CN103936978A - Polyamide resin and polyamide composition composed of polyamide resin - Google Patents
Polyamide resin and polyamide composition composed of polyamide resin Download PDFInfo
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- CN103936978A CN103936978A CN201410049496.1A CN201410049496A CN103936978A CN 103936978 A CN103936978 A CN 103936978A CN 201410049496 A CN201410049496 A CN 201410049496A CN 103936978 A CN103936978 A CN 103936978A
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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
-
- 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
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
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Abstract
The invention discloses a polyamide resin. The polyamide resin is composed of following repeat unit ingredients: 80 to 99mol% of an ingredient A, which is 10T unit composed of decamethylene diamine and terephthalic acid; and 1 to 20mol% of an ingredient B, which is 1010 unit composed of decamethylene diamine and decanedioic acid; wherein decanedioic acid is substituted by isophthalic acid or other aliphatic dicarboxylic acids with 2 to 14 carbon atoms. The invention also discloses a polyamide composition containing the polyamide resin. The polyamide composition comprises, by weight, 30 to 99.9% of the polyamide resin, 0 to 60% of a reinforcing filler, 0 to 50% of a flame retardant, and 0.1 to 10% of other auxiliary agents. Saturated water absorptivity of the polyamide resin and the polyamide composition is less than 0.8wt%, so that the polyamide resin and the polyamide composition can be used for components, such as engine oil tubes, with relatively high requirements on saturated water absorptivity; melting point is higher than 260 DEG C, and heat resistance is high, so that the polyamide resin and the polyamide composition can be used for environments with a reflow soldering temperature more than 260 DEG C, and the like; elongation at break ranges from 14 to 45%; notch impact strength ranges from 6.9 to 12.0kJ/m<2> (23 DEG C); toughness is high, so that the polyamide resin and the polyamide composition can be used for components, such as engine oil tubes, with relatively high requirements on toughness.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of polyamide resin and consisting of daiamid composition.
Background technology
Polymeric amide is because having good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, there is certain flame retardant resistance, be easy to processing etc., it is extensively suitable for, by glass fibre and other filler filling enhancing modified, improves the aspects such as performance and broadened application scope.In recent years semiaromatic polyamide composition due to its resistance toheat and mechanical property more excellent and by focus development.
Semi-aromatic heat resistant polyamide PA6T multipolymer is known already, and it has high mobility and resistance to elevated temperatures.But, similar with PA66, because PA6T amido linkage concentration is higher, cause its water-intake rate higher, thereby cause a series of restrictions in use.Meanwhile, also there is the problem of toughness deficiency in the multipolymer that PA6T is relevant, needs improvement badly.In addition, the floating fine problem on injection-molded item surface also has a strong impact on product surface form, becomes the obstacle that Application Areas is expanded.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide the polyamide resin of a kind of low saturated water absorption, high heat resistance and high tenacity.
A kind of polyamide resin, by mole% meter, is made up of following repeating unit component:
The 10T unit being formed by decamethylene diamine and terephthalic acid of component A:80-99mol%;
The Unit 1010 that formed by decamethylene diamine and sebacic acid of B component: 1-20mol%;
Wherein, sebacic acid is replaced by m-phthalic acid or other aliphatic dicarboxylic acid of containing 2 ~ 14 carbon atoms.
Described other aliphatic dicarboxylic acid that contains 2 ~ 14 carbon atoms is selected from one or more of oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, undecandioic acid, 13 diacid or 14 diacid.
The fusing point of described polyamide resin is higher than 260
oc, is preferably 280
oc-320
oc; Melting point resin is too low, and under the pyroprocessing of reflow soldering, goods are easily out of shape; Melting point resin is too high, causes its processing characteristics to decline.And the too high decomposition temperature that approaches of fusing point, easily makes goods various aspects of performance all decline.
The saturated water absorption of described polyamide resin is lower than 0.8wt%, and lower water-intake rate can ensure that resin is used for reflow soldering etc. and under high water absorbing capacity, may produces the occasion that goods bubble.
