CN101724260B - Flame retardant type high tenacity polyamide composition and preparation method thereof - Google Patents
Flame retardant type high tenacity polyamide composition and preparation method thereof Download PDFInfo
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- CN101724260B CN101724260B CN200810224874XA CN200810224874A CN101724260B CN 101724260 B CN101724260 B CN 101724260B CN 200810224874X A CN200810224874X A CN 200810224874XA CN 200810224874 A CN200810224874 A CN 200810224874A CN 101724260 B CN101724260 B CN 101724260B
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Abstract
The invention provides a flame retardant type high tenacity polyamide composition, comprising blended polyamide and silicone rubber powder in a weight ratio of 100:(0.5-100). The mean grain size of the silicone rubber powder is 20-1000nm. The polyamide composition has good flame retardancy and tenacity. Meanwhile, a preparation method of the composition is simple in process and easy to operate.
Description
Technical field
The present invention relates to a kind of daiamid composition.Specifically, relate to a kind of daiamid composition and preparation method thereof with flame retardant resistance, H.T..
Technical background
Along with the development of petrochemical complex, plastics and goods thereof have obtained widely using, and their are natural polymers such as traditional steel, metal, cement and the timber of instead of part, cotton just rapidly, are widely used in each department of national economy such as industry, agricultural, military affairs.Global plastic raw materials ultimate production was 206000kt in 2003, and wherein, the more thermoplastic resin of general-purpose plastics output is Vilaterm, SE, Vestolen PP 7052, PS etc., and polymeric amide occupies the first place in the output of engineering plastics.These thermoplasticss belong to inflammable material, and HRR is big during burning, and calorific value is high; Produce a large amount of molten drops during burning, flame propagation speed is difficult for extinguishing; Sometimes also produce thick smoke and toxic gas, cause harm, people's the huge threat of life security formation to environment.
In recent years, various countries' fire statistics analysis revealed, occurrence index and all be obvious ascendant trend by the loss that fire causes, and the fire of a large portion is to be caused by igniting by macromolecular material.So, inflammable and combustible polymer is carried out fire-retardant finish, reduce fire losses as far as possible, eliminate disaster hidden-trouble, be of great immediate significance.For this reason, countries in the world have all been formulated the fire-retardant rules of a series of relevant macromolecular materials in succession, and more and more stricter to its requirement of standard, index and supervision aspect, particularly limit or forbid the use of halogen containing flame-retardant in polymer materials.Therefore, research, exploitation and the application to fire-retardant, low cigarette, low (nothing) malicious polymkeric substance more and more receives the attention of government, research institution and enterprise.
At present, a large amount of research concentrates on the halogen-free flame retardants, like mineral filler and organosilicon etc.Yet common inorganic combustion inhibitor is not very effective, need add 60% amount at least and could obtain satisfied flame retardant effect.High filler loading capacity makes the toughness and the poor processability of material, in order to remedy the flexible loss, can add rubber usually.And the adding of rubber makes processing become difficult more.Research to the organosilicon halogen-free flame-retardant system mostly concentrates on thermoplastic resin such as polycarbonate, the PS etc. that modification contains aromatics, and organosilyl adding also reduces the toughness of resin.
Summary of the invention
The inventor finds through a large amount of experimental study, adopts a kind of special silicon rubber powder to come modified polyamide, when making daiamid composition have fine flame retardant resistance, has good toughening effect again.
Therefore, one of the object of the invention provides above-mentioned this flame retardant type high tenacity polyamide composition.
Another object of the present invention has provided the preparation method of above-mentioned flame retardant type high tenacity polyamide composition.
A kind of flame retardant type high tenacity polyamide composition of the present invention includes the following component of blend: polymeric amide and silicon rubber powder; Wherein the weight ratio of silicon rubber powder and polymeric amide is (0.5～100): 100; The median size of wherein said silicon rubber powder is 20～1000nm.
In compsn of the present invention, the weight ratio of silicon rubber powder and polymeric amide preferred (1～50): 100, more preferably (1～40): 100.
In compsn of the present invention, described polymeric amide comprises the disclosed various types of polymeric amide of prior art, and for example nylon 6, nylon 66, nylon 46 and nylon 1010 etc.
