CN103333335A - High-fluidity PA10T polyamide resin and polyamide composition comprising same - Google Patents
High-fluidity PA10T polyamide resin and polyamide composition comprising same Download PDFInfo
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- CN103333335A CN103333335A CN2013102497531A CN201310249753A CN103333335A CN 103333335 A CN103333335 A CN 103333335A CN 2013102497531 A CN2013102497531 A CN 2013102497531A CN 201310249753 A CN201310249753 A CN 201310249753A CN 103333335 A CN103333335 A CN 103333335A
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-fluidity PA10T polyamide resin A. The relative viscosity of the PA10T polyamide resin A is 1.2-1.8 in 98% concentrated sulfuric acid at the temperature of 25 DEG C; the amino end group value of the PA10T polyamide resin A is 20-60mol/t and the carboxyl end group value is 70-130mol/t; and benzoic acid accounts for 2-20mol% of repetitive units in the PA10T polyamide resin A. A polyamide composition comprises the following components in percentage by weight: 5-29.8wt% of the PA10T polyamide resin A, 50-94wt% of PA10T polyamide resin B, 0.8-40wt% of mineral filler and 0.2-1wt% of other auxiliaries. The PA10T polyamide resin A disclosed by the invention has the advantages that the apparent viscosity is low and the fluidity is high under the melting condition; and when a certain proportion of the PA10T polyamide resin A is added in semi-aromatic polyamide, the obtained polyamide composition has high fluidity and basically-equal mechanical property and can be applied to occasions with high dimensional requirement on injection molding products.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of high workability PA10T polyamide resin reaches by its daiamid composition of forming.
Background technology
Polymeric amide is because having good comprehensive performances, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, certain flame retardant resistance is arranged, be easy to processing etc., it extensively is suitable for improves performance and broadened application scope with glass fibre and other filler filling enhancing modified.In recent years semiaromatic polyamide composition because its resistance toheat and mechanical property are more excellent by focus development.
By the PA10T polyamide resin that decamethylene diamine and terephthalic acid are polymerized, water-intake rate is low, the fusing point height, and development at present is rapidly.Yet with respect to the PA6T polyamide resin, the melt viscosity of PA10T polyamide resin is higher.In the time of big of needs injection moulding or the part with complicated structure, high melt viscosity is very disadvantageous, needs raising mould temperature or back pressure to realize.The aforesaid operations means are inevitably brought the problem of resin degraded, have limited the application of PA10T polyamide resin in a lot of fields.Therefore, industry is needed a kind of PA10T polyamide resin of high workability badly and by its daiamid composition of forming.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide a kind of PA10T polyamide resin with high workability.
The present invention is achieved by the following technical solutions;
A kind of high workability PA10T polyamide resin A is 25
oC, the relative viscosity in 98% vitriol oil is 1.2-1.8; The amino value of the end of described PA10T polyamide resin A is 20-60mol/t, and end carboxyl value is 70-130mol/t; Among the described PA10T polyamide resin A, the ratio that phenylformic acid accounts for repeating unit is 2-20mol%.
Preferably, described PA10T polyamide resin A is 25
oC, the relative viscosity in 98% vitriol oil is 1.4-1.6; The amino value of the end of described PA10T polyamide resin A is 30-50mol/t, and end carboxyl value is 80-110mol/t; Among the described PA10T polyamide resin A, the ratio that phenylformic acid accounts for repeating unit is 4-20mol%.
A kind of daiamid composition that comprises described high workability PA10T polyamide resin A, percentage ratio meter by weight comprises following component:
PA10T polyamide resin A 5 ~ 29.8%;
PA10T polyamide resin B 50 ~ 94%;
Mineral filler 0.8 ~ 40%;
Other auxiliary agents 0.2 ~ 1%;
Wherein, described PA10T polyamide resin B is 25
oC, the relative viscosity in 98% vitriol oil is 2.0-2.4; The amino value of the end of described PA10T polyamide resin B is 20-60mol/t, and end carboxyl value is 70-130mol/t; Among the described PA10T polyamide resin B, the ratio that phenylformic acid accounts for repeating unit is 0.5-4mol%.