The elongation at break of described polyamide resin is 14 ~ 45%, and the notched Izod impact strength of described polyamide resin is 6.9 ~ 12.0 kJ/m
2(23
oc), give thus resin or the enough toughness of its composition.
A daiamid composition that comprises described polyamide resin, by weight percentage, comprises following component:
Polyamide resin 30 ~ 99.9%;
Reinforcing filler 0 ~ 60%;
Fire retardant 0 ~ 50%;
Other auxiliary agents 0.1 ~ 10%;
The content of described reinforcing filler is preferably 10 ~ 50wt%, more preferably 15-40%; Filler content is too low, causes daiamid composition mechanical property poor; Filler content is too high, and daiamid composition product surface is floating fine serious, affects product appearance.
Being shaped as of described reinforcing filler is fibrous, and its mean length is 0.01-20mm, is preferably 0.1 ~ 6mm; Its length-to-diameter ratio is 5 ~ 2000:1, is preferably 30 ~ 600:1, in the time that fibrous reinforcing filler content is in above-mentioned scope, and the high temperature rigid that daiamid composition will show high heat distortion temperature and increase, above-mentioned size can obtain fiber measurement by milscale.
Described reinforcing filler is inorganic reinforcing filler or organic reinforcing filler;
Described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre; Use glass fibre not only can improve the mouldability of daiamid composition, and can improve mechanical property for example tensile strength, flexural strength and modulus in flexure, and heat-drawn wire when improving thermotolerance for example thermoplastic resin composition carrying out molding.
Described organic reinforcing filler is selected from Kevlar and/or carbon fiber.
Being shaped as of described reinforcing filler is non-fibrous, for example Powdered, particulate state, tabular, needle-like, fabric or felted, its median size is 0.001～10 μ m, is preferably 0.01～5 μ m, will cause the poor melt processable of polyamide resin when the median size of reinforcing filler is less than 0.001 μ m; When the median size of reinforcing filler is greater than 10 μ m, bad injection-molded article appearance will be caused.The median size of above-mentioned reinforcing filler is measured by absorption method, it can be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.These reinforcing fillers can be hollow; In addition,, for swelling property layered silicates such as wilkinite, polynite, lithium montmorillonite, synthetic micas, can use and adopt organic ammonium salt that interlayer ion is carried out to the organic montmorillonoid after cationic exchange.
In order to make daiamid composition obtain more good mechanical property, can adopt coupling agent to carry out functional processing to inorganic reinforcing filler, wherein coupling agent is selected from isocyanic ester based compound, organosilane based compound, organic titanate based compound, organo-borane based compound, epoxy compounds; Be preferably organosilane based compound;
Wherein, described organosilane based compound be selected from the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains epoxy group(ing), the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains sulfydryl, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate group, contain amino alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains hydroxyl, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains carbon-to-carbon unsaturated group, one or more of alkoxysilane compound containing trialkylsilyl group in molecular structure that contain anhydride group.
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains epoxy group(ing) is selected from one or more of γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains sulfydryl is selected from γ mercaptopropyitrimethoxy silane and/or γ-sulfydryl propyl-triethoxysilicane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains urea groups is selected from one or more of γ-urea groups propyl-triethoxysilicane, γ-urea groups propyl trimethoxy silicane, γ-(2-urea groups ethyl) TSL 8330;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate group is selected from one or more of γ-isocyanate group propyl-triethoxysilicane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group propyl group methyl dimethoxysilane, γ-isocyanate group propyl group methyldiethoxysilane, γ-isocyanate group propyl group ethyl dimethoxy silane, γ-isocyanate group propyl group ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan;
Describedly contain amino alkoxysilane compound containing trialkylsilyl group in molecular structure and be selected from one or more of γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains hydroxyl is selected from γ-hydroxypropyl Trimethoxy silane and/or γ-hydroxypropyl triethoxyl silane;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains carbon-to-carbon unsaturated group is selected from one or more of γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride;
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains anhydride group is selected from 3-trimethoxy-silylpropyl succinyl oxide;
Described organosilane based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane or 3-trimethoxy-silylpropyl succinyl oxide.
