CN101421336A - High-fluidity polyamide - Google Patents
High-fluidity polyamide Download PDFInfo
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- CN101421336A CN101421336A CNA2007800110315A CN200780011031A CN101421336A CN 101421336 A CN101421336 A CN 101421336A CN A2007800110315 A CNA2007800110315 A CN A2007800110315A CN 200780011031 A CN200780011031 A CN 200780011031A CN 101421336 A CN101421336 A CN 101421336A
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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
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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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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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 composition that comprises it.Be particularly related to by diacid and the diamine monomer polymeric amide that polymerization obtains in the presence of multifunctional and monofunctional compound, described multifunctional and monofunctional compound can by or react with amine functional group or acid functional group and to form amide functional group.This polymeric amide is particularly useful for preparation example as will be by the composition of molding.
The polyamide based thermoplastic composition can be transformed the parent material that is used to prepare plastic assembly by molding, particularly injection moulding.
For these polyamide-based compositions, 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 to have to when their fusions be abundant mobile so that can be transmitted and handle for example injection moulding easily and apace in some shaped devices.
Also having a purpose is the mechanical property that strengthens these compositions.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, as glass fibre.
At last, under the situation of the assembly that forms by these thermoplastic compounds moldings, expectation cleaning and uniform appearance.This is constrained to and is insoluble problem, particularly uses when having the thermoplastic compounds of high capacity glass fibre, and these glass fibre influence the appearance of molding assembly unfriendly.In order to obtain acceptable appearance, known use has the thermoplastic compounds of high workability.Yet the increase of this flowability causes the mechanical property of the goods that obtained to worsen.
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 by the polymerization of dicarboxylic acid and diamine monomer, polyfunctional compound and monofunctional compound, described polyfunctional compound has at least 3 acid or the amine functional groups that can form amido linkage with the functional group of described dicarboxylic acid and diamine monomer, and described 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 described dicarboxylic acid and diamine monomer with described polyfunctional compound.Polymerization technique is traditional and is generally used for polymeric amide based on diacid and diamine monomer, as the polymerization process 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) dicarboxylic acid 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 dicarboxylic acid 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 dicarboxylic acid adds the mole number of diamines, can choose wantonly the latter appoint with the shape of salt 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 by dicarboxylic acid and diamine monomer or its salt, single type (ii) with the monofunctional compound of single type (iii) polymerization and obtain.
Dicarboxylic acid 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 poly-(m xylylene adipamide) (MXD6), poly-terephthaloyl amine, as polyamide 6 .T and 6.6.6T, poly-different benzene diamide, as polyamide 6 .I and 6.6.6I,
-polyaramide,
-or their multipolymer.
These dicarboxylic acid 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, as 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, as hexamethylene-diamine, butanediamine, 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 as hexanodioic acid hexa-methylene two ammoniums, optional known nylon salt or N salt.
In the method according to the invention, preferably can use the dicarboxylic acid and the diamines of equimolar amount, a kind of excessive in the perhaps described compound, to obtain carboxylic or amine-terminated unbalanced, this knows to those skilled in the art.
Can comprise one or more dissimilar dicarboxylic acid and one or more diamines according to modified polyamide of the present invention.Therefore, for example in polymerization, can add the dicarboxylic acid of equimolar amount and the another kind of dicarboxylic acid of diamines and a certain proportion of another kind of form.
Amino acid or its lactan can also be added, as hexanolactam in dicarboxylic acid and diamine monomer.Especially can add 1 to 15mol% amino acid or lactan in reaction medium, 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 US 5 346 984, and US 5 959 069, is mentioned among WO 9635739 and the EP 672 703.
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 described 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 as ethyl, propyl group or butyl, perhaps polyoxy alkylidene group is as 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-triazine, 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, acid from phthalocyanine and naphthalene phthalocyanine, 3,5,3 ', 5 '-xenyl tetracarboxylic acid, 1,3,5, the 7-naphthalene tetracarboxylic acid, 2,4, the 6-pyridinetricarboxylic acid, 3,5,3 ', 5 '-dipyridyl tetracarboxylic acid, 3,5,3 ', 5 '-benzophenone 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 diethylenetriamine, 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 carries out compound that amination obtains (from the Jeffamine of Huntsman 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 bases or propane-1,2,3-three groups and A represent polyoxy ethylidene group.
Can use the Jeffamine that for example makes by Huntsman
(polyoxyethylene triamine) conduct is 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, 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 dicarboxylic acid and diamines, when carry out polymerization when not having multifunctional and monofunctional compound.
Such polymerization process can comprise, briefly:
-stir and 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 keep the scheduled time under the temperature greater than the mixture fusing point then particularly under nitrogen or vacuum, thereby continues polymerization by 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 dicarboxylic acid and diamine monomer and polyfunctional compound.
In case withdraw from from polymerization, 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 process of the present invention.
In polymerization process 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 process 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 composition 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, described filler is preferably selected from fibrous packing such as glass fibre, 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 composition of the present invention and plan normally used additive in the preparation of daiamid composition of molding.Therefore, can mention that the reagent of lubricant, fire retardant, softening agent, nucleator, catalyzer, enhancing mechanical property is as optional grafted elastomerics, light and/or thermo-stabilizer, oxidation inhibitor, static inhibitor, tinting material, matting agent, molding auxiliary agent or other common additive.
