CN112029280B - Halogen-free flame-retardant polyamide composite material and preparation method thereof - Google Patents
Halogen-free flame-retardant polyamide composite material and preparation method thereof Download PDFInfo
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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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
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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
Abstract
The invention relates to a halogen-free flame-retardant polyamide composite material and a preparation method thereof. The flame-retardant synergist used in the invention has a remarkable improvement effect on flame-retardant performance, can improve the heat resistance and stability of the material, and has no negative influence on other mechanical properties or electrical properties.
Description
Technical Field
The invention belongs to the field of polyamide composite materials, and particularly relates to a halogen-free flame-retardant polyamide composite material and a preparation method thereof.
Background
The halogen-free flame-retardant reinforced polyamide has excellent electrical property, mechanical property, flame retardant property and the like, and is widely applied to the fields of electronics, electrics, new energy automobiles and the like. With the development trend of miniaturization and thinning of a plurality of products, higher requirements are put forward on the flame retardant property of the material, and the flame retardant V-0 grade with the thickness of less than 1.0mm becomes the mainstream requirement. The phosphorus flame retardant is a high-efficiency environment-friendly flame retardant with great application prospect in nylon materials, wherein diethyl aluminum phosphinate is the most typical. Pure aluminum diethylphosphinate is mainly gas-phase flame retardant in the combustion process, a large amount of aluminum diethylphosphinate is mainly involved in condensed phase flame retardant after melamine derivatives and borate are introduced as synergists, aluminum boron phosphate and the like generated by the aluminum diethylphosphinate and the synergists cover the surface layer of a combustion product, and only a small amount of aluminum diethylphosphinate is involved in gas-phase flame retardant. However, in the face of ever-increasing flame retardant requirements, how to further increase flame retardant efficiency becomes the focus of research.
The existing methods for improving the flame retardant efficiency by using the phosphorus-containing flame retardant can be classified into two methods: the scheme is that a novel phosphorus-containing flame retardant with higher flame retardant efficiency is used in a synthesis mode, and a novel synergist is added in the scheme, so that the flame retardant efficiency of an original flame retardant system is higher. The technology for synthesizing the novel phosphorus-containing flame retardant by adopting the scheme I is continuously emerging, for example, in the patent CN1950436A, an organic phosphate containing a benzene ring structure is adopted as the flame retardant, and the organic phosphate and the melamine derivative form a synergistic effect, so that the combustion time can be reduced to 13 seconds from 42 seconds in polypropylene. Similar patents for synthesizing novel phosphorus-containing flame retardants also include, for example, CN109180731A, CN111218089A, CN111205619A, CN110903512A, CN109762022A, and the like. And the second scheme also searches for novel synergists, for example, CN101128541A adopts antimony oxide, antimonate, fluoride, silicon-containing compounds and the like as flame retardant auxiliaries, and compounds the flame retardant auxiliaries with halogen-containing flame retardants and organic phosphates to realize the flame retardant effect of flame retardant V-0 grade. In patent CN 1599776a, fluorine oligomer or silicone resin is introduced as a stabilizing aid in phosphorus-containing flame retardant thermoplastic resin, which can effectively improve the flame retardant property of the material. Similar patents such as CN107641318A (phosphate glass powder as a synergist), CN106832419B (dipentaerythritol, MCA and the like as a synergist) and the like all seek a novel synergist which forms a synergist with a phosphorus-containing flame retardant to improve the flame retardant performance of the material.
However, the current scheme has certain limitation, a mature and efficient novel phosphorus-containing flame retardant is not available in the market to replace the currently widely used aluminum diethylphosphinate, and a more efficient novel phosphorus-containing flame retardant is still in the development process from the aspects of cost economy, flame retardant efficiency and the like. For the second scheme, researchers mostly try to achieve synergistic effect by using the existing compounds and phosphorus-containing flame retardants, such as the problems of disputes in using halogen and antimony white, the problems of sacrificing other properties of the resin, and the problems of silicon inhibition of some products, etc. in the above-mentioned patents.