Can adopt above-mentioned organosilane based compound to carry out surface treatment to inorganic reinforcing filler according to conventional method, and then itself and polyamide resin are carried out to melting mixing, to prepare described daiamid composition; Also can, directly in inorganic reinforcing filler and polyamide resin melting mixing, add organosilane based compound to carry out in-situ blending;
Wherein, the consumption of described coupling agent is with respect to 0.05 ~ 10wt% of inorganic reinforcing filler weight, is preferably 0.1 ~ 5wt%; In the time that the consumption of coupling agent is less than 0.05wt%, it does not reach the effect of obvious improved mechanical properties; In the time that the consumption of coupling agent is greater than 10wt%, inorganic reinforcing filler easily condenses, and in polyamide resin, disperses bad risk, finally causes mechanical property to decline.
Described fire retardant is the composition of fire retardant or fire retardant and fire-retardant assistance agent, and its content is preferably 10 ~ 40wt%; The too low flame retardant effect variation that causes of flame retardant agent content, the too high material mechanical performance that causes of flame retardant agent content declines.
Described fire retardant is halogenated flame retardant or halogen-free flame retardants;
Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecanes or brominated aromatic cross-linked polymer, is preferably preferred brominated Polystyrene;
Described halogen-free flame retardants is selected from one or more containing the fire retardant of nitrogen combustion inhibitor, phosphonium flame retardant or nitrogenous and phosphorus; Be preferably phosphonium flame retardant.
It is that phosphoric acid ester, butylbenzene are one or more of phosphoric acid ester or hypophosphite that described phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene; Be preferably hypophosphite;
Described hypophosphite has the hypophosphite of following structure formula I:
In formula, R
1, R
2identical or different, be expressed as straight chain or alkyl and/or aryl or phenyl containing 1 ~ 6 carbon atom of side chain; M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or by protonated nitrogenous base; M is 1 ~ 3.
Described other auxiliary agents are selected from one or more of softening agent, thickening material, antistatic agent, releasing agent, toner, staining agent or nucleator.
The present invention compared with prior art, has following beneficial effect:
1) saturated water absorption of polyamide resin of the present invention, lower than 0.8wt%, has lower saturated water absorption, can be applicable to the occasion that engine oil tube etc. is had relatively high expectations to saturated water absorption;
2) fusing point of polyamide resin of the present invention is higher than 260
oc, thermotolerance is strong, can be applied to and exceed 260 as reflow soldering temperature
othe occasion of C;
3) elongation at break of polyamide resin of the present invention is 14 ~ 45%; Notched Izod impact strength is 6.9 ~ 12.0 kJ/m
2(23
oc), there is high tenacity, can be used for the occasions higher to toughness reguirements such as engine oil tube;
4) daiamid composition of preparing gained by polyamide resin of the present invention also has low saturated water absorption, high heat resistance and high tenacity, can be used for the occasions higher to above-mentioned performance requriements such as engine oil tube.
Embodiment
Further illustrate the present invention below by embodiment, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
The saturated water absorption testing method of polymeric amide: sample is injection molded into the product of 20mm × 20 mm × 2mm, its weight is designated as a0; Then be placed on 35
oin the environment of C, humidity 85%, after 168h, weigh its weight and be designated as a1; Saturated water absorption=(a1-a0)/a0*100%.
Product surface floats fine situation detection method: get 3000g polymer particle and carry out, after injection moulding, obtaining the colour table of one-sided smooth; This colour table is placed in and on Quadratic Finite Element survey meter, observes its floating fine situation.
