CN102532600B - Melamine salt flame retardant, flame-retardant polyamide film and preparation method thereof - Google Patents
Melamine salt flame retardant, flame-retardant polyamide film and preparation method thereof Download PDFInfo
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- CN102532600B CN102532600B CN2012100192534A CN201210019253A CN102532600B CN 102532600 B CN102532600 B CN 102532600B CN 2012100192534 A CN2012100192534 A CN 2012100192534A CN 201210019253 A CN201210019253 A CN 201210019253A CN 102532600 B CN102532600 B CN 102532600B
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- 0 *C(C(*)P(*)(O)=O)C(OCC1O*CC1)=O Chemical compound *C(C(*)P(*)(O)=O)C(OCC1O*CC1)=O 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Nc1nc(N)nc(N)n1 Chemical compound Nc1nc(N)nc(N)n1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- PKZLNMGYULVQOK-UHFFFAOYSA-N CC(CP(c1ccccc1)(O)=O)C(OCC1OCCC1)=O Chemical compound CC(CP(c1ccccc1)(O)=O)C(OCC1OCCC1)=O PKZLNMGYULVQOK-UHFFFAOYSA-N 0.000 description 2
- ABNNDNALPAVVDO-UHFFFAOYSA-N CC(CP(c1ccccc1)(O)=O)C(Cl)=O Chemical compound CC(CP(c1ccccc1)(O)=O)C(Cl)=O ABNNDNALPAVVDO-UHFFFAOYSA-N 0.000 description 1
- JZMFMCJQUSQTQY-UHFFFAOYSA-N CC(CP(c1ccccc1)(O)=O)C(O)=O Chemical compound CC(CP(c1ccccc1)(O)=O)C(O)=O JZMFMCJQUSQTQY-UHFFFAOYSA-N 0.000 description 1
- JNODDICFTDYODH-UHFFFAOYSA-N OC1OCCC1 Chemical compound OC1OCCC1 JNODDICFTDYODH-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N OCC1OCCC1 Chemical compound OCC1OCCC1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of polyamide films, in particular to a melamine salt flame retardant, a flame-retardant polyamide film and the preparation method thereof, and aims to solve the problems in the prior art that the overall properties (including flame retardancy and mechanical property) of the flame-retardant polyamide film are poor. The invention provides the melamine salt flame retardant, the flame-retardant polyamide film containing the melamine salt flame retardant, and the preparation method thereof. The flame retardant is a melamine phosphate salt with the tetrahydrofuran ring structure. The addition of the melamine salt flame retardant does not reduce the viscosity of polyamide, the film product has excellent overall properties and is environment-friendly, and the preparation method is simple and favorable to industrial production.
Description
Technical field
The present invention relates to the polyamide layer technical field, relate in particular to a kind of melamine salt fire retardant, Flameproof polyamide film and preparation method thereof.
Background technology
Two-way stretching polyamide film (BOPA film) has the not available various good over-all propertieies of other film, comprise mechanical property, thermotolerance, wearability, chemical proofing, dimensional stability etc., because two-way stretching polyamide film has these good characteristics, therefore, be used widely at aspects such as automobile, electric installation, mechanical part, transportation equipments.Along with electronics, electric, communication, household electrical appliances, intelligent, the microminiaturized development of electromechanical equipment, people begin to study improving the two-way stretching polyamide film flame retardant properties.
In prior art, Flameproof polyamide thin film technology method mainly contains two kinds, first method is to adopt the fire retardant of copoly type and hexanolactam or nylon salt (nylon salt) to carry out copolymerization, and the preparation Flameproof polyamide is cut into slices, then makes film by stretch processes.But adopt the method to prepare polyamide layer, the copolymerization cost is high, complex process, and facility investment is large.Second method is that blend is carried out in fire retardant and the polymeric amide section of commixed type, extrudes and makes fire-retardant master granule, and then make film by stretch processes; At present main research concentrates on small molecules fire retardants such as sneaking into bromine system, phosphorus system, nitrogen system in polyamide layer.But because polymeric amide is all responsive for the soda acid of humidity and low concentration, the small molecules fire retardant add the reduction that usually can induce polymeric amide viscosity, reduce the mechanical property of two-way stretching polyamide film, and then reduce the range of application of polyamide layer.Therefore how to improve Flameproof polyamide film mechanics and fire-retardant contradiction, become the problem of polyamide layer field growing interest.
Monsanto Company is US4193914 (date of publication: announced in patent application on March 18th, 1980) and add 15% chloride hydroxyethylidene diphosphonic acid polymkeric substance in polymeric amide, prepared Halogen Flameproof polyamide film in the patent No..
MIT is US2005203223 (date of publication: U.S. Patent application on September 15th, 2005) in publication No., publication No. is JP2003226764 (date of publication: announced in Japanese Patent on August 12nd, 2003), add 20% triazine flame retardant in nylon 6, fire-retardant nylon film (thickness is below 1.2mm) is prepared in injection moulding, its glossiness is 40%, mist degree is below 5%, oxygen index is more than 26, but the vertical combustion grade of fire-retardant nylon film is still the VTM-2 level.Publication number is that JP2001031780 (open day: described and add 20% melamine cyanurate in nylon by Japanese Patent February 6 calendar year 2001), preparing thickness is the fire-retardant nylon film of 0.01-0.1mm, and film vertical combustion grade is the VTM-2 level.
