CN101735609A - Halogen-free fire-retarding reinforced polyamide composition and molded product prepared by using same - Google Patents
Halogen-free fire-retarding reinforced polyamide composition and molded product prepared by using same Download PDFInfo
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- CN101735609A CN101735609A CN200910213967A CN200910213967A CN101735609A CN 101735609 A CN101735609 A CN 101735609A CN 200910213967 A CN200910213967 A CN 200910213967A CN 200910213967 A CN200910213967 A CN 200910213967A CN 101735609 A CN101735609 A CN 101735609A
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Abstract
The invention discloses a halogen-free fire-retarding reinforced polyamide composition and a molded product prepared by using the same. The hlogen-free fire-retarding reinforced polyamide composition comprises the following components: 35 to 70 weight percent of semi-aromatic polyamide resin, 10 to 35 weight percent of fire retardant, 0 to 5 weight percent of fire-retarding synergist, 15 to 50 weight percent of inorganic reinforcing filler, at least one antioxidant and at least one inorganic nano material, wherein the total weight of the components is 100 percent. The halogen-free fire-retarding reinforced polyamide composition prepared according to the formula of the invention has high color stability, is applicable to electronic connectors that can be used in all kinds of electronic equipment such as computers, televisions, mobile phones, industrial instruments and meters and other electronic circuit board devices.
Description
Technical field
The present invention relates to a kind of daiamid composition.
Background technology
Polyamide resin has excellent physical strength, thermotolerance, chemical proofing, wearability and self lubricity, and frictional coefficient is low, its widespread use field comprises electronic apparatus, trolley part, furniture, building materials and fiber, has become one of most important engineering plastics.Material require as trolley part and electrical and electronic component has good thermotolerance, formability and low water absorbable, therefore needs to adopt the hot higher and low various aromatic polyamides of water-intake rate of patience.
On the viewpoint of environment protection,, develop a kind of lead-free solder of surface mounting in recent years as the method for carrying out high-density installation.The reflux temperature of lead-free solder is often than the temperature height of widely used lead and tin eutectic solder so far.When adopting this surface mounting technique (SMT), the element of surface mounting must be exposed in 250-260 ℃ the high temperature.Therefore, when welding printed circuit board (PCB) and electric element with lead-free solder, the resin that is used to form electric element must have higher heat-resisting stablizing, and this requirement is particularly arranged in unleaded solder reflow process.
The polyamide resin of some semi-aromatics all has very high fusing point, thereby cause its processing temperature also very high, often under high like this processing temperature, the halogen fire retardant that has that always uses can decompose in the past, fire retardant decomposes the sour gas cognition that produces has more serious etching problem to the twin screw extruder surface, and makes that the product surface ratio is more coarse.Add that halogen has very big harm for environment, consider, must develop eco-friendly halogen-free flame retardants from this two aspect.
The based flame retardant that patent WO 9609344 discloses phosphoric acid salt or hypophosphite mixture uses with pyrrolotriazine derivatives, but these fire retardants are at high temperature unstable, in mold process, especially can decompose or degraded under high humidity.Therefore need good thermal stability, itself does not have the halogen-free flame retardants of disadvantageous effect for resin properties.Patent US5773556 discloses and has comprised the phosphatic composition of polymeric amide and hypophosphite or secondary.Patent US 6255371 discloses the polymer composition that comprises polymeric amide or polyester, wherein comprises the fire retardant of hypophosphite or two hypophosphite and melamine derivative.
This class new life's halogen-free flame retardants has good heat endurance, highly stable under the course of processing of high-temperature resistant polymeric amide, the phenomenon that does not have decomposition, but also bring a very significantly problem, the daiamid composition that contains halogen-free flame retardants is easy to degraded under the condition of light and heat photograph, thus colorific variation, the polymeric amide product of Natural color and light color particularly, the variable color situation is just more obvious.Because this variable color is very tangible, for some junctors that uses on personal electric is electric, shows out face, this is a such variable color situation beyond affordability for the user, so this metachromatism is badly in need of being resolved.