The testing method of the relative viscosity of gained prepolymer product and polymeric amide: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: 25 ± 0.01
oin 98% the vitriol oil of C, measure the relative viscosity η r that concentration is the polymeric amide of 0.25g/dl;
The testing method of the fusing point of polymeric amide: with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; Concrete testing method is: the fusing point that adopts Perkin Elmer Dimond dsc analysis instrument test sample; Nitrogen atmosphere, flow velocity is 40mL/min; First with 10 when test
oc/min is warming up to 340
oc, 340
oc keeps 2min, then with 10
oc/min is cooled to 50
oc, then with 10
oc/min is warming up to 340
oc, is made as fusing point by endotherm peak temperature now
t m;
The testing method of gained polymeric amide terminal amino group content: with autopotentiometric titrator titration sample terminal amino group content; Get 0.5g polymkeric substance, add phenol 45mL and anhydrous methanol 3mL, reflux, after observation sample dissolves completely, 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 autopotentiometric titrator titration sample content of carboxyl end group; Get 0.5g polymkeric substance, add ortho-cresol 50mL, reflux and dissolve, let cool the rear 400 μ L formaldehyde solutions that add rapidly, with the KOH-ethanolic soln titration content of carboxyl end group of having demarcated;
The testing method of gained polyamide resin brightness L value: use Standard colour board mould, get 3000g polymer particle and carry out, after injection moulding, obtaining the colour table of one-sided smooth.This colour table is placed on the precious Color-Eye7000A Computer color testing instrument of reason and obtains brightness value L value;
Elongation at break: measure according to ISO 527-2, test condition is 23
oc and 10mm/min;
Notched Izod impact strength: measure according to ISO 180/1A, test condition is 23
oc, breach type is A type.
embodiment 1 ~ 11 and comparative example 1 ~ 8
In the autoclave pressure of being furnished with magnetic coupling stirring, prolong, gas phase mouth, charging opening, pressure explosion-proof mouth, add reaction raw materials in the ratio in form; Add again phenylformic acid, sodium hypophosphite and deionized water; Phenylformic acid amount of substance is 2.5% of diamines, diacid, lactan and the total amount of substance of amino acid, and 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 be filled with high pure nitrogen as protection gas, under agitation 2 hours, be warmed up to 220
oc, by reaction mixture 220
oc stirs 1 hour, then under agitation makes the temperature of reactant be elevated to 230
oc; Reaction is 230
ounder the constant temperature of C and the constant voltage of 2.2MPa, proceed 2 hours, keep constant pressure by removing formed water, reacted rear discharging, prepolymer is in 80
ounder C, vacuum-drying 24 hours, obtains prepolymer product, and described prepolymer product is 250
ounder C, 50Pa vacuum condition, solid-phase tack producing 10 hours, obtains polymeric amide.The relative viscosity of polymeric amide, fusing point, saturated water absorption etc. are listed in table 1.
Table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| Terephthalic acid/mol | 16 | 18 | 19 | 19.8 | 16 | 18 | 19 | 18 | 19 | 18 | 19 |