Beyer Co., Ltd (Bayer company) has released nylon 6 barrier films (commodity are called Dure than LPDU) that organized clay is filled, and have good barrier property and mechanical property, but the vertical combustion grade is still very low.DSM (DSM) company has released and has contained nitrogen combustion inhibitor melam (white powder of commodity Melapur200 by name), and it is applicable to the nylon 66 of thin-gage goods.What add 25%-30% in nylon 66 contains nitrogen combustion inhibitor melam, and its flame retardant resistance grade can reach UL94 VTM-1 standard.
In fire-retardant nylon is produced, due to adding in a large number of fire retardant, the product impact property is reduced very fast, during special nylon film goods below producing 400 μ m, goods are difficult to moulding, and breakage rate is higher, raw material availability is low, cost up, thus limited it in the application in some field.In order to overcome this shortcoming, Liu appoints the (development of toughness fire-retardant nylon-6 recklessly, " plastics science and technology ", 06 phase in 1997, the 14th page) develop toughness fire-retardant nylon product, not only kept its original premium properties, and good toughness, shock strength are high, can be used for producing the thin-gage goods that reaches fire-retardant requirement.Reach intelligent virtue (preparation of expansion nylon-6/graphite composite material and conductivity research, " Hebei Normal University's mastership Diplomarbeit ", 2007) adopt ultrasonic oscillation to pulverize, and carry out nylon 6 surface graft modifications and prepare expanded graphite, collaborative phosphonate fire retardant adopts solution casting method to prepare the fire-retardant nylon film.But above-mentioned these flame-proof composite materials all are not suitable for the following polyamide layer of melting slab suitability for industrialized production 400 μ m.
From international and domestic present Research, use the suitability for industrialized production that prior art fails to realize to have the desirable Flameproof polyamide film of good flame-retardance and stable mechanical property.With regard to blending fire retardant modified polyamide film, solve the fire-retardant thinking of polyamide layer and be all on phosphorus, nitrogen are the basis of main fire retardant and go to strengthen from particle diameter and two angles of consistency, but the reduced viscosity of polymeric amide is obvious, and the mechanical property of film reduces significantly.
Summary of the invention
For the flame retardant resistance that solves the Flameproof polyamide film that exists in prior art and the relatively poor defective of over-all properties of mechanical property, the invention provides a kind of melamine salt fire retardant, add Flameproof polyamide film of this fire retardant and preparation method thereof.Add this melamine salt fire retardant and can not reduce the viscosity of polymeric amide, the excellent combination property of gained film flame retardant resistance and mechanical property, free from environmental pollution, its preparation method is simple, is conducive to suitability for industrialized production.
In order to solve the problems of the technologies described above, the invention provides following technical proposals:
A kind of melamine salt fire retardant, its feature be, described fire retardant is the phosphonic acids melamine salt that contains the tetrahydrofuran (THF) ring structure, and its general structure is as follows:
Further, described aryl functional group comprises the phenyl that phenyl, naphthyl, monoalkyl replace, the naphthyl that monoalkyl replaces; Described alkyl, alkoxyl group comprise C
1-C
6Alkyl or alkoxyl group; Described C
1-C
6Alkyl comprise methyl, ethyl, propyl group, butyl, amyl group, hexyl, described C
1-C
6Alkoxyl group comprise methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy.
A kind of Flameproof polyamide film, its feature are that totally 100 parts of described polyamide layer materials comprise the melamine salt fire retardant that 5-10 part is above-mentioned; Described Flameproof polyamide film also comprises the polymeric amide of 85-94 part, the oxidation inhibitor of 0.5-2 part, the catalyzer of 1-3 part.Described umber is weight part.
Further, described polymeric amide comprises aliphatics nylon; Described catalyzer comprises the metal lewis acid; Described oxidation inhibitor comprises β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (oxidation inhibitor JX-1076), N; N '-two-betanaphthyl-Ursol D (oxidation inhibitor DNP), N; N '-two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098) or inorganic phosphate (nylon high-efficiency anti-oxidant BRUGGOLEN H10).
Described aliphatics nylon comprises nylon 6, （Fen Mo/Ke Li） Nylon11 in powder/granular form, nylon 12, nylon 66, NYLON610, nylon 612; Described metal lewis acid comprises metal oxide, molecular sieve catalyst (molecular sieve or doping vario-property molecular sieve, the silicate of crystal form or silico-aluminate) or tungstate, as phospho-wolframic acid, silicotungstic acid etc.; Wherein metal oxide comprises titanium dioxide, zinc oxide, ferric oxide, molybdic oxide or tungstic oxide.
Further, described polyamide layer comprises the melamine salt fire retardant of 5-8 part; Described Flameproof polyamide film also comprises the polymeric amide of 88-92 part, the oxidation inhibitor of 1-2 part, the catalyzer of 2-3 part.
Further, the thickness of described Flameproof polyamide film is 50-200 μ m.
Further, the thickness of described Flameproof polyamide film is 60-100 μ m.