Patent US5380774A discloses a kind of nylon moulding compound of tackling and has been exposed under the ultraviolet light and heat and causes degrading and the method for variable color, in this patent, the moulding compound of the nylon based that contains optothermal stabilizer has been discussed, said composition mainly comprises: 1) a kind of hindered phenol anti-oxidants, 2) a kind of bi-ester of phosphite; 3) a kind of hindered amine light stabilizer.Be applicable to aliphatics nylon 6, nylon 66, NYLON610, nylon 612, Ni Long11 and nylon 12 etc.In this patent example, mainly be to use composite stablizer, comprising:
1010,
626,
144 Hes
234.
Patent EP1950238 discloses a kind ofly has the fire-retardant semiaromatic polyamide composition composition that improves colour stability, and this fire-retardant and composition colour stable mainly comprises: 1) at least a semiaromatic polyamide composition resin (P); 2) at least a fire retardant of forming by hypophosphite or two hypophosphite (FR); 3) at least a Hinered phenols stablizer (HPS); 4) at least a phosphite ester stabilizer (PS); But wherein do not comprise hindered amines stablizer (ASHS) or the content of such stablizer in all stablizers is not higher than 15% (HPS)+(PS)+(ASHS).In the example of this patent, FR is
OP1230, HPS is
1010; PS uses
626, what ASHS used is
S-EED.
The applicant has attempted the effect at halogen-free flameproof semiaromatic polyamide composition composition as patent US5380774A and the described compound stabilizer of patent EP1950238, the result shows that method colour stability in halogen-free flameproof enhancing semiaromatic polyamide composition composition system of patent US5380774A description is poor, and the described method of patent EP1950238 will increase compared with the method colour stability that patent US5380774A describes, but colour-change still is apparent in view in high temperature resistant test.
Summary of the invention
Purpose of the present invention overcomes the defective that prior art exists, and provides the good halogen-free flameproof of a kind of colour stability to strengthen semiaromatic polyamide composition.
To achieve these goals, the present invention adopts following technical scheme:
A kind of halogen-free fire-retarding reinforced polyamide composition comprises following component:
(1) the semiaromatic polyamide composition resin of 35-70 weight %;
(2) hypophosphite fire retardant of 10-35 weight %;
(3) fire retarding synergist of 0-5 weight %;
(4) inorganic reinforcing filler of 15-50 weight %;
(5) at least a antioxidant;
(6) at least a inorganic nano material;
(1)-(6) summation is a weight 100%;
The structural formula of described fire retardant is suc as formula (I) or formula (II) or its combination,
R wherein
1And R
2Identical or different, all be selected from the C of straight or branched
1-C
6Alkyl or aryl; R
3Be the C of straight or branched
1-C
10Alkylidene group, C
6-C
10Arylidene, alkyl arylene or aryl alkylene.
M is calcium, magnesium, aluminium or zine ion; M is 2 or 3, and n is 1 or 3, and x is 1 or 2.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, R
1And R
2All be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl and phenyl; R
3Be methylene radical, ethylidene, positive propylidene, isopropylidene, positive butylidene, uncle's butylidene, positive pentylidene, just octylene, positive inferior undecyl or phenylene or naphthylidene, methylphenylene, ethyl phenylene, tertiary butyl phenylene, methyl naphthylidene, ethyl naphthylidene, tertiary butyl naphthylidene or phenylmethylene, phenyl ethylidene, phenyl propylidene and phenyl butylidene; M is preferably aluminum ion or zine ion.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, described semiaromatic polyamide composition resin is made up of di-carboxylic acid unit and two amine units, the di-carboxylic acid unit contains the aromatic dicarboxylic acid unit of 45-100 mole % and the aliphatic dicarboxylic acid unit that 0-55 mole % has 4-12 carbon atom, and two amine units are made up of the aliphatics Alkylenediamine unit with 4-12 carbon atom.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, described semiaromatic polyamide composition resin is made up of di-carboxylic acid unit and two amine units, the di-carboxylic acid unit contains the aromatic dicarboxylic acid unit of 45-100 mole % and the aliphatic dicarboxylic acid unit that 0-55 mole % has 4-12 carbon atom, and two amine units are made up of the aliphatics Alkylenediamine unit with 4-12 carbon atom.