Preferably, described PA10T polyamide resin B is 25
oC, the relative viscosity in 98% vitriol oil is 2.1-2.3; The amino value of the end of described PA10T polyamide resin B is 30-50mol/t, and end carboxyl value is 80-110mol/t; Among the described PA10T polyamide resin B, the ratio that phenylformic acid accounts for repeating unit is 1-3.5mol%.
When PA10T polyamide resin consumption during less than 5wt%, be difficult to play the mobile effect of improving; And because PA10T polyamide resin A molecular weight is lower, when its consumption during greater than 29.8wt%, must cause the decline of resin property.
Described mineral filler is selected from titanium dioxide, nano zine oxide, talcous one or more mixtures.
The particle diameter of described titanium dioxide is selected from 0.2-0.3um; The purity of described nano zine oxide 〉=98%, particle diameter are selected from 20-80 nm; Described talcous particle diameter is selected from the 500-2000 order.
Described other auxiliary agent is selected from one or more mixtures of antioxidant, photostabilizer, flow ability modifying agent;
Described antioxidant is selected from Hinered phenols antioxidant and/or phosphite ester kind antioxidant;
Preferably, described Hinered phenols antioxidant is selected from 1,3-benzene diamide-N, N '-two (2,2,6,6-tetramethyl--4-piperidyl), β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl alcohol ester, N, N '-two [β-(3,5-di-tert-butyl-hydroxy phenyl) propionyl]-1, the 6-hexanediamine, 1,3,5-three (3,5-di-t-butyl-4-convulsion base Bian Ji) 2,4,6-Three methyl Benzene, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl Bian Ji) 1,3,5-triazines-2,4,6-(1H, 3H, 5H) one or more mixtures of triketone; Described phosphite ester kind antioxidant is selected from one or more mixtures of three (2,4-DI-tert-butylphenol compounds) phosphorous acid ester, two (3,5-di-tert-butyl-phenyl) pentaerythritol diphosphites.
Described photostabilizer is selected from one or more mixtures of benzophenone cpd, salicylate compound, azimidobenzene compound; Described flow ability modifying agent is selected from one or more mixtures of E wax, EBS, montanic acid sodium salt, hyperbranched polymer.
A kind of preparation method of above-mentioned daiamid composition, after comprising the steps: to place high-speed mixer and mixing evenly PA10T polyamide resin A, PA10T polyamide resin B, mineral filler, other auxiliary agents, add in the twin screw extruder by main spout, reinforcing filler is fed by side feeding scale side, 310
oC ~ 330
oUnder the C, extrude, cross water cooling, obtain product after granulation and the drying.
The present invention compared with prior art has following beneficial effect:
PA10T polyamide resin A of the present invention, apparent viscosity under melting condition is lower, has higher flowability, when in semiaromatic polyamide composition, adding a certain proportion of PA10T polyamide resin A, the daiamid composition of preparation gained has high flowability and suitable substantially mechanical property, can be used for the occasion higher to the injection-molded item dimensional requirement.
Embodiment
Now embodiment and the used starting material of Comparative Examples are done following explanation, but are not limited to these materials:
Used titanium dioxide is the rutile titanium dioxide R103 of the particle diameter 0.2-0.3 μ m of E.I.Du Pont Company;
Used oxidation inhibitor is the efficient anti-xanthochromia agent oxidation inhibitor 1098 of amine nylon of two key chemical companies;
Used flow ability modifying agent is the montanic acid sodium salt Licowax OP that the part of Clariant company replaces.
The performance test of embodiment and Comparative Examples is undertaken by following standard or method:
The testing method of gained polymeric amide relative viscosity: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: 25 ± 0.01
oMeasuring concentration in 98% the vitriol oil of C is the relative viscosity η r of the polymeric amide of 0.25g/dl;
The testing method of gained polymeric amide terminal amino group content: with full-automatic current potential titration apparatus titration sample terminal amino group content; Get the 0.5g polymkeric substance, add phenol 45mL and anhydrous methanol 3mL, reflux after the observation sample dissolves fully, is chilled to room temperature, with the hydrochloric acid standard solution titration terminal amino group content of having demarcated;
The testing method of gained polymeric amide content of carboxyl end group: with full-automatic current potential titration apparatus titration sample content of carboxyl end group; Get the 0.5g polymkeric substance, add ortho-cresol 50mL, the dissolving that refluxes is put cold back and is added 400 μ L formaldehyde solutions rapidly, with the KOH-ethanolic soln titration content of carboxyl end group of having demarcated;
The testing method of gained polymeric amide apparent viscosity: carry out with the LCR-7000 of Dynisco company type capillary rheometer, adopt CZ394-20 type mouth mould, shearing rate is 1000s
-1, probe temperature is 330
oC, the fusion time is 5min.