These fillers and additive can for example join in the modified polyamide in melting mixing or polymerization process by being suitable for the standard manner of various fillers or additive.
According to polymeric amide of the present invention can also the masterbatch type composition 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 composition 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, as 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 composition of the present invention as the parent material in engineering plastics field, as by in by injection moulding, by injection moulding/blowing, preparation by the goods extruding or obtain by 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 by 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 convenience.Yet, be to be understood that the use of these concrete terms is not considered as limiting scope of invention.Term " and/or " comprise implication and or and all of this term coherent element may make up.
By the following example other details of the present invention or advantage are described more clearly, described embodiment is only used for illustrating 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 distilled water, 81g2,2,6,6-four-(β-propyloic) pimelinketone (0.25mol%), 80g phenylformic acid (0.78mol%) and 40g defoamer (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.
By 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 feature 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 by 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 by the potentiometric analysis method quantitative measurement, and notch shock is measured according to standard ISO 179/1eU and ISO 179/1eA, and tensile strength, elongation and tensile modulus are measured under 23 ℃ temperature according to standard ISO 527.
Embodiment 3: the composition that contains filler
Add 50 weight % glass fibre to the polymeric amide that comprises above-mentioned preparation in as the composition of polyamide matrix by have in venting port (venting) twin screw extruder (L/D=36) melting mixing in Werner-Pfleiderer ZSK 40 types.Described glass fibre is Vetrotex 99B.It is as follows to extrude parameter: extrusion temperature has distribution 235-280 ℃ of increase; The screw rod speed of rotation: per minute 260 changes; Composition 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 composition of filler is collected in the following table 2.In order to measure some performances, the specimen that preparation is produced by 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 by the flowability of following quantized sets compound, promptly by with the pellet fusion be injected under the injection pressure of 275 ℃ of barrel zone temperatures, 80 ℃ of die temperatures and 80bar in BM-Biraghi 85T press (press) in the volution mould of semi-circular cross-section, thickness 2mm and diameter 4cm (result is expressed as the length of the mould that is full of composition suitably).
Embodiment 4:Comprise linear polyamidoamine and according to the composition that contains filler of the mixture of polymeric amide of the present invention
Exist under the 30 weight % glass fibre, preparing the composition of the polyamide 66 (PA C1) of the polymeric amide that comprises embodiment 4 (PA4) and various ratios by melting mixing in the twin screw extruder that has venting port (L/D=36) in Werner-Pfleiderer ZSK 40 types.It is as follows to extrude parameter: extrusion temperature has distribution 250-285 ℃ of increase; The screw rod speed of rotation: per minute 260 changes; Composition output: 40kg/h; The motor output of motor torque and absorption changes according to polymeric amide.
The performance that contains the composition of filler is collected in the following table 3.In order to measure some performances, the specimen that preparation is produced by injection moulding.
Table 3
| 4 | 5 | 6 | 7 | |
| Daiamid composition | 100％PA 4 | 80％ PA 4+20％ PA C1 | 70％ PA 4+30％ PA C1 | 50％ PA 4+50％ PA C1 |
| 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 STM D1238, is measured with g/10min under load 2160g in 275 ℃.
Charpy impact is measured according to standard ISO 179/1eA.
Observe in polymeric amide according to the present invention and to add the mechanical property that linear polyamidoamine 66 can improve the composition 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 according to testing 4 monomer ratio and adding 5 or 10 weight % hexanolactams (therefore replacing 5 or 10 weight %N salt).
The fused polymkeric substance is extruded with bar-shaped subsequently, cools off fast in water then and is cut into particle.
The feature 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 (22)
1. polymeric amide can obtain by polymerization in the presence of following at least material:
(i) dicarboxylic acid 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 dicarboxylic acid 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. each described polymeric amide of claim 1 to 3, the compositing monomer that it is characterized in that polymeric amide is hexanodioic acid and hexamethylene-diamine or their salt.
5. each described polymeric amide of claim 1 to 4 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 can comprise one or more heteroatomss;
-A is covalent linkage or aliphatic hydrocarbon groups, and described aliphatic hydrocarbon groups can comprise one or more heteroatomss and comprise 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. each described polymeric amide of claim 1 to 5 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 can comprise one or more heteroatomss.
7. each described polymeric amide of claim 1 to 6 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, acid from phthalocyanine and naphthalene phthalocyanine, 3,5,3 ', 5 '-biphenyltetracarboxyacid acid, 1,3,5, the 7-naphthalene tetracarboxylic acid, 2,4, the 6-pyridinetricarboxylic acid, 3,5,3 ', 5 '-dipyridyl tetracarboxylic acid, 3,5,3 ', 5 '-benzophenone 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. each described polymeric amide of claim 1 to 7, it is characterized in that the polyfunctional compound who has amine functional group X2 (ii) is selected from particularly nitrilo triethylamine of nitrilo trialkylamine, two alkylene triamine are diethylenetriamine, bis hexamethylene triamine particularly, three alkylidene group tetramines and four alkylidene groups, five amine, alkylidene group is ethylidene preferably, 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 bases or propane-1,2,3-three groups and A represent polyoxy ethylidene group.