In summary, the currently mature aluminum diethylphosphinate-melamine polyphosphate-zinc borate compound flame retardant system is still the mainstream of the organic phosphine flame retardant system, and novel efficient phosphorus-containing flame retardants and flame retardant synergists still need to be researched and explored continuously.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a halogen-free flame-retardant polyamide composite material and a preparation method thereof, wherein the flame-retardant synergist is adopted to remarkably improve the flame-retardant property, simultaneously improve the heat resistance and stability of the material, and have no negative influence on other mechanical properties or electrical properties.
The invention provides a halogen-free flame-retardant polyamide composite material, which comprises the following components in percentage by weight:
30-80% of polyamide resin;
5-55% of a filler;
1-25% of phosphinate;
1-5% of melamine derivative;
1-5% of borate;
0.02-5% of flame-retardant synergist;
0.1 to 1 percent of other auxiliary agents;
wherein the flame retardant synergist comprises at least one of a carbon radical scavenger, a primary antioxidant and a secondary antioxidant; when the flame-retardant synergist is a carbon free radical scavenger, the main antioxidant and/or the auxiliary antioxidant are not necessary, but the flame-retardant effect is better when the flame-retardant synergist is compounded with a small amount of the main antioxidant and/or the auxiliary antioxidant for use;
the carbon free radical scavenger accounts for 0.02-5% of the total mass of the polyamide composite material; the main antioxidant accounts for 0.2-5% of the total mass of the polyamide composite material; the auxiliary antioxidant accounts for 0.2-5% of the total mass of the polyamide composite material;
wherein the carbon free radical scavenger is at least one of hydroxylamines, bisphenol monoacrylates, ortho-propenyl substituted phenols and benzofuranone.
Further, the carbon radical scavenger is hydroxylamine (e.g., bis (octadecyl) hydroxylamine, CAS No.143925-92-2), bisphenol monoacrylates (e.g., 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, CAS number 61167-58-6), ortho-propenyl-substituted phenols, benzofuranones (e.g., 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) benzofuran-2 (3H) -one, CAS number 164391-52-0; [ 4-tert-butyl-2- (5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl) phenyl ]3, 5-di-tert-butyl-4-hydroxybenzoate, CAS No. 1261240-30-5). The carbon radical scavenger also includes other types of carbon radical scavengers (e.g., p-cresol and dicyclopentadiene copolymer, CAS number 68610-51-5; 2- [1- (2-hydroxy-3, 5-di-t-pentylphenyl) ethyl ] -4, 6-di-t-pentylphenyl acrylate, CAS number 123968-25-2).
The main antioxidant is at least one of a phenol antioxidant and an amine antioxidant. Phenolic antioxidants include, but are not limited to, monophenol type, bisphenol type, polyphenol type, and complex type, typically antioxidants such as 54, 730, BHA, SP, BHT, 1010, 1076, 1098, 1024, 1135, 1222, 1790, 3114, PCRBF, 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol, AO series hindered phenol antioxidants, and the like. The amine antioxidant includes, but is not limited to, aromatic amine antioxidants, typically derivatives of aromatic secondary amines, such as Naugard445 and the like.
The auxiliary antioxidant is at least one of thioester antioxidant and phosphite antioxidant. The thioester antioxidant includes but is not limited to antioxidants DLTDP, DSTDP, DMTDP, DTDTDTP, etc. Phosphite antioxidants include, but are not limited to, antioxidants 168, 626, TP80, PEP-36, Ultranox626, 398, and the like.