Further, the thickness of described Flameproof polyamide film is 120-180 μ m.
A kind of preparation method of above-mentioned melamine salt fire retardant, its feature is that described preparation method comprises the steps:
(1) diprotic acid compound and thionyl chloride are joined in reaction vessel, react 3～5h under 70～78 ℃, generate acyl chlorides, remaining thionyl chloride is removed in underpressure distillation; Mole proportioning of described diprotic acid compound and thionyl chloride is 0.8～1.0: 1;
(2) step (1) gained acyl chlorides and tetrahydrofurfuryl alcohol are carried out esterification, under 85～100 ℃, reaction 1～2h, being warming up to solution has backflow, react 3～4h, after reaction finished, raw material was removed in underpressure distillation again, mixture is poured in frozen water, regulates PH to 5～7, obtains intermediate; The mol ratio of described tetrahydrofurfuryl alcohol and diprotic acid compound is 1～1.2: 1;
(3) step (2) gained intermediate is dissolved in dehydrated alcohol, adds trimeric cyanamide backflow 45-50h, cooling, filtration, washing, drying get the white powder product; The mol ratio of described trimeric cyanamide and diprotic acid compound is 1: 1;
Its reaction expression is as follows:
Wherein, raw material I is the diprotic acid compound; Raw material II is thionyl chloride, and raw material II I is tetrahydrofurfuryl alcohol; Raw material IV is trimeric cyanamide.
A kind of above-mentioned Flameproof polyamide thin film technology method, its feature is that described preparation method comprises the steps:
(1) mechanical pre-mixing: polymeric amide is dry, its moisture content is reached below 100ppm, mix with the phosphonic acids melamine salt fire retardant, catalyzer and the oxidation inhibitor high-speed stirring that contain the tetrahydrofuran (THF) ring structure, the stirrer rotating speed is 750r/min, is prepared into to process material; Described polymeric amide can be 120-140 ℃ of drying;
(2) melting mixing: step (1) gained is processed material and is made sheet vacuumizing to melt extrude under condition; Melt temperature is different according to polyamide material adopts temperature ranges commonly used in prior art, for example, can be at 230-260 ℃, or 260-290 ℃ melt extrude, and the conversion zone temperature of forcing machine is greater than 250 ℃;
(3) two-way stretch: step (2) gained sheet is made the Flameproof polyamide film through overcooling slab, stretch processes.
In step (2), each section of forcing machine temperature is preferably 240 ℃ (feeding sections), and 255 ℃, 255 ℃, 255 ℃, 240 ℃ (conversion zone and head), screw speed is 45r/min.
Be US 4626592 in the patent No., the day for announcing is (application number 06/685 on December 2nd, 1986,854, the applying date: United States Patent (USP) on December 24th, 1984), the patent No. is US 4798894, the day for announcing be on January 17th, 1989 (application number: 07/048,585 applying date: mention in United States Patent (USP) on May 11st, 1987) Gem-cyclodialkylation reaction, this reaction be the nineties report terminal amido and five yuan of Oxygenic heterocyclic compounds between the substitution reaction that occurs.Productive rate and the selectivity of Gem-cyclodialkylation reaction are good, and no matter the acid amides of aromatic amine, fatty amine or different carbon chain can have certain transformation efficiency.Should reaction effectively occur rapidly in high temperature section (250 ℃～300 ℃) simultaneously, and be difficult to carry out under low temperature (＜250 ℃).
In above-mentioned Flameproof polyamide thin film technology process, polymeric amide (PA) adopts suitably higher forcing machine conversion zone temperature in melt extruding process, with the phosphonic acids melamine salt fire retardant generation situ-formed graft reaction that contains the tetrahydrofuran (THF) ring structure.Gem-cyclodialkylation reaction as follows occurs in the tetrahydrofuran (THF) ring structure in the end group-amido linkage of polymeric amide and described melamine salt fire retardant,
The terminal amido of polymeric amide under the effect of catalyzer with tetrahydrofuran (THF) generation substitution reaction.
Above-mentioned reaction not only helps lend some impetus to polymeric amide and produces suitable crosslinking structure; Simultaneously also make fire retardant more directly contact with its base material, thereby better bring into play the effect of fire retardant.By utilizing the gem-cyclodialkylation substitution reaction to delay the thermooxidative degradation process of polymeric amide, produce more flammable micromolecular compound thereby slow down.The gem-cyclodialkylation reaction occurs by the terminal amide key with PA6 in the phosphonic acids melamine salt fire retardant that contains the tetrahydrofuran (THF) ring structure, makes the degraded product of PA6 generate stable material, thereby forms Flameproof polyamide system preferably.