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, described aromatic dicarboxylic acid unit is terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-is dioctyl phthalate, 1 how, 4-is dioctyl phthalate, 4 how, 4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid; Described aliphatic dicarboxylic acid unit is 1,4-Succinic Acid, 1,6-hexanodioic acid, 1,8-suberic acid, 1,9-nonane diacid, 1,10-sebacic acid, 1,11-undecane diacid or 1,12-dodecanedioic acid; Described straight chain aliphatic diamine is 1,4-butanediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 carbon diamines or 1,12-12 carbon diamines; Described side chain aliphatic diamine is the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine; Described cycloalphatic diamine is cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, described fire retardant is the hypophosphite of (I) or two hypophosphite (II); Be preferably diethyl hypo-aluminum orthophosphate or methylethyl hypo-aluminum orthophosphate or both mixtures.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, described fire retarding synergist is preferably one or more the mixture in zinc borate, zinc sulphide or the aluminum oxide; Fire retarding synergist content is preferably 0.5-3 weight %.The adding of fire retarding synergist can reduce the consumption of halogen-free flame retardants.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, described antioxidant is preferably one or more mixture of hindered phenol anti-oxidants, thioether class antioxidant, thiophenol class antioxidant, hindered amines antioxidant, phosphorous acid esters antioxidant and phosphorous acid salt antioxidant; Described oxidation preventive content is 0.1-2 weight %.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, described inorganic nano material is preferably in nano zine oxide, nano magnesia, nano aluminium oxide, nano molecular sieve and the nano intercalated material one or more mixture; Inorganic nano material content is 0.1-3 weight %.The use of inorganic nano material, particularly nano molecular sieve can absorb the acidic substance that bittern-free flame-proof material discharges in the course of processing, thereby improve the colour stability of product.
In above-mentioned halogen-free fire-retarding reinforced polyamide composition, described inorganic reinforcing filler is preferably one or more mixing in carbon fiber, glass fibre, potassium titanate fiber, glass microballon, glass flake, talcum powder, mica, clay, kaolin, silicon-dioxide, silicon dirt, diatomite, the lime carbonate, and inorganic reinforcing filler content is 15-45 weight %.Optimum fiber shape filler, special preferred glass fibers.By using glass fibre, when improving composition molding, improved the tensile strength of the formed formed body of resin combination, flexural strength, the heat-resistant quality of mechanical characteristics such as modulus in flexure and thermal distortion intensity etc.
Another object of the present invention provides the moulded product that utilizes above-mentioned halogen-free fire-retarding reinforced polyamide composition preparation.
Halogen-free fire-retarding reinforced polyamide composition of the present invention is by melting mixing, can be by any known manufacture method manufacturing, use single screw rod or twin screw extruder, blending machine, melting mixing such as Banbury mixer, mill machine mixes all components, makes halogen-free fire-retarding reinforced polyamide composition.
Can use composition of the present invention, by any known shaping, comprise injection moulding, blowing, extrude or moulded product of the present invention is made in thermoforming.
Compared with prior art, the present invention has following beneficial effect: the colour stability according to the halogen-free fire-retarding reinforced polyamide composition of formulation of the present invention is very good.Be suitable for above the electric power connector, electric power connector can be used to any electronics, for example computer, TV, mobile telephone, industrial device instrument and other electronic circuit panel assemblies.Electric power connector preferred surface field engineering, with the formed junctor of halogen-free fire-retarding reinforced polyamide composition of the present invention, with about 300 seconds when having more than 255 ℃ pyritous infrared reflow soldering furnace the product color have satisfactory stability.
Embodiment
The present invention is described further below to introduce specific embodiment, but these specific embodiments are not to limit the invention.