| Sebacic acid/mol | 4 | 2 | 1 | 0.2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| M-phthalic acid/mol | 0 | 0 | 0 | 0 | 4 | 2 | 1 | 0 | 0 | 0 | 0 |
| Oxalic acid/mol | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 2 | 1 | 0 | 0 |
| Hexanodioic acid/mol | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 2 | 1 |
| 1，10-diaminodecane/mol | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| End amino/mol/t | 42 | 43 | 40 | 38 | 39 | 44 | 45 | 39 | 48 | 44 | 47 |
| End carboxyl/mol/t | 80 | 90 | 85 | 82 | 83 | 84 | 91 | 92 | 88 | 94 | 84 |
| Relative viscosity | 2.230 | 2.240 | 2.233 | 2.245 | 2.233 | 2.245 | 2.238 | 2.269 | 2.254 | 2.213 | 2.249 |
| Fusing point/ oC | 271 | 285 | 302 | 312 | 273 | 288 | 303 | 296 | 308 | 294 | 304 |
| Saturated water absorption/% | 0.2 | 0.2 | 0.4 | 0.7 | 0.3 | 0.3 | 0.5 | 0.5 | 0.4 | 0.4 | 0.3 |
| Water free breaking elongation rate/% | 41 | 25 | 18 | 14 | 43 | 26 | 17 | 25 | 14 | 28 | 17 |
| Hygrometric state elongation at break/% | 43 | 26 | 17 | 15 | 43 | 24 | 16 | 24 | 14 | 26 | 15 |
| Notched Izod impact strength/kJ/m 2(23℃) | 11.2 | 9.3 | 7.8 | 6.9 | 10.1 | 8.4 | 7.0 | 8.0 | 6.9 | 8.5 | 7.1 |
Continued 1
| ? | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| Terephthalic acid/mol | 9 | 11 | 11 | 13 | 18 | 19 | 20 | 9 |
| Sebacic acid/mol | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 11 |
| M-phthalic acid/mol | 0 | 0 | 9 | 7 | 0 | 0 | 0 | 0 |
| 1,6-hexanodioic acid/mol | 11 | 9 | 0 | 0 | 2 | 1 | 0 | 0 |
| 1,6-hexanediamine/mol | 20 | 20 | 20 | 20 | 2 | 1 | 0 | 0 |
| 1，10-diaminodecane/mol | 0 | 0 | 0 | 0 | 18 | 19 | 20 | 20 |
| End amino/mol/t | 40 | 38 | 45 | 44 | 38 | 44 | 46 | 38 |
| End carboxyl/mol/t | 82 | 71 | 88 | 80 | 92 | 89 | 92 | 88 |
| Relative viscosity | 2.233 | 2.228 | 2.263 | 2.279 | 2.220 | 2.231 | 2.210 | 2.269 |
| Fusing point/ oC | 292 | 311 | 294 | 315 | 292 | 304 | 316 | 255 |
| Saturated water absorption/% | 1.6 | 1.9 | 1.8 | 2.0 | 0.9 | 0.8 | 0.7 | 0.5 |
| Water free breaking elongation rate/% | 7 | 6 | 6 | 8 | 9 | 8 | 9 | 42 |
| Hygrometric state elongation at break/% | 9 | 8 | 7 | 7 | 10 | 9 | 8 | 40 |
| Notched Izod impact strength/kJ/m 2(23 oC) | 4.1 | 4.0 | 3.9 | 3.7 | 4.6 | 4.1 | 6.1 | 13.6 |
From relatively can finding out of embodiment 1 ~ 11 and comparative example 1 ~ 8, embodiment of the present invention, the saturated water absorption of its resin all below 0.8wt%, and in comparative example the resinoid saturated water absorption of 6T generally more than 1.6wt%; And the elongation at break of resin is far above 6T class in comparative example and 10T resinoid in embodiment, notched Izod impact strength is also higher than the latter.Although comparative example 8 water-intake rates are very low, shock strength is also very high, and due to sebacic acid too high levels, fusing point is very low, is difficult to be applied in high temperature occasion.
embodiment 12-17 and comparative example 9 ~ 13
The formula of pressing table 2 by polyamide resin, fire retardant, other auxiliary agents high-speed mixer and mixing evenly after, add in twin screw extruder by main spout, reinforcing filler is fed by side feeding scale side, extrudes, cross water cooling, granulation obtains described daiamid composition after being also dried.Wherein, extrusion temperature is 330
oc.