Compared with prior art, the phosphonic acids melamine salt fire retardant that contains the tetrahydrofuran (THF) ring structure provided by the invention can not reduce the viscosity of polymeric amide, it melt extrudes process polymeric amide, can with polymeric amide generation reaction in－situ (as above-mentioned gem-cyclodialkylation reaction), make fire retardant more directly contact with base material, significantly improve flame retarding efficiency, reduced the consumption of fire retardant; Fire retardant and polymeric amide generation reaction in－situ can also improve the consistency of fire retardant and base material, make the mechanical property of fire retardant material be improved, and fire retardant is difficult for oozing out from film surface, can guarantee Flame Retardancy can weather resistance; And this reaction has reduced the interaction force between polyamide chains, has reduced the crystallizing power of polymeric amide, makes polymeric amide have better film forming properties; In addition, the phosphonic acids melamine salt fire retardant that contains the tetrahydrofuran (THF) ring structure provided by the invention is not halogen-containing, is conducive to environmental protection, and its preparation method is simple, and is harmless to environment, its flame retardant properties is better than traditional halogenated flame retardant, has a good application prospect.Be added with the excellent combination properties such as the flame retardant resistance of Flameproof polyamide film of melamine salt fire retardant provided by the invention and mechanical property, its preparation method is simple, is conducive to suitability for industrialized production.
Description of drawings
Fig. 1 is Flameproof polyamide membrane structure schematic diagram provided by the invention.
Fig. 2 is 3-(hydroxyl-phenyl-phosphoryl)-tetrahydrofurfuryl propionate melamine salt
1The H-NMR collection of illustrative plates;
Fig. 3 is the FTIR collection of illustrative plates of 3-(hydroxyl-phenyl-phosphoryl)-tetrahydrofurfuryl propionate melamine salt;
Fig. 4 is Flameproof polyamide thin film technology schema provided by the invention.
Wherein, 1 is the Flameproof polyamide film.
Embodiment
As shown in Figure 1, Flameproof polyamide film 1 provided by the invention is extruded structure for individual layer.
As shown in Figure 2, CEPPTHF-M provided by the invention
1The H-NMR spectrum,
1H-NMR (Nuclear Magnetic Resonance) is the hydrogen nuclear magnetic resonance spectrogram.Wherein, chemical shift is to be connected with oxygen on the tetrahydrofuran (THF) ring-CH at δ=3.8～4.0ppm
2The characteristic peak of-upper proton, δ=1.3～1.9ppm is another one CH on the tetrahydrofuran (THF) ring
2The characteristic peak of-upper proton, δ=2.28～2.3ppm are between phenyl phosphinic acid and carbonyl-CH
2-CH
2The characteristic peak of-upper proton, δ=7.4～7.7ppm is the characteristic peak of proton on phenyl ring, above-mentioned peak value explanation contains the tetrahydrofuran (THF) ring, carbonyl, C in the structure of CEPPTHF-M
6H
5-,-CH
2-CH
2-structure.
As shown in Figure 3, the infrared spectrogram of CEPPTHF-M provided by the invention, FTIR (Fourier Transform infrared spectroscopy) is Fu Shi conversion infrared spectrum analysis.At wave number 3386cm
-1The place is trimeric cyanamide NH
2Absorption peak, at wave number 3107cm
-1The place is NH
3 +Absorption peak, wave number 2901cm
-1The place is the stretching vibration peak of methylene radical, at wave number 699cm
-1Place and wave number 724cm
-1Two peaks at place are single peak, wave number 1680cm of replacing of phenyl ring
-1The place is the peak of carbonyl on ester group; Wave number 1333cm
-1Place and wave number 1256cm
-1The place is the stretching vibration peak of ester group C-O-C, and above-mentioned peak value explanation contains ester group in the structure of CEPPTHF-M, phenyl, carbonyl, NH
2, NH
3 +
As shown in Figure 4, Flameproof polyamide thin film technology schema provided by the invention.Dried polymeric amide is mixed with fire retardant, catalyzer high-speed stirring, melt extrude by twin screw extruder and make sheet, the gained sheet is first cooling rapidly, then preheating, carry out longitudinal stretching, heat treatment, cross directional stretch, heat treatment are carried out in preheating again, cooling, rolling afterwards, are packaged to be the Flameproof polyamide film.Also can add oxidation inhibitor in above-mentioned high-speed stirring mixing process.
Other raw material that the following embodiment of the present invention is used and reagent are product common on market, can adopt:
3-(hydroxyl-phenyl-phosphoryl)-propionic acid (CEPP), 3-(hydroxyl-naphthyl-phosphoryl)-propionic acid (CENP), 3-(hydroxyl-phenyl-phosphoryl)-2-phenyl-propionic acid (CEPEP), 3-(hydroxyl-phenyl-phosphoryl)-2-methyl-propionic acid (CEMEP), 3-(hydroxyl-benzyl-phosphoryl)-2-phenyl-propionic acid (CEBP), buying is from east, Qingdao chemical industry company limited of section (chemical pure);
Tetrahydrofurfuryl alcohol, analytical pure; Buying is from traditional Chinese medicines group's chemical reagent Chengdu company limited;
Thionyl chloride, analytical pure; Buying is from traditional Chinese medicines group's chemical reagent Chengdu company limited;
Trimeric cyanamide, pyridine, 2,6-lutidine, 4-dimethyl amido-pyridine, toluene, dimethylbenzene, ethanol, methyl alcohol, chemical pure; Buying is from Chengdu Ke Long chemical reagent work;
PA6 (polyamide 6 or nylon 6), PA66 (polyamide 66 or nylon 66) available from new can Mei Da-DSM nylon chips company limited produces, limiting viscosity is 3.4dl/g;
Titanium dioxide, zinc oxide, ferric oxide, molybdic oxide, tungstic oxide are chemical pure, and buying is from Tianjin Wals chemical industry company limited;
Phospho-wolframic acid, silicotungstic acid, molecular sieve are chemical pure, and buying is sincere chemical reagent company limited from Shanghai;
β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester (oxidation inhibitor JX-1076); N; N '-two-betanaphthyl-Ursol D (oxidation inhibitor DNP); N; N '-two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine (oxidation inhibitor 1098) is technical pure, and buying is from the chemical company limited of Hua Xing (Suqian).