Embodiment 1-7 and comparative example 1-4
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |
| Polyamide 6 T/66 (50/50) | ??54 | ??- | ??- | ??54 | ??54 | ??39 | ??67 | ??50.5 | ??56.5 | ??- | ??- |
| Polyamide 6 T/6I (50/50) | ??- | ??50 | ??- | ??- | ??- | ??- | ??- | ???- | ??52.5 | ??- | |
| Polymeric amide 10T | ??- | ??- | ??53 | ??- | ??- | ??- | ??- | ???- | ??55.5 | ||
| Fire retardant | ??12 | ??16 | ??13 | ??12 | ??12 | ??12 | ??14 | ??18 | ??12 | ??16 | ??13 |
| Glass fibre | ??30 | ??30 | ??30 | ??30 | ??30 | ??45 | ??15 | ??30 | ??30 | ??30 | ??30 |
| Fire retarding synergist | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??- | ??1 | ??1 | ??1 |
| Oxidation inhibitor | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 | ??0.5 |
| Nano molecular sieve | ??1 | ??1 | ??1 | ??1.5 | ???- | ??1 | ??1 | ??- | ??- | ??- | ??- |
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |
| Nano zine oxide | ??0.5 | ??0.5 | ??0.5 | ??- | ??1.5 | ??0.5 | ??0.5 | ??- | ??- | ??- | ??- |
| Other auxiliary agents | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| Color (range estimation) | Fine | Better | Better | Good | Good | Better | Good | Generally | Generally | Generally | Generally |
| Color (whiteness) | ??81 | ??78 | ??79 | ??76 | ??76 | ??78 | ??79 | ??70 | ??74 | ??70 | ??72 |
| UL94 flame retardant rating (0.8mm) | ??V0 | ??V0 | ??V0 | ??V0 | ??V0 | ??V0 | ??V0 | ??V0 | ??V0 | ??V0 | ??V0 |
| ??ΔE(SMT) | ??1.7 | ??2.0 | ??2.5 | ??2.5 | ??2.8 | ??2.0 | ??1.9 | ??4.8 | ??4.0 | ??4.5 | ??4.2 |
| ??ΔE??(180℃，24h) | ??7.2 | ??8.2 | ??9.3 | ??10.3 | ??11.2 | ??9.3 | ??8.4 | ??21.5 | ??17.4 | ??19.3 | ??18.4 |
Part is composed as follows shown in the table 1:
Fire retardant: diethyl hypo-aluminum orthophosphate (OP1230 is available from Clariant company)
Glass fibre: PREFORMAX 807A (available from OC company)
Fire retarding synergist: zinc borate (ZB-500 is available from opening the company of flying)
Oxidation inhibitor: 4,4 '-two (, '-dimethyl benzyl) pentanoic, (Naugard 445, available from Chemtura Corporation).
Composition (not containing glass) according to table 1 is pre-mixed evenly, and with screw speed and the glass fibre melting mixing of the twin screw extruder that makes up at rotating speed 300rpm, glass fibre is carried out the side feeding again.Barrel temperature among embodiment and the comparative example is about 310 ℃, and being blended under 260-310 ℃ the temperature of each component carried out.Molten polymer leaves water quenching, granulation then behind the forcing machine.
The granulation material is tested by the standard injection moulding behind the dry 4h down at 120 ℃.
Is that the sample of 0.8mm carries out the flame retardant properties test according to the UL-94 standard to thickness.
Resin combination be molded into standard testing side's plate of 60mm * 60mm * 1.0mm, pass through Reflow Soldering baker (SMT) then, the value of chromatism (Δ E) of measuring Reflow Soldering front and back plate with color difference meter is weighed the stability of resin combination color.
The thermal spike of reflow soldering is 260 ℃, is about 200s in the time more than 200 ℃.
Claims (10)
1. halogen-free fire-retarding reinforced polyamide composition is characterized in that comprising following component:
(1) the semiaromatic polyamide composition resin of 35-70 weight %;
(2) fire retardant of 10-35 weight %;
(3) fire retarding synergist of 0-5 weight %;
(4) inorganic reinforcing filler of 15-50 weight %;
(5) at least a antioxidant;
(6) at least a inorganic nano material;
(1)-(6) summation is a weight 100%;
The structural formula of described fire retardant is suc as formula (I) or formula (II) or its combination,
R wherein
1And R
2Identical or different, all be selected from the C of straight or branched
1-C
6Alkyl or aryl; R
3Be the C of straight or branched
1-C
10Alkylidene group, C
6-C
10Arylidene, alkyl arylene or aryl alkylene.
M is calcium, magnesium, aluminium or zine ion; M is 2 or 3, and n is 1 or 3, and x is 1 or 2.
2. halogen-free fire-retarding reinforced polyamide composition according to claim 1 is characterized in that: R
1And R
2All be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl and phenyl; R
3Be methylene radical, ethylidene, positive propylidene, isopropylidene, positive butylidene, uncle's butylidene, positive pentylidene, just octylene, positive inferior undecyl or phenylene or naphthylidene, methylphenylene, ethyl phenylene, tertiary butyl phenylene, methyl naphthylidene, ethyl naphthylidene, tertiary butyl naphthylidene or phenylmethylene, phenyl ethylidene, phenyl propylidene and phenyl butylidene; M is aluminum ion or zine ion
2, halogen-free fire-retarding reinforced polyamide composition according to claim 1, it is characterized in that: described semiaromatic polyamide composition resin is made up of di-carboxylic acid unit and two amine units, the di-carboxylic acid unit contains the aromatic dicarboxylic acid unit of 45-100 mole % and the aliphatic dicarboxylic acid unit that 0-55 mole % has 4-12 carbon atom, and two amine units are 4～14 straight chain aliphatic diamine, side chain aliphatic diamine or cycloalphatic diamine.