In table 2 following table, formula is weight part
| ? | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Comparative example 9 | Comparative example 10 | Comparative example 11 | Comparative example 12 | Comparative example 13 |
| Polyamide resin | Embodiment 2 | Embodiment 2 | Embodiment 4 | Embodiment 7 | Embodiment 2 | Embodiment 2 | Comparative example 1 | Comparative example 1 | Comparative example 5 | Comparative example 5 | Comparative example 1 |
| Resin content | 70 | 50 | 70 | 50 | 30 | 99.9 | 70 | 50 | 70 | 50 | 99.9 |
| Glass fibre | 29 | 30 | 29 | 30 | 60 | 0 | 29 | 30 | 29 | 30 | 0 |
| Hypophosphite fire retardant | 0 | 15 | 0 | 15 | 5 | 0 | 0 | 15 | 0 | 15 | 0 |
| Polybutene | 0 | 2 | 0 | 2 | 2 | 0 | 0 | 2 | 0 | 2 | 0 |
| Dipentaerythritol | 0 | 1 | 0 | 1 | 1 | 0 | 0 | 1 | 0 | 1 | 0 |
| Zinc borate | 0 | 1 | 0 | 1 | 1 | 0 | 0 | 1 | 0 | 1 | 0 |
| Phenolic antioxidant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.05 | 0.5 | 0.5 | 0.5 | 0.5 | 0.05 |
| Polyethylene wax | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.05 | 0.5 | 0.5 | 0.5 | 0.5 | 0.05 |
| Saturated water absorption/% | 0.2 | 0.3 | 0.3 | 0.3 | 0.1 | 0.2 | 1.4 | 1.6 | 0.9 | 0.8 | 1.6 |
| Water free breaking elongation rate/% | 13 | 11 | 12 | 10 | 8 | 26 | 3 | 2 | 4 | 2 | 7 |
| Hygrometric state elongation at break/% | 12 | 11 | 11 | 11 | 7 | 27 | 3 | 3 | 3 | 2 | 9 |
| Notched Izod impact strength/kJ/m 2(23 oC) | 13.3 | 11.2 | 10.8 | 9.5 | 7.9 | 9.2 | 5.6 | 4.1 | 5.5 | 4.2 | 4.1 |
| Floating fine | ◎ | ○ | ◎ | ○ | ○ | ◎ | ¤ | ¤ | ¤ | ¤ | ◎ |
◎ surface is very smooth; Zero surface trace is floating fine; ¤ surface is a large amount of floating fine
As can be seen from Table 2, the saturated water absorption of the composition that the polyamide resin that the embodiment of the present application prepares prepares all below 0.3wt%, and in comparative example the resinoid water-intake rate of 6T generally more than 1.4wt%; The elongation at break of the daiamid composition of embodiment and notched Izod impact strength are also higher than comparative example; Comparative example detects floating fine, also very serious on Quadratic Finite Element survey meter.
Claims (12)
1. a polyamide resin, is characterized in that, by mole% meter, is made up of following repeating unit component:
The 10T unit being formed by decamethylene diamine and terephthalic acid of component A:80-99mol%;
The Unit 1010 that formed by decamethylene diamine and sebacic acid of B component: 1-20mol%;
Wherein, sebacic acid is replaced by m-phthalic acid or other aliphatic dicarboxylic acid of containing 2 ~ 14 carbon atoms.
2. polyamide resin according to claim 1, it is characterized in that, described in contain 2 ~ 14 carbon atoms other aliphatic dicarboxylic acid be selected from one or more of oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, 2-methyl suberic acid, nonane diacid, undecandioic acid, 13 diacid or 14 diacid.
3. the resin of polymeric amide according to claim 1, is characterized in that, the fusing point of described polyamide resin is higher than 260
oc, preferably 280-330
oc.
4. polyamide resin according to claim 1, is characterized in that, the saturated water absorption of described polyamide resin is lower than 0.8wt%.
5. polyamide resin according to claim 1, is characterized in that, the elongation at break of described polyamide resin is 14 ~ 45%.
6. polyamide resin according to claim 1, is characterized in that, the notched Izod impact strength of described polyamide resin is 6.9 ~ 12.0 kJ/m
2(23
oc).
7. a daiamid composition that comprises the polyamide resin described in claim 1 ~ 6 any one, by weight percentage, comprises following component:
Polyamide resin 30 ~ 99.9%;
Reinforcing filler 0 ~ 60%;
Fire retardant 0 ~ 50%;
Other auxiliary agents 0.1 ~ 10%.