Tensile strength: measure according to ISO 527-2, test condition is 23
oC and 10mm/min;
Elongation at break: measure according to ISO 527-2, test condition is 23
oC and 10mm/min;
Flexural strength and modulus in flexure: measure according to ISO 178, test condition is 23
oC and 2mm/min;
Notched Izod impact strength: measure according to ISO 180/1A, test condition is 23
oC, the breach type is the A type.
Unnotched impact strength: measure according to ISO 180/1A, test condition is 23
oC.
Helicoidal flow line length: adopt self-control Archimedean screw line of flow mould, the groove width 5mm that flows, high 2.5mm.
Amount of deflection: with reference to GB9341-2000 plastics bending property test method.
Further specify the present invention below by embodiment, following examples are preferred implementation of the present invention, but embodiments of the present invention are not subjected to the restriction of following embodiment.
Embodiment A 1 ~ A4:The preparation of PA10T polyamide resin A
In the autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add reaction raw materials in the ratio in the table 1, add phenylformic acid, sodium hypophosphite and deionized water again; Sodium hypophosphite weight is 0.1% of outer other weight that feed intake of deionizing water, and deionized water weight is 30% of the weight that always feeds intake; Vacuumize and charge into high pure nitrogen as protection gas, be warmed up to 220 under agitation 2 hours
oC, with reaction mixture 220
oC stirred 1 hour, under agitation made the temperature of reactant be elevated to 230 then
oC; Be reflected at 230
oProceed 2 hours under the constant temperature of C and the constant voltage of 2.2Mpa, by remove formed water keep-up pressure constant, the reaction finish after discharging, prepolymer is in 80
oVacuum-drying is 24 hours under the C, obtains prepolymer product, and described prepolymer product is 250
oSolid-phase tack producing is 10 hours under C, the 50Pa vacuum condition, obtains PA10T polyamide resin A; Performance test sees Table 1.
Table 1
| ? | Embodiment A 1 | Embodiment A 2 | Embodiment A 3 | Embodiment A 4 |
| Terephthalic acid/mol | 20 | 20 | 20 | 20 |
| Decamethylene diamine/mol | 20 | 20 | 20 | 20 |
| Phenylformic acid/mol | 1 | 2 | 3 | 4 |
| End amino/mol/t | 39 | 41 | 36 | 31 |
| End carboxyl/mol/t | 88 | 87 | 84 | 89 |
| Relative viscosity | 1.786 | 1.593 | 1.412 | 1.255 |
| Apparent viscosity/Pas | 35 | 28 | 19 | 15 |
| The resin numbering | A1 | A2 | A3 | A4 |
Embodiment B 1 ~ B4:The preparation of PA10T polyamide resin B
In the autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add reaction raw materials in the ratio in the table 2, add phenylformic acid, sodium hypophosphite and deionized water again; Sodium hypophosphite weight is 0.1% of outer other weight that feed intake of deionizing water, and deionized water weight is 30% of the weight that always feeds intake; Vacuumize and charge into high pure nitrogen as protection gas, be warmed up to 220 under agitation 2 hours
oC, with reaction mixture 220
oC stirred 1 hour, under agitation made the temperature of reactant be elevated to 230 then
oC.Be reflected at 230
oProceed 2 hours under the constant temperature of C and the constant voltage of 2.2Mpa, by remove formed water keep-up pressure constant, the reaction finish after discharging, prepolymer is in 80
oVacuum-drying is 24 hours under the C, obtains prepolymer product, and described prepolymer product is 250
oSolid-phase tack producing is 10 hours under C, the 50Pa vacuum condition, obtains PA10T polyamide resin B; Performance test sees Table 2.