9. each described polymeric amide of claim 1 to 8 is characterized in that monofunctional compound (iii) is aliphatics, cyclic aliphatic or the aromatic hydrocarbon compound that comprises at least 2 carbon atoms, and it can comprise heteroatoms.
10. each described polymeric amide of claim 1 to 9, it is characterized in that monofunctional compound (iii) is selected from n-hexadecyl amine, Octadecane base amine and dodecyl amine, acetate, lauric acid, benzylamine, phenylformic acid, propionic acid and 4-amino-2,2,6, the 6-tetramethyl piperidine.
11. each described polymeric amide of claim 1 to 10 is characterized in that the polyfunctional compound X1 of functional group (ii) is identical with the monofunctional compound X2 of functional group (iii).
12. each described polymeric amide of claim 1 to 11 is characterized in that using 0.2 to 0.5mol% polyfunctional compound (ii), with respect to the total mole number of the compositing monomer of polymeric amide.
13. each described polymeric amide of claim 1 to 12 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. each described polymeric amide of claim 1 to 13 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. each described polymeric amide of claim 1 to 14 is characterized in that being aggregated under the condition that has amino acid or lactan and carries out.
16. each described polymeric amide of claim 1 to 15 is characterized in that according to standard ISO 307 viscosity that this modified polyamide has is 80 to 120 in solution, described solution be 0.5% polymkeric substance in 90% formic acid, under 25 ℃ of temperature, measure.
17. a composition comprises each described polymeric amide of claim 1 to 16 at least.
18. the described composition of claim 17 comprises each described polymeric amide of claim 1 to 16 as matrix.
19. the described composition of claim 17 comprises the mixture of each described polymeric amide of thermoplastic polymer and claim 1 to 16.
20. the described composition of claim 19 comprises the mixture of (being total to) polymeric amide and each described polymeric amide of claim 1 to 16.
21. each described composition of claim 17 to 20 comprises at least a reinforcing filler and/or loose filler.
22. goods, its by each described composition of claim 17 to 21 is carried out injection moulding, injection moulding/blowing, by extruding or obtaining by extrusion-blown modling.
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 true CN101421336A (en) | 2009-04-29 |
| CN101421336B CN101421336B (en) | 2012-06-27 |
Family
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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) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153857A (en) * | 2011-03-16 | 2011-08-17 | 金发科技股份有限公司 | High-filled modified-surface strengthened polyamide composition |
| CN102549045A (en) * | 2009-09-30 | 2012-07-04 | 罗地亚经营管理公司 | High-flow polyamides |
| CN102911355A (en) * | 2012-11-20 | 2013-02-06 | 中国石油化工股份有限公司 | Preparation method of high-luster and high-fluidity PA6 (polyamide6) |
| 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 |
| 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 |
| CN105873665A (en) * | 2013-12-02 | 2016-08-17 | 陶氏环球技术有限责任公司 | 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0345648B2 (en) * | 1988-06-07 | 2000-04-05 | Ems-Inventa Ag | Thermoplastically processable polyamides |
| DE19543161A1 (en) * | 1995-11-18 | 1997-05-22 | Basf Ag | Process for the production of branched polyamides |
| FR2766197B1 (en) * | 1997-07-17 | 1999-09-03 | Nyltech Italia | THERMOPLASTIC COPOLYAMIDE, COMPOSITION BASED ON THIS THERMOPLASTIC COPOLYAMIDE |
| FR2810326B1 (en) * | 2000-06-16 | 2006-08-04 | Rhodia Eng Plastics Srl | MODIFIED POLYAMIDES, COMPOSITIONS BASED ON SUCH POLYAMIDES, AND METHOD FOR THE PRODUCTION THEREOF |
-
2006
- 2006-03-31 FR FR0602784A patent/FR2899232B1/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102549045A (en) * | 2009-09-30 | 2012-07-04 | 罗地亚经营管理公司 | High-flow polyamides |
| CN106750269A (en) * | 2009-09-30 | 2017-05-31 | 罗地亚经营管理公司 | The polyamide of high fluidity |
| CN102153857A (en) * | 2011-03-16 | 2011-08-17 | 金发科技股份有限公司 | High-filled modified-surface strengthened polyamide composition |
| 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 |
| CN102911355A (en) * | 2012-11-20 | 2013-02-06 | 中国石油化工股份有限公司 | Preparation method of high-luster and high-fluidity PA6 (polyamide6) |
| 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 |
| CN105873665A (en) * | 2013-12-02 | 2016-08-17 | 陶氏环球技术有限责任公司 | Composite polyamide membrane post treated with nitrious acid |
| CN105873665B (en) * | 2013-12-02 | 2019-01-01 | 陶氏环球技术有限责任公司 | The composite polyamide membranes post-processed with nitrous 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101421336B (en) | 2012-06-27 |
| FR2899232B1 (en) | 2008-05-16 |
| FR2899232A1 (en) | 2007-10-05 |
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