8. daiamid composition according to claim 7, is characterized in that, being shaped as of described reinforcing filler is fibrous, and its mean length is 0.01-20mm, is preferably 0.1 ~ 6mm; Its length-to-diameter ratio is 5 ~ 2000:1, is preferably 30 ~ 600:1; The content of described reinforcing filler is 10 ~ 50wt%.
9. daiamid composition according to claim 8, it is characterized in that, described reinforcing filler is inorganic reinforcing filler or organic reinforcing filler, described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre; Described organic reinforcing filler is selected from Kevlar and/or carbon fiber.
10. daiamid composition according to claim 7, it is characterized in that, being shaped as of described reinforcing filler is non-fibrous, its median size is 0.001～10 μ m, be preferably 0.01～5 μ m, be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.
11. daiamid compositions according to claim 7, it is characterized in that, described fire retardant is halogenated flame retardant or halogen-free flame retardants, described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecanes or brominated aromatic cross-linked polymer, is preferably preferred brominated Polystyrene; Described halogen-free flame retardants is selected from one or more containing the fire retardant of nitrogen combustion inhibitor, phosphonium flame retardant or nitrogenous and phosphorus; Be preferably phosphonium flame retardant; The content of described fire retardant is 10 ~ 40wt%.
12. daiamid compositions according to claim 11, it is characterized in that, it is that phosphoric acid ester, butylbenzene are one or more of phosphoric acid ester, hypophosphite that described phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene; Be preferably the hypophosphite with following structure formula I:
In formula, R
1, R
2identical or different, be expressed as straight chain or alkyl and/or aryl or phenyl containing 1 ~ 6 carbon atom of side chain; M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or by protonated nitrogenous base; M is 1 ~ 3.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410049496.1A CN103936978A (en) | 2013-05-20 | 2014-02-13 | Polyamide resin and polyamide composition composed of polyamide resin |
| PCT/CN2014/073045 WO2014187183A1 (en) | 2013-05-20 | 2014-03-07 | Polyamide resin and polyamide combination formed of same |
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| CN2013101862472A CN103254423A (en) | 2013-05-20 | 2013-05-20 | Polyamide resin and polyamide composition composed thereof |
| CN201310186247.2 | 2013-05-20 | ||
| CN201410049496.1A CN103936978A (en) | 2013-05-20 | 2014-02-13 | Polyamide resin and polyamide composition composed of polyamide resin |
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| CN104497390A (en) * | 2014-11-27 | 2015-04-08 | 界首市东威塑业有限公司 | Novel process for granulating modified recycled plastic particles |
| CN113444241A (en) * | 2021-06-28 | 2021-09-28 | 广州辰东新材料有限公司 | Polyamide and preparation method thereof |
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| CN104017204B (en) * | 2014-05-20 | 2017-11-17 | 珠海万通化工有限公司 | A kind of polyamide and the daiamid composition being made from it |
| CN104262952B (en) * | 2014-09-19 | 2016-03-30 | 金发科技股份有限公司 | A kind of low potential of hydrogen polyamide moulding composition |
| CN104804413B (en) * | 2015-03-26 | 2018-11-06 | 珠海万通特种工程塑料有限公司 | A kind of polyamide moulding composition |
| CN111057233B (en) * | 2019-12-29 | 2023-05-05 | 无锡殷达尼龙有限公司 | Copolymerized semi-aromatic polyamide and preparation method thereof |
| CN112341812B (en) * | 2020-11-05 | 2022-04-19 | 金发科技股份有限公司 | Self-assembled network polyamide composition and preparation method and application thereof |
| CN114276677B (en) * | 2021-12-17 | 2023-09-26 | 金发科技股份有限公司 | Flame-retardant nylon composite material and preparation method and application thereof |
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Also Published As
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| WO2014187183A1 (en) | 2014-11-27 |
| CN103254423A (en) | 2013-08-21 |
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