The structure of melamine salt fire retardant provided by the invention and purity, the testing standard of Flameproof polyamide thin film mechanical performance, thermal property and flame retardant properties is as follows:
The structure of melamine salt fire retardant and purity: the employing proton nmr spectra (
1HNMR is called for short the hydrogen spectrum) and infrared spectrum test technology (abbreviation infrared inspection).
Film thickness: adopt the ISO4593-1993 standard, adopt digimatic micrometer to measure.
Oxygen index: adopt the GB/T2406-2009 standard, adopt the test of JF-3 oxygen index measurer.
Tensile property: press the GB/T1040-2006 standard testing, adopt Instron 1185 type universal testing machines, clamping length is 150mm, draw speed 100mm/min.
Percent thermal shrinkage: adopt the GB/T13542.2-2009 standard detection; Get the sample of two 100mm * 100mm from the Flameproof polyamide film, and do vertical, traversal marker, measure laterally and longitudinal length L
0Film is placed on naturally in the baking oven of 150 ℃ keeps respectively 30 minutes (or keeping respectively 1 hour) in the baking oven of 135 ℃, then take out sample from baking oven, sample is cooled to room temperature.Redeterminate horizontal and longitudinal length L
1,
Vertical combustion: press the ANSL-UL94-2009 standard, adopt the test of CZF-5 type vertical combustion instrument.
The preparation method of melamine salt fire retardant provided by the invention comprises the steps:
(1) diprotic acid compound and thionyl chloride are joined in reaction vessel, react 3～5h under 70～78 ℃, generate acyl chlorides, remaining thionyl chloride is removed in underpressure distillation; Mole proportioning of described diprotic acid compound and thionyl chloride is 0.8～1.0: 1;
(2) step (1) gained acyl chlorides and tetrahydrofurfuryl alcohol are carried out esterification, under 85～100 ℃, reaction 1～2h, being warming up to solution has backflow, react 3～4h, after reaction finished, raw material was removed in underpressure distillation again, mixture is poured in frozen water, regulates PH to 5～7, obtains intermediate; Take the mole number of the diprotic acid compound described in step (1) as benchmark, the mol ratio of described tetrahydrofurfuryl alcohol and diprotic acid compound is 1～1.2: 1;
(3) step (2) gained intermediate is dissolved in dehydrated alcohol, adds trimeric cyanamide backflow 45-50h, cooling, filter after, washing, drying get white powder product (melamine salt fire retardant); Take the mole number of the diprotic acid compound described in step (1) as benchmark, the mol ratio of described trimeric cyanamide and diprotic acid compound is 1: 1;
Its reaction expression is as follows:
Wherein, raw material I is the diprotic acid compound, R
1Be benzyl or aryl functional group, R
2, R
3Be alkyl, alkoxyl group, aryl or hydrogen; Raw material II is thionyl chloride, and raw material II I is tetrahydrofurfuryl alcohol; Raw material IV is trimeric cyanamide.
Flameproof polyamide thin film technology method provided by the invention comprises the steps:
(1) mechanical pre-mixing: according to 100 parts of polyamide layer materials, after 85-94 part polymeric amide drying, its moisture content is reached below 100ppm, mix with melamine salt fire retardant 5-10 part, 1-3 part catalyzer and 0.5-2 part oxidation inhibitor high-speed stirring, the stirrer rotating speed is 750r/min, is prepared into to process material;
(2) melting mixing: step (1) gained is processed material and is made sheet vacuumizing to melt extrude under condition; Melt temperature is different according to polyamide material adopts temperature ranges commonly used in prior art, for example, can be at 230-260 ℃, or 260-290 ℃ melt extrude, and the conversion zone temperature of forcing machine is greater than 250 ℃;
(3) two-way stretch: with step (2) gained sheet through (110 ℃ of overcooling slab (40 ℃), longitudinal stretchings, 3.2 doubly), cross directional stretch (100 ℃, 3 times), heat setting type (200 ℃ and 170 ℃), winding process make the Flameproof polyamide film that thickness is 50-200 μ m.Above-mentioned stretch processes parameter can be adjusted by practical situation, as, can also adopt following processing parameter: cooling slab (40 ℃), longitudinal stretching (100 ℃, 3.2 times), cross directional stretch (90 ℃, 3 times), heat setting type (180 ℃ and 150 ℃).
Following embodiment 1-5 products therefrom is melamine salt fire retardant provided by the invention, prepares the melamine salt fire retardant according to above-mentioned reaction expression.