In compsn of the present invention, the preferred median size of described silicon rubber powder is 50～500nm, is more preferably 50～200nm.
Described silicon rubber powder preferably adopts the prepared fully sulfurized silicon rubber powder of having applied for according to the applicant of Chinese patent ZL01801656.1.This kind fully vulcanized powder rubber gel content reaches 60 weight % or higher, preferred 75% weight or higher.The median size of Zylox particle is 20～1000nm, is preferably 50～500nm, more preferably 50～200nm.Each particulate in this fully sulfurized silicon rubber powder all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and under the observation of existing microtechnique, does not find layering in the particulate, divides the phenomenon that equates uneven phase.This fully sulfurized silicon rubber powder gets through to the silicone rubber latex cross-linking radiation rubber particles particle diameter being fixed.
The preparation method of flame retardant type high tenacity polyamide composition of the present invention comprises the component that includes said polymeric amide and silicon rubber powder is compared melt blending by said set of dispense.
Adopt the rubber plastic blend method to prepare in the flame retardant type high tenacity polyamide plastics composite process of the present invention, the blending temperature of material is the general processing temperature of polyamide resin, selects not only guaranteeing the complete fusion of matrix resin but also can not make in the scope of its decomposition.In 230～250 ℃ scope, and the blending temperature of nylon 66 is generally in 250～275 ℃ scope as the blending temperature of nylon 6.In addition, according to the processing needs, can in the blend material, add the conventional auxiliary agent and the expanding material of plastic working in right amount.
The employed blending equipment of present method is the general blending equipment in the rubber and plastic processing industry, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
Flame retardant type high tenacity polyamide composition of the present invention is controlled as the form of the fire-retardant toughened component of disperse phase and the particle diameter and the weight of the silicon rubber powder with crosslinking structure that size distribution can be passed through to be sneaked into, and has good flame retardant type, toughness.
Preparing method's technology of the flame retardant type high tenacity polyamide composition of the present invention's preparation is simple, and the modified plastics of gained promptly has good flame retardant type and has good toughness again.
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention does not receive the restriction of these embodiment.Scope of the present invention proposes in claims.
One, the preparation of silicon rubber powder:
Embodiment 1:
Silicone oil (Beijing company of section, the trade mark: KH-L10) place container, press 3% of the dried glue weight of silicone oil emulsion and add the crosslinking coagent Viscoat 295 with commercially available solid content 30%wt.Through radiovulcanization, irradiation dose is 15Mrad, spray-dried after, obtaining median size is 150nm, the fully sulfurized silicon rubber powder of gel content 80.8%.
Two, the preparation of daiamid composition:
Embodiment 2:
With nylon 6 (BASF AG; The trade mark is B4), the fully sulfurized silicon rubber powder and antioxidant 1010 (the Switzerland vapour Ba Jiaji production) mix that obtain among the embodiment 1; Parts by weight in nylon 6 are 100 parts; It specifically consists of: 100 parts of nylon, 5 parts of fully sulfurized silicon rubber powders, 0.3 part in oxidation inhibitor.Adopt the ZSK-25 twin screw extruder blend granulation of German WP company, each section of forcing machine temperature is respectively: 223 ℃, 236 ℃, 237 ℃, 242 ℃, 241 ℃ and 235 ℃ (head temperature).Pellet is processed the standard batten through injection, carries out the test of each item mechanical property and combustionproperty, and its result is as shown in table 1.
Embodiment 3:
Except the umber that adds silicon rubber powder is 10 parts.All the other conditions are identical with embodiment 2.Mechanical property and combustionproperty result are as shown in table 1.
Embodiment 4:
Except the umber that adds silicon rubber powder is 20 parts.All the other conditions are identical with embodiment 2.Mechanical property and combustionproperty result are as shown in table 1.
Comparative example 1:
Except that not adding the silicon rubber powder, all the other conditions are identical with embodiment 2.Concrete mechanics and combustionproperty result list in table 1.