3. halogen-free fire-retarding reinforced polyamide composition according to claim 2, it is characterized in that: described aromatic dicarboxylic acid unit is terephthalic acid, m-phthalic acid, 2-methyl terephthalic acid, 2,5-dichloroterephthalicacid acid, 2,6-is dioctyl phthalate, 1 how, 4-is dioctyl phthalate, 4 how, 4 '-biphenyl dicarboxylic acid or 2,2 '-biphenyl dicarboxylic acid; Described aliphatic dicarboxylic acid unit is 1,4-Succinic Acid, 1,6-hexanodioic acid, 1,8-suberic acid, 1,9-nonane diacid, 1,10-sebacic acid, 1,11-undecane diacid or 1,12-dodecanedioic acid; Described straight chain aliphatic diamine is 1,4-butanediamine, 1,6-hexanediamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,1,11-11 carbon diamines or 1,12-12 carbon diamines; Described side chain aliphatic diamine is the 2-methyl isophthalic acid, 5-pentamethylene diamine, 3-methyl isophthalic acid, 5-pentamethylene diamine, 2,4-dimethyl-1,6-hexanediamine, 2,2,4-trimethylammonium-1,6-hexanediamine, 2,4,4-trimethylammonium-1,6-hexanediamine, 2-methyl isophthalic acid, 8-octamethylenediamine or 5-methyl isophthalic acid, 9-nonamethylene diamine; Described cycloalphatic diamine is cyclohexane diamine, methylcyclohexane diamines or 4,4 '-diamino-dicyclohexyl methane.
4. halogen-free fire-retarding reinforced polyamide composition according to claim 1 is characterized in that: described fire retardant is the hypophosphite of (I) or two hypophosphite (II).
5. halogen-free fire-retarding reinforced polyamide composition according to claim 4 is characterized in that: described fire retardant is diethyl hypo-aluminum orthophosphate or methylethyl hypo-aluminum orthophosphate or both mixtures.
6. halogen-free fire-retarding reinforced polyamide composition according to claim 1 is characterized in that: described fire retarding synergist is one or more the mixture in zinc borate, zinc sulphide, zinc oxide, alkali type aluminium oxide or the aluminum oxide; Fire retarding synergist content is 0.5-3 weight %.
7. halogen-free fire-retarding reinforced polyamide composition according to claim 1 is characterized in that: described antioxidant is one or more a mixture of hindered phenol anti-oxidants, thioether class antioxidant, thiophenol class antioxidant, hindered amines antioxidant, phosphorous acid esters antioxidant and phosphorous acid salt antioxidant; Described oxidation preventive content is 0.1-2 weight %.
8. halogen-free fire-retarding reinforced polyamide composition according to claim 1 is characterized in that: described inorganic nano material is one or more a mixture in nano zine oxide, nano magnesia, nano aluminium oxide, nano molecular sieve and the nano intercalated material; Inorganic nano material content is 0.1-3 weight %.
9. halogen-free fire-retarding reinforced polyamide composition according to claim 1, it is characterized in that: described inorganic reinforcing filler is one or more mixing in carbon fiber, glass fibre, potassium titanate fiber, glass microballon, glass flake, talcum powder, mica, clay, kaolin, silicon-dioxide, silicon dirt, diatomite, the lime carbonate, and inorganic reinforcing filler content is 15-45 weight %.
10. a moulded product comprises each described halogen-free fire-retarding reinforced polyamide composition of aforesaid right requirement.
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| US7294661B2 (en) * | 2003-10-03 | 2007-11-13 | E.I. Du Pont De Nemours And Company | Flame resistant aromatic polyamide resin composition and articles therefrom |
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| US20090275682A1 (en) * | 2005-11-10 | 2009-11-05 | Asahi Kasei Chemicals Corporation | Resin Composition Excellent in Flame Retardance |
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