Table 2
| ? | Embodiment B 1 | Embodiment B 2 | Embodiment B 3 | Embodiment B 4 |
| Terephthalic acid/mol | 20 | 20 | 20 | 20 |
| Decamethylene diamine/mol | 20 | 20 | 20 | 20 |
| Phenylformic acid/mol | 0.1 | 0.2 | 0.4 | 0.7 |
| End amino/mol/t | 42 | 43 | 38 | 33 |
| End carboxyl/mol/t | 90 | 89 | 86 | 91 |
| Relative viscosity | 2.386 | 2.293 | 2.112 | 2.055 |
| Apparent viscosity/Pas | 145 | 122 | 105 | 91 |
| The resin numbering | B1 | B2 | B3 | B4 |
Embodiment C 1 ~ C8 and Comparative Examples 1 ~ 3:The preparation of daiamid composition
By the prescription of table 3-4 with PA10T polyamide resin A, B, titanium dioxide, talcum powder, other auxiliary agents high-speed mixer and mixing evenly after, add in the twin screw extruder by main spout, reinforcing filler is fed by side feeding scale side, extrude, cross water cooling, obtain described daiamid composition after granulation and the drying; Wherein, extrusion temperature is 330
oC.
Table 3
Table 4
| ? | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| PA10T polymeric amide A/wt% | 0 | 40 | 0 |
| PA10T polymeric amide B/wt% | 60 | 50 | 0 |
| Polyamide 6 T/66/wt% | 0 | 0 | 60 |
| Titanium dioxide/wt% | 30 | 9 | 30 |
| Talcum powder/wt% | 9.8 | 0.8 | 9.8 |
| Oxidation inhibitor 1098/wt% | 0.1 | 0.1 | 0.1 |
| Licowax OP/wt% | 0.1 | 0.1 | 0.1 |
| Apparent viscosity/Pas | 180 | 20 | 105 |
| Helicoidal flow line length/mm | 250 | 2250 | 429 |
| Tensile strength/MPa | 57 | 10 | 68 |
| Elongation at break/% | 3.03 | 0.59 | 3.52 |
| Flexural strength/MPa | 107.3 | 32.8 | 121.4 |
| Modulus in flexure/MPa | 4719 | 2210 | 5638 |
| Notched Izod impact strength/kJ/m 2 | 4.8 | 1.1 | 6.8 |
| Unnotched impact strength/kJ/m 2 | 20 | 3 | 28 |
| Amount of deflection/mm | 5.4 | 1.3 | 7.1 |
By embodiment and Comparative Examples more as can be seen, use the apparent viscosity of PA10T polyamide resin B to be 180Pas separately, flowability is not high; If add 40wt%PA10T polyamide resin A in PA10T polymeric amide B, addition is too much, will cause resin property greatly to descend; As the PA10T polyamide resin A that adds 5 ~ 29.8wt% in PA10T polymeric amide B, apparent viscosity can reduce significantly, and flowing property is greatly improved, and can keep the mechanical property suitable with polyamide resin 6T/66 substantially.
Claims (8)
1. high workability PA10T polyamide resin A, it is characterized in that: described PA10T polyamide resin A is 25
oC, the relative viscosity in 98% vitriol oil is 1.2-1.8; The amino value of the end of described PA10T polyamide resin A is 20-60mol/t, and end carboxyl value is 70-130mol/t; Among the described PA10T polyamide resin A, the ratio that phenylformic acid accounts for repeating unit is 2-20mol%.
2. high workability PA10T polyamide resin A according to claim 1 is characterized in that, described PA10T polyamide resin A is 25
oC, the relative viscosity in 98% vitriol oil is 1.4-1.6; The amino value of the end of described PA10T polyamide resin A is 30-50mol/t, and end carboxyl value is 80-110mol/t; Among the described PA10T polyamide resin A, the ratio that phenylformic acid accounts for repeating unit is 4-20mol%.
3. daiamid composition that comprises each described high workability PA10T polyamide resin A of claim 1 ~ 2, percentage ratio meter by weight comprises following component:
PA10T polyamide resin A 5 ~ 29.8%;
PA10T polyamide resin B 50 ~ 94%;
Mineral filler 0.8 ~ 40%;
Other auxiliary agents 0.2 ~ 1%;
Wherein, described PA10T polyamide resin B is 25
oC, the relative viscosity in 98% vitriol oil is 2.0-2.4; The amino value of the end of described PA10T polyamide resin B is 20-60mol/t, and end carboxyl value is 70-130mol/t; Among the described PA10T polyamide resin B, the ratio that phenylformic acid accounts for repeating unit is 0.5-4mol%.