Figure below is the composite diagram of fire retardant 3-(hydroxyl-phenyl-phosphoryl)-tetrahydrofurfuryl propionate melamine salt (CEPPTHF-M):
In the four-necked bottle that whipping appts, thermometer, dropping funnel are housed; add respectively the 3-(hydroxyl-phenyl-phosphoryl)-propionic acid (CEPP) of 1 mole and the thionyl chloride of 1 mole; heating makes the CEPP dissolving; then drip two pyridines of drying treatment; keep 78 ℃ of certain temperatures, reaction 3h.After having reacted, underpressure distillation also adds appropriate toluene and repeats underpressure distillation to remove thionyl chloride.Add toluene to make its dissolving, then drip the tetrahydrofurfuryl alcohol of 1 mole, keep 96 ℃ of certain temperatures, reaction 1.5h dropwises and has been warming up to backflow, then reacts 3h.After reaction finished, raw material was removed in underpressure distillation.Cooling, mixture is poured in frozen water, with hcl acidifying and regulate pH value, has brown oil to generate, and gets intermediate 3-(hydroxyl-phenyl-phosphoryl)-propionic acid tetrahydrofurfuryl alcohol ester.
The 3-(hydroxyl-phenyl-phosphoryl) of gained-propionic acid tetrahydrofurfuryl alcohol ester is dissolved in dehydrated alcohol, adds the trimeric cyanamide of 1 mole, 48h refluxes in being furnished with three neck round-bottomed flasks of drying tube; cold filtration ethanol; washing, vacuum-drying gets the white powder product.Product carries out hydrogen spectral test and infrared inspection.Productive rate is 81%, product
1The H-NMR collection of illustrative plates as shown in Figure 2, the FTIR collection of illustrative plates of product is as shown in Figure 3.
But two kinds of different reactive functionality are contained at the two ends of CEPP, one end is organic carboxyl acid, and the other end is organic phospho acid, and the functional group at two ends all demonstrates different acidity and reactive behavior, wherein the pka of organic phospho acid is that 1.94 (pKa is acidity quotient, has another name called acid dissociation constant.The ionization constant Ka of acid gets negative logarithm, namely-lgKa.The degree of ionization of acid can be described, i.e. Acidity, acid is more weak, and Ka is less, pKa is larger), the pka of organic carboxyl acid is 2.21.When reacting with alcohols material, owing to being nucleophilic addition(Adn)-elimination reaction mechanism, positive polarity on carbonyl carbon and carbon sterically hindered determined that the organic carboxyl acid functional group of CEPP shows higher reactive behavior, easily and alcohols material generation condensation reaction, generate ester bond, and the organic phospho acid of an other end is difficult and alcohols generation substitution reaction, and speed of response is slower.Thionyl chloride is common carboxylic acyloxy chlorination reagent, easily removes because boiling point is low simultaneously, is widely used in esterification.Because the heat decomposition temperature of the intermediate esterification product that obtains is on the low side, the present embodiment takes to improve with the method for trimeric cyanamide salify the thermostability of fire retardant.
Figure below is the composite diagram of fire retardant 3-(hydroxyl-naphthyl-phosphoryl)-tetrahydrofurfuryl propionate melamine salt (CENPTHF-M):
In the four-necked bottle that whipping appts, thermometer, dropping funnel are housed; add respectively the 3-(hydroxyl-naphthyl-phosphoryl)-propionic acid (CENP) of 0.8 mole and the thionyl chloride of 1 mole; heating makes the CEPP dissolving; then drip two pyridines of drying treatment; keep 70 ℃ of certain temperatures, reaction 5h.After having reacted, underpressure distillation also adds appropriate toluene and repeats underpressure distillation to remove thionyl chloride.Add dimethylbenzene (DMB) to make its dissolving, then drip the tetrahydrofurfuryl alcohol of 0.9 mole, keep 100 ℃ of certain temperatures, reaction 1h dropwises and has been warming up to backflow, then reacts 3h.After reaction finished, raw material was removed in underpressure distillation.Cooling, mixture is poured in frozen water, with hcl acidifying and regulate pH value, has oily matter to generate, and gets intermediate 3-(hydroxyl-naphthyl-phosphoryl)-propionic acid tetrahydrofurfuryl alcohol ester.
The 3-(hydroxyl-naphthyl-phosphoryl) of gained-propionic acid tetrahydrofurfuryl alcohol ester is dissolved in dehydrated alcohol, adds the trimeric cyanamide of 0.8 mole, 45h refluxes in being furnished with three neck round-bottomed flasks of drying tube.Cooling, filter ethanol, washing, vacuum-drying gets the white powder product.Product is surveyed hydrogen spectral test and infrared inspection.Productive rate is 74%.