The polyamide resins include polyamides obtained by polycondensation of at least one aliphatic dicarboxylic acid with an aliphatic or cyclic or cycloaliphatic or arylaliphatic diamine, such as PA66, PA610, PA612, PA1010, PA106, PA1212, PA46, MXD 6; or polyamides obtained by polycondensation between at least one aromatic dicarboxylic acid and an aliphatic or aromatic diamine, such as polyterephthalamides of the type PA9T, PA10T, PA11T, PA12T, PA13T or PA6T/6I, PA6T/66, PA66/6T, polyisophthalamides of the type PA6I, PA6I/6T, polynaphthalenemethylenamides of the type PA10N, PA11N, PA12N, polyaramides, such as aramid, or blends and copolyamide resins thereof. The polyamide resin of the invention can also be chosen from polyamide resins obtained by polycondensation of at least one amino acid or lactam with itself, it being possible for this amino acid to be produced by hydrolytic opening of the lactam ring, such as PA6, PA7, PA11, PA12 or PA13, or blends thereof and copolyamide resins thereof. Types of copolyamide resins which may be mentioned in particular include polyamide 6/66, polyamide 6/11, polyamide 6/12 and polyamide 11/12.
The filler is at least one of chopped glass fiber, carbon fiber, talcum powder, mica, calcium carbonate, barium sulfate, wollastonite, kaolin, clay and titanium dioxide. The chopped glass fibers preferably have a typical length in the range of 1.5mm to 6.0mm, and the milled glass fibers are preferably 7-16 μm, more preferably 8-12 μm directly. Meanwhile, the ground glass fiber strands comprise A-, E-, C-, D-, S-and R-glass fibers, and the cross sections of the fibers have other cross section shapes such as round, oval or square.
The phosphinate is a phosphinate of the following structure:
A diphosphinate of the structure:
and/or polymers thereof;
wherein R is6And R7Linear or branched C1-C6 alkyl and/or aryl groups of the same or different structure; r3Is a linear or branched C1-C10 alkylene, C6-C10 arylene, alkylarylene or arylalkylene group; m is selected from one or more of alkali metals, alkaline earth metals, Al, Zn, Fe and boron, particularly preferably Ca or Mg, wherein M is 1 to 4; n is 1 or 3; x is 1 or 2. R6And R7Preferably one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, phenyl. R3Preferred are methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene. Aluminum diethylphosphinate is preferred in the present invention.
The melamine derivative is melamine polyphosphate, the average condensation degree is 20-200, and the phosphorus content is 10-20wt%, preferably 12-18 wt%. More preferred are melamine polyphosphates derived from 1,3, 5-triazine compounds having an average degree of condensation of 20 to 200 and a1, 3, 5-triazine content of 1.1 to 2.0mol per mol of phosphorus atom, and 1,3, 5-triazine compounds selected from the group consisting of melamine, melam, melem, melamine diamide, melamine monoamide, 2-ureidomelamine, acylmelamine, benzoguanamine, and diaminophenyl triazine. Most preferred are 1,3, 5-triazine compounds having an average degree of condensation of 40 to 150: the ratio of the molar phosphorus atoms is 1.2 to 1.8. The pH of a10 wt% aqueous salt slurry (as prepared in EP1095030B 1) is typically above 4.5, preferably at least 5.0.
The borate is zinc borate.
The other auxiliary agent is a lubricant and is selected from at least one of stearamides, alcohol stearates, stearates and long-chain saturated linear carboxylates.
The invention provides a preparation method of a halogen-free flame-retardant polyamide composite material, which comprises the following steps:
weighing the raw materials according to the proportion, mixing, and extruding and granulating by a double-screw extruder to obtain the halogen-free flame-retardant polyamide composite material.
The flame-retardant synergist comprises a carbon free radical trapping agent acting on a free radical chain type degradation first stage, a main antioxidant of a second stage and an auxiliary antioxidant of a third stage. The carbon free radical trapping agent is used as a synergist, so that the gas-phase flame-retardant process is enhanced on the basis of keeping high-efficiency condensed phase flame retardance, and the flame-retardant efficiency is further improved.