4. daiamid composition according to claim 3 is characterized in that, described PA10T polyamide resin B is 25
oC, the relative viscosity in 98% vitriol oil is 2.1-2.3; The amino value of the end of described PA10T polyamide resin B is 30-50mol/t, and end carboxyl value is 80-110mol/t; Among the described PA10T polyamide resin B, the ratio that phenylformic acid accounts for repeating unit is 1-3.5mol%.
5. daiamid composition according to claim 3 is characterized in that, described mineral filler is selected from titanium dioxide, nano zine oxide, talcous one or more mixtures.
6. daiamid composition according to claim 5 is characterized in that, the particle diameter of described titanium dioxide is selected from 0.2-0.3um; The purity of described nano zine oxide 〉=98%, particle diameter are selected from 20-80 nm; Described talcous particle diameter is selected from the 500-2000 order.
7. daiamid composition according to claim 5 is characterized in that, described other auxiliary agent is selected from one or more mixtures of antioxidant, photostabilizer, flow ability modifying agent; Described antioxidant is selected from Hinered phenols antioxidant and/or phosphite ester kind antioxidant; Described photostabilizer is selected from one or more mixtures of benzophenone cpd, salicylate compound, azimidobenzene compound; Described flow ability modifying agent is selected from one or more mixtures of E wax, EBS, montanic acid sodium salt, hyperbranched polymer.
8. the preparation method of a daiamid composition as claimed in claim 3, it is characterized in that, after comprising the steps: to place high-speed mixer and mixing evenly PA10T polyamide resin A, PA10T polyamide resin B, mineral filler, other auxiliary agents, add in the twin screw extruder by main spout, reinforcing filler is fed by side feeding scale side, 310
oC ~ 330
oUnder the C, extrude, cross water cooling, obtain product after granulation and the drying.
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| CN2013102497531A CN103333335A (en) | 2013-06-21 | 2013-06-21 | High-fluidity PA10T polyamide resin and polyamide composition comprising same |
| PCT/CN2014/070036 WO2014201859A1 (en) | 2013-06-21 | 2014-01-02 | High-fluidity pa10t polyamide resin, and polyamide composition consisting of same |
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| CN103804682A (en) * | 2013-12-24 | 2014-05-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition consisting of same |
| WO2014201859A1 (en) * | 2013-06-21 | 2014-12-24 | 金发科技股份有限公司 | High-fluidity pa10t polyamide resin, and polyamide composition consisting of same |
| CN112745672A (en) * | 2020-12-16 | 2021-05-04 | 金发科技股份有限公司 | Polyamide molding composition and preparation method and application thereof |
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| WO2014201859A1 (en) * | 2013-06-21 | 2014-12-24 | 金发科技股份有限公司 | High-fluidity pa10t polyamide resin, and polyamide composition consisting of same |
| 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 |
| CN103642036A (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 |
| CN103665373A (en) * | 2013-11-12 | 2014-03-26 | 金发科技股份有限公司 | PA10T polyamide resin and polyamide composition composed of same |
| CN103665373B (en) * | 2013-11-12 | 2016-08-17 | 金发科技股份有限公司 | A kind of PA10T polyamide and consisting of daiamid composition |
| CN103804682A (en) * | 2013-12-24 | 2014-05-21 | 金发科技股份有限公司 | Polyamide resin and polyamide composition consisting of same |
| WO2015096196A1 (en) * | 2013-12-24 | 2015-07-02 | 金发科技股份有限公司 | Polyamide resin and polyamide composition consisting of same |
| CN112745672A (en) * | 2020-12-16 | 2021-05-04 | 金发科技股份有限公司 | Polyamide molding composition and preparation method and application thereof |
| CN112745672B (en) * | 2020-12-16 | 2022-06-14 | 金发科技股份有限公司 | Polyamide molding composition and preparation method and application thereof |
| WO2022127249A1 (en) * | 2020-12-16 | 2022-06-23 | 金发科技股份有限公司 | Polyamide molding composition, preparation method therefor, and application thereof |
| CN113150542A (en) * | 2021-04-12 | 2021-07-23 | 河南华盈新材料有限公司 | Self-plasticizing PA6T |
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| Publication number | Publication date |
|---|---|
| WO2014201859A1 (en) | 2014-12-24 |
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