamides |
| CN1264397A (en) * | 1997-07-17 | 2000-08-23 | 罗狄亚工程塑料有限责任公司 | Thermoplastic copolyamide and its composition |
| US20040030057A1 (en) * | 2000-06-16 | 2004-02-12 | Nicolangelo Peduto | Modified polyamides, polyamide compositions, and method for making same |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2899232A1 (en) | 2007-10-05 |
| FR2899232B1 (en) | 2008-05-16 |
| CN101421336A (en) | 2009-04-29 |
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Effective date of registration: 20200220 Address after: Fa Guobali Patentee after: POLYAMIDE HIGH PERFORMANCE GmbH Address before: Obervillier, France Patentee before: RHODIA OPERATIONS |