Advantageous effects
The flame-retardant synergist used in the invention has a remarkable improvement effect on flame-retardant performance, can improve the heat resistance and stability of the material, and has no negative influence on other mechanical properties or electrical properties.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The examples and comparative examples used the following starting materials:
polyamide resins and glass fibers are commercially available, aluminum diethylphosphinate is OP 1230 (from clariant chemical), melamine polyphosphate is Melapur 20070 and Amgard PA1 (from solvay), zinc borate is Firebrake ZB (from dyna), antioxidant Irganox 1098 (from BASF), Naugard445 (from koppe), PEP-36 (from adidae), Revonox 501 and Revonox 608 (from chipec), light stabilizer Chimassorb 944 (from clariant), and lubricant is TR044W (from Struktol) and liconav 101 PWD (from clariant chemical).
The present invention will be further described with reference to comparative examples 1 to 7 and examples 1 to 31.
Weighing the raw materials according to the proportion of table 1-table 6, mixing in a high mixing machine, and then extruding and granulating by a double-screw extruder (the diameter of a screw is 65mm, the extrusion temperature is 220-. The prepared composite material is injection-molded into combustion sample bars with the size of 125mm 13mm 1.0mm, the test is carried out according to UL 94 vertical combustion, in order to increase the reliability of data, 10 sample bars are tested in each group, after flame time t1 and t2 and after flame time t3 (the flame-retardant system t3 is 0s without detailed comparison), the flame-retardant grades are judged to be V-0, V-1 and V-2 according to the warranty, and the average (t1+ t 2)/s) of 10 sample bars in each group is calculated for comparing the flame-retardant efficiency, wherein the average time error range of (t1+ t2) is about +/-0.5 s due to the adoption of a button timing mode.
TABLE 1 comparative examples 1-4 and examples 1-4 ratios and results of flame retardant testing
TABLE 2 comparative examples 5-7 and examples 5-9 compounding ratio and results of flame retardant property test
Table 3 examples 10-14 formulation and flame retardant performance test results
TABLE 4 examples 15-20 compounding ratio and flame retardant test results
TABLE 5 examples 21-27 compounding ratios and flame retardant test results
TABLE 6 examples 28-31 compounding ratios and flame retardant test results
From comparative examples 1-2 in Table 1 it is concluded that after fixing the proportions of aluminium diethylphosphinate OP 1230, melamine polyphosphate Melapur 20070, zinc borate Firebake ZB, the composites have an average (t1+ t2) of 14.5s in the absence of an antioxidant and are V-1 flame retardant rating. After 0.2 percent of hindered phenol main antioxidant Irganox 1098 is added, the flame retardant time is not obviously changed, which is the conventional use proportion of Irganox 1098 as an anti-aging function. Comparative examples 3 to 4, the average (t1+ t2) gradually decreased as the proportion of OP 1230 was gradually increased, and the average (t1+ t2) decreased to around 2.2s as the proportion of OP 1230 was increased to 20%. In examples 1-4, when Irganox 1098 breaks through the conventional use ratio and is increased to 0.5%, the average (t1+ t2) is reduced to 8.3s, the flame retardant grade reaches V-0, the average (t1+ t2) is gradually reduced with the increase of the Irganox 1098 ratio, and when Irganox 1098 is increased to 5%, the average (t1+ t2) is reduced to 2.0s, and the flame retardant efficiency is obviously improved.
Comparative examples 5 to 7 in Table 2 show that as the proportion of the hindered amine based stabilizer Chimassorb 944 was gradually increased, the average (t1+ t2) was rather increased, showing a negative effect on flame retardant properties. The aromatic amine main antioxidant Naugard445 has a very obvious positive effect on the improvement of the flame retardant efficiency. The 0.2% Naugard445 can make the material stably maintain V-0 flame retardant grade, the 0.5% Naugard445 can reduce the average (t1+ t2) to 6.1s, the Naugard445 with the content of more than 1.0% can reduce the average (t1+ t2) to within 2s, and when the content is increased to 5%, the material can basically achieve the degree of extinguishing when being away from the fire.