The testing method explanation of combustionproperty
Taper calorimeter method:
The taper calorimeter is that the American National Institute Of Science And Technology proposed in nineteen eighty-two.It is the polymer materials burning determinator of new generation that is the basis with the oxygen consumption principle; The oxygen consumption principle is meant the oxygen of every consumption 1g; The heat that material is discharged in burning is 13.1kJ (error is 5% or better), and receives fuel type and whether perfect combustion takes place to influence very little.Just can obtain HRR accurately as long as can accurately determine the oxygen amount of material consumption when burning.HRR is one of most important fire behavior parameter, and it is meant the speed of unit surface sample release of heat, with KW/m
2Be unit, be defined as fire intensity again.Simultaneously, it also can provide the HRR dynamic change in time of polymeric material fuel combustion process.The peak of HRR is the HRR peak value.HRR or HRR peak value are littler, and the danger of this polymer materials in fire is just little.The standard of this combustionproperty testing method is ISO5660.
Table 1
| The HRR peak | The evenly heat rate of release | Tension fracture elongation rate | 23 ℃ of cantilever beam impact strengths | Cantilever beam impact strength-20 ℃ | Modulus in flexure | Heat-drawn wire | |
| Unit | (kW/m 2) | (kW/m 2) | (％) | (J/m) | (J/m) | (GPa) | (℃) |
| Embodiment 2 | 332 | 143 | 50 | 63.2 | 53.9 | 2.32 | 54.6 |
| Embodiment 3 | 317 | 129 | 55 | 71.9 | 54.4 | 2.27 | 54.1 |
| Embodiment 4 | 281 | 124 | 48 | 74.3 | 68.9 | 2.19 | 52.3 |
| Comparative example 1 | 790 | 370 | 51 | 41.2 | 34.9 | 2.44 | 54.0 |
| Testing standard | ISO5660 | ISO5660 | ASTMD638 | ASTMD256 | ASTMD2656 | ASTMD790 | ASTMD648 |
The embodiment that from table 1, lists and the result of Comparative Examples can find out; The flame retardant properties of having added the polymeric amide of silicon rubber powder obviously is superior to not adding the polymeric amide of silicon rubber powder; Adding owing to silicon rubber powder simultaneously makes that the shock strength of material is improved significantly, and rigidity and resistance toheat are constant basically.
Claims (8)
1. flame retardant type high tenacity polyamide composition includes the following component of blend: polymeric amide and fully sulfurized silicon rubber powder; Wherein the weight ratio of fully sulfurized silicon rubber powder and polymeric amide is (0.5～100): 100; The median size of wherein said fully sulfurized silicon rubber powder is 20～1000nm, and the gel content of fully sulfurized silicon rubber powder is 60 weight % or higher.
2. flame retardant type high tenacity polyamide composition according to claim 1 is characterized in that the weight ratio of fully sulfurized silicon rubber powder and polymeric amide is (1～50): 100.
3. flame retardant type high tenacity polyamide composition according to claim 2 is characterized in that the weight ratio of fully sulfurized silicon rubber powder and polymeric amide is (1～40): 100.
4. flame retardant type high tenacity polyamide composition according to claim 1, the median size that it is characterized in that described fully sulfurized silicon rubber powder is 50～500nm.
5. flame retardant type high tenacity polyamide composition according to claim 4, the median size that it is characterized in that described fully sulfurized silicon rubber powder is 50～200nm.
6. flame retardant type high tenacity polyamide composition according to claim 1, the gel content that it is characterized in that described fully sulfurized silicon rubber powder are 75 weight % or higher.
7. flame retardant type high tenacity polyamide composition according to claim 1 is characterized in that described fully sulfurized silicon rubber powder is the rubber particles of equal phase structure.
8. a preparation method who prepares each the described flame retardant type high tenacity polyamide composition in the claim 1～7 is characterized in that said polymeric amide and said fully sulfurized silicon rubber powder are made daiamid composition by said weight ratio melt blending.
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| CN101724260B true CN101724260B (en) | 2012-05-30 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5610223A (en) * | 1995-07-13 | 1997-03-11 | Bayer Corporation | Impact modified polyamide-based molding composition |
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- 2008-10-24 CN CN200810224874XA patent/CN101724260B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5610223A (en) * | 1995-07-13 | 1997-03-11 | Bayer Corporation | Impact modified polyamide-based molding composition |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平5-148417A 1993.06.15 |
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