Figure below is the composite diagram of fire retardant 3-(hydroxyl-phenyl-phosphoryl)-2-phenyl-tetrahydrofurfuryl propionate melamine salt (CEPEPTHF-M):
In the four-necked bottle that whipping appts, thermometer, dropping funnel are housed; add respectively the 3-(hydroxyl-phenyl-phosphoryl)-2-phenyl-propionic acid (CEPEP) of 1 mole and the thionyl chloride of 1.1 moles; heating makes the CEPEP dissolving; then drip two pyridines of drying treatment; keep 75 ℃ of certain temperatures, reaction 3h.After having reacted, underpressure distillation also adds appropriate toluene and repeats underpressure distillation to remove thionyl chloride.Add toluene to make its dissolving, then drip the tetrahydrofurfuryl alcohol of 1.2 moles, keep 85 ℃ of certain temperatures, reaction 1.5h dropwises and has been warming up to backflow, then reacts 4h.After reaction finished, raw material was removed in underpressure distillation.Cooling, mixture is poured in frozen water, with hcl acidifying and regulate pH value, gets intermediate 3-(hydroxyl-phenyl-phosphoryl)-2-phenyl-propionic acid tetrahydrofurfuryl alcohol ester.
The 3-(hydroxyl-phenyl-phosphoryl) of gained-2-phenyl-propionic acid tetrahydrofurfuryl alcohol ester is dissolved in anhydrous methanol, adds the trimeric cyanamide of 1 mole, 50h refluxes in being furnished with three neck round-bottomed flasks of drying tube.Cooling, filter ethanol, washing, vacuum-drying gets the white powder product.Product carries out hydrogen spectral test and infrared inspection.Productive rate is 78%.
Figure below is the composite diagram of fire retardant 3-(hydroxyl-phenyl-phosphoryl)-2-methyl-tetrahydrofurfuryl propionate melamine salt (CEMEPTHF-M):
In the four-necked bottle that whipping appts, thermometer, dropping funnel are housed; add respectively the 3-(hydroxyl-phenyl-phosphoryl)-2-methyl-propionic acid (CEMEP) of 0.8 mole and the thionyl chloride of 1 mole; heating makes the CEMEP dissolving; then drip two drying treatment 2; 6-lutidine (DMP); keep 70 ℃ of certain temperatures, reaction 5h.After having reacted, underpressure distillation also adds appropriate toluene and repeats underpressure distillation to remove thionyl chloride.Add toluene to make its dissolving, then drip the tetrahydrofurfuryl alcohol of 0.96 mole, keep 100 ℃ of certain temperatures, reaction 2h dropwises and has been warming up to backflow, then reacts 4h.After reaction finished, raw material was removed in underpressure distillation.Cooling, mixture is poured in frozen water, with hcl acidifying and regulate pH value, has oily matter to generate, and gets intermediate 3-(hydroxyl-phenyl-phosphoryl)-2-methyl-propionic acid tetrahydrofurfuryl alcohol ester.
The 3-(hydroxyl-phenyl-phosphoryl) of gained-2-methyl-propionic acid tetrahydrofurfuryl alcohol ester is dissolved in dehydrated alcohol, adds the trimeric cyanamide of 0.8 mole, 48h refluxes in being furnished with three neck round-bottomed flasks of drying tube.Cooling, filter ethanol, washing, vacuum-drying gets the white powder product.Products therefrom carries out hydrogen spectrum and infrared inspection.Productive rate is 79%.
Figure below is the composite diagram of fire retardant 3-(hydroxyl-benzyl-phosphoryl)-2-phenyl-tetrahydrofurfuryl propionate melamine salt (CEBPTHF-M):
In the four-necked bottle that whipping appts, thermometer, dropping funnel are housed; add respectively the 3-(hydroxyl-benzyl-phosphoryl)-2-phenyl-propionic acid (CEBP) of 0.9 mole and the thionyl chloride of 1 mole; heating makes its dissolving; then drip two drying treatment 2; the 6-lutidine; keep 78 ℃ of certain temperatures, reaction 3h.After having reacted, underpressure distillation also adds appropriate toluene and repeats underpressure distillation to remove thionyl chloride.Add toluene to make its dissolving, then drip the tetrahydrofurfuryl alcohol of 1 mole, keep 96 ℃ of certain temperatures, reaction 1.5h dropwises and has been warming up to backflow, then reacts 3h.After reaction finished, raw material was removed in underpressure distillation.Cooling, mixture is poured in frozen water, with hcl acidifying and regulate pH value, has oily matter to generate, and gets intermediate 3-(hydroxyl-benzyl-phosphoryl)-2-phenyl-propionic acid tetrahydrofurfuryl alcohol ester.
The 3-(hydroxyl-benzyl-phosphoryl) of gained-2-phenyl-propionic acid tetrahydrofurfuryl alcohol ester is dissolved in dehydrated alcohol, adds the trimeric cyanamide of 0.9 mole, 46h refluxes in being furnished with three neck round-bottomed flasks of drying tube.Cooling, filter ethanol, washing, vacuum-drying gets the white powder product.Product carries out hydrogen spectrum and infrared inspection.Productive rate is 82%.
The end product of embodiment 1 to 5 gained is the melamine salt fire retardant, and it is carried out hydrogen spectrum and infrared spectra detection, and it is as shown in table 1 that the gained compound structure characterizes spectral data.
The melamine salt fire retardant structural characterization spectral data of table 1 embodiment 1 to 5 gained
Known, same functional group, the chemical shift meeting that goes out the peak on infrared spectra is subjected to various condition influence and has a little to change.By data shown in table 1, in conjunction with Fig. 2 and Fig. 3, can draw, the end product of embodiment 1 to 5 gained is the phosphonic acids melamine salt fire retardant that contains the tetrahydrofuran (THF) ring structure.