Table 3 shows the influence rule of the phosphite ester auxiliary antioxidant PEP-36 on flame retardance, and with the increase of the use proportion, the average (t1+ t2) is obviously reduced, and the improvement effect on the flame retardance efficiency is obvious.
Table 4 shows the effect of carbon radical scavenger Revonox 501 on the flame retardant performance. Because the capability of the carbon free radical scavenger for catching free radicals is far higher than that of the conventional main or auxiliary antioxidant, a small amount of Revonox 501 and the conventional dose of Irganox 1098 have a very obvious effect of improving flame retardance when being compounded and used. When the addition proportion of Revonox 501 is 0.02%, the flame retardant performance can be only slightly improved and the range is not large no matter whether 0.2% Irganox 1098 is compounded or not, and the flame retardant grade is still V-1. Fixing 0.2% Irganox 1098, gradually increasing the proportion of Revonox 501, for example 0.05% and 0.1%, the average (t1+ t2) was reduced to 6.8s and 3.5s, respectively, showing a very high boosting effect on flame retardance. When Revonox 501 is increased to 1% or even 5%, the lifting effect cannot be accurately tested due to the equipment testing limit, but the Revonox is basically in a state of going away from the fire and extinguishing.
In Table 5, examples 21 to 24 show the flame retardant status of the material when the carbon radical scavenger and the secondary antioxidant are compounded, the proportion of the secondary antioxidant is fixed, the proportion of the carbon radical scavenger is gradually increased, and the average (t1+ t2) is remarkably reduced. In examples 25 to 27, the flame retardant efficiency was better when the carbon radical scavenger, the primary antioxidant, and the secondary antioxidant were used in combination.
In examples 28-31 of Table 6, the flame retardant rating of 1.0mm V-0 was achieved by fixing the proportions of the flame retardants OP 1230, Amgard PA1 and Firebrake ZB, while fixing the proportions of the synergist and adjusting the proportions of the resin and glass fibers, and the flame retardant time decreased with decreasing resin proportions. The experimental data show that the proportion of the lubricant has no obvious influence on the flame retardant effect.
Theoretically, the mechanism of improving the gas-phase flame retardance by adopting the free radical scavenger is also applicable to other thermoplastic resins with free radical chain type degradation reaction mechanisms.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (4)
1. The halogen-free flame-retardant polyamide composite material is characterized by comprising the following components in percentage by weight:
30-80% of polyamide resin;
5-55% of a filler;
1-25% of phosphinate;
1-5% of melamine derivative;
1-5% of borate;
0.02-5% of flame-retardant synergist;
0.1 to 1 percent of other auxiliary agents;
wherein the flame retardant synergist is any one of a carbon free radical trapping agent and a main antioxidant, a carbon free radical trapping agent and an auxiliary antioxidant, and a carbon free radical trapping agent and a main antioxidant and an auxiliary antioxidant; the carbon free radical scavenger accounts for 0.05-5% of the total mass of the polyamide composite material; the main antioxidant accounts for 0.2-5% of the total mass of the polyamide composite material; the auxiliary antioxidant accounts for 0.2-5% of the total mass of the polyamide composite material; wherein the carbon radical scavenger is Revonox 501; the auxiliary antioxidant is phosphite ester antioxidant; the main antioxidant is at least one of phenolic antioxidant and amine antioxidant;
wherein the melamine derivative is melamine polyphosphate, the average condensation degree is 20-200, and the phosphorus content is 10-20 wt%.
2. The composite material of claim 1, wherein: the other auxiliary agent is a lubricant.
3. The composite material of claim 2, wherein: the lubricant is at least one of stearamides, alcohol stearates, stearates and long-chain saturated linear carboxylate lubricants.
4. A method for preparing the halogen-free flame-retardant polyamide composite material of claim 1, comprising:
weighing the raw materials according to the proportion of claim 1, mixing, and performing extrusion granulation by a double-screw extruder to obtain the halogen-free flame-retardant polyamide composite material.
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