In following embodiment, Flameproof polyamide thin film technology method is identical with above-mentioned Flameproof polyamide thin film technology method, and just material and consumption are different, and described umber is parts by weight.
Embodiment 7:
Embodiment 8:
Embodiment 9:
Embodiment 10:
Embodiment 11:
Adopt above-mentioned detection method that the Flameproof polyamide film that embodiment 6-11 makes is tested, its test result is as shown in table 2.
Table 2
MD is that vertically TD is horizontal
Embodiment 12
Embodiment 13:
Embodiment 14:
Embodiment 15:
Embodiment 16:
Embodiment 17:
Adopt above-mentioned detection method that the Flameproof polyamide film that embodiment 12-17 makes is tested, its test result is as shown in table 3.
Table 3
MD is that vertically TD is horizontal
Can draw by data shown in table 2 and table 3, the over-all propertieies such as the Flameproof polyamide film flame retardant resistance of embodiment 6 to 17 gained and mechanical property are better.
The above is only preferred embodiment of the present invention, is not for limiting protection scope of the present invention.Every equalization that content is done according to the present invention changes and modifies, and all is encompassed in the scope of the claims of the present invention.
Claims (10)
1. a melamine salt fire retardant, is characterized in that, described fire retardant is the phosphonic acids melamine salt that contains the tetrahydrofuran (THF) ring structure, and its general structure is as follows:
R wherein
1Be benzyl or aryl functional group, R
2, R
3Be alkyl, alkoxyl group, aryl or hydrogen, described alkyl or alkoxyl group comprise C
1-C
12Alkyl or alkoxyl group.
2. a melamine salt fire retardant as claimed in claim 1, is characterized in that, described aryl functional group comprises the phenyl that phenyl, naphthyl, monoalkyl replace, the naphthyl that monoalkyl replaces; Described alkyl, alkoxyl group comprise C
1-C
6Alkyl or alkoxyl group.
3. a Flameproof polyamide film, is characterized in that, totally 100 parts of described polyamide layer materials comprise the described melamine salt fire retardant of claim 1 or 2 of 5-10 part; Described Flameproof polyamide film also comprises the polymeric amide of 85-94 part, the oxidation inhibitor of 0.5-2 part, the catalyzer of 1-3 part.
4. a Flameproof polyamide film as claimed in claim 3, is characterized in that, described polymeric amide comprises aliphatics nylon; Described catalyzer comprises the metal lewis acid; Described oxidation inhibitor comprises β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, N; N '-two-betanaphthyl-Ursol D, N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine or inorganic phosphate.
5. a Flameproof polyamide film as claimed in claim 3, is characterized in that, described polyamide layer comprises the melamine salt fire retardant of 5-8 part; Described Flameproof polyamide film also comprises the polymeric amide of 88-92 part, the oxidation inhibitor of 1-2 part, the catalyzer of 2-3 part.
6. a Flameproof polyamide film as claimed in claim 3, is characterized in that, the thickness of described polyamide layer is 50-200 μ m.
7. a Flameproof polyamide film as claimed in claim 3, is characterized in that, the thickness of described polyamide layer is 60-100 μ m.
8. a Flameproof polyamide film as claimed in claim 3, is characterized in that, the thickness of described Flameproof polyamide film is 120-180 μ m.
9. the preparation method of a melamine salt fire retardant as claimed in claim 1 or 2, is characterized in that, described preparation method comprises the steps:
(1) diprotic acid compound and thionyl chloride are joined in reaction vessel, react 3～5h under 70～78 ℃, generate acyl chlorides, remaining thionyl chloride is removed in underpressure distillation; Mole proportioning of described diprotic acid compound and thionyl chloride is 0.8～1.0:1;
(2) step (1) gained acyl chlorides and tetrahydrofurfuryl alcohol are carried out esterification, under 85～100 ℃, reaction 1～2h, being warming up to solution has backflow, react 3～4h, after reaction finished, raw material was removed in underpressure distillation again, mixture is poured in frozen water, regulates pH to 5～7, obtains intermediate; The mol ratio of described tetrahydrofurfuryl alcohol and diprotic acid compound is 1～1.2:1;
(3) step (2) gained intermediate is dissolved in dehydrated alcohol, adds trimeric cyanamide backflow 45-50h, cooling, filtration, washing, drying get the white powder product; The mol ratio of described trimeric cyanamide and diprotic acid compound is 1:1;
Its reaction expression is as follows:
10. a Flameproof polyamide thin film technology method as described in one of claim 3-8, is characterized in that, described preparation method comprises the steps:
(1) mechanical pre-mixing: polymeric amide is dry, mix with the phosphonic acids melamine salt fire retardant, catalyzer and the oxidation inhibitor high-speed stirring that contain the tetrahydrofuran (THF) ring structure, be prepared into and process material;
(2) melting mixing: step (1) gained is processed material make sheet vacuumizing to melt extrude under condition;
(3) two-way stretch: step (2) gained sheet is made the Flameproof polyamide film through overcooling slab, stretch processes.
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