CN102850622B - Organic halogen-free flame-retardant silane cross-linked polyethylene and its preparation method and composition - Google Patents
Organic halogen-free flame-retardant silane cross-linked polyethylene and its preparation method and composition Download PDFInfo
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Abstract
The invention discloses an organic halogen-free flame-retardant silane cross-linked polyethylene and its preparation method and composition. The composition comprises a silane grafting material A and a catalyst master batch B. A flame retardant in the catalyst master batch B is a hydroxyl-containing organic halogen-free flame retardant. The preparation method comprises that the silane grafting material A and the catalyst master batch B are fully mixed and then are stood for 1 to 3 days after molding so that organic halogen-free flame-retardant silane cross-linked polyethylene is obtained. Through efficient synergistic flame retardation of flame retardant elements and groups, the organic halogen-free flame-retardant silane cross-linked polyethylene has an oxygen index more than 27 in the presence of less flame retardant elements, has flame retardation reaching to a UL94V-0 grade, has mechanical, insulating and heat-resisting properties which are not influenced, and can be used for manufacture of cables or tubes.
Description
Technical field
The present invention relates to flame-retardant polyethylene plastic field, specifically a kind of organic halogen-free organosilane crosslinked polyethylene and preparation method thereof and composition.
Background technology
Polyethylene is owing to having excellent insulation and dielectric properties, and having replaced gradually polyvinyl chloride becomes the main raw for the manufacture of electric wire and cable jacket.But the obvious problem that polyethylene exists as cable material is the not good and easy burning of resistance toheat.From the sixties in last century, cables manufacturing producer just starts polyethylene to carry out cross-linking modified, and sub polyethylene subchain is linked mutually, forms three-dimensional net structure, thereby greatly improves the performances such as its high temperature resistant and resistance to creep.Cross-linking method mainly contains peroxide crosslinking, cross-linking radiation and crosslinked with silicane.The more difficult control quality of item of peroxide crosslinking, irradiation crosslinking technological are complicated and investment is large, and crosslinked with silicane is simple and can better ensure the over-all properties of goods, so silane crosslinking process has become the main production of domestic and international mesolow cables manufacturing.
Poly oxygen index is only 17 left and right, also only has 19~20 by the polyethylene oxygen index of crosslinked with silicane, and the requirement of the oxygen index that does not reach CABLE MATERIALS completely more than 25, is also difficult to reach the fire-retardant rank of UL94V-0.This has limited the application of organosilane crosslinked polyethylene to a certain extent.In order to give organosilane crosslinked polyethylene good flame retardant properties, patent CN 1345893A and CN 1223628C disclose respectively a kind of preparation method of crosslinked with silicane fire-retardant polyethylene cable material.The former obtains non-halogen flame-retardant cable with the inorganic combustion inhibitor blend such as magnesium hydroxide, red phosphorus, expanded graphite when polyethylene is carried out to Silane Grafted modification.Although simple and easy to do, inorganic combustion inhibitor and organic polymer Miscibility are not high, the introducing of fire retardant simultaneously also can cause detrimentally affect to dielectric properties.The latter adopts two-step approach, prepares Silane Grafted masterbatch and brominated flame-retardant master batch, then by both hybrid process.Utilize this method can obtain the good organosilane crosslinked polyethylene of flame retardant properties, but belong to the category that has halogen fire-retardant.Patent CN 102304254A and CN 101880417A, all adopting metal oxide or metal hydroxides is that main flame retardant, organic phosphates are auxiliary fire retardant, prepares flame-retardant organosilane cross-linked poly-ethylene.Because the introducing of organic constituent plays lubrication to a certain extent, improve the consistency between inorganic combustion inhibitor and organic polymer, prepared organosilane cross-linked poly-ethylene cable material over-all properties increases, but still does not solve the difficult problem that additive flame retardant causes material over-all properties to decline., non-halogen fire-retardant element is introduced in molecular chain, giving the lasting anti-flaming function of macromolecular material (being intrinsic flame retardant resistance) has become a kind of effectively solution route for this reason.But for obtaining certain flame retardant effect, main dependence improved single ignition-proof element consumption, causes introducing too much chemical weak bond, causes the obvious decline of the performances such as material is heat-resisting at present.Therefore, must manage to reduce the chemical weak bond content that ignition-proof element forms and just likely reduce the negative impact that it causes performances such as material are heat-resisting, relevant approach mainly comprises: bring into play multiple ignition-proof element cooperative flame retardant function, give ignition-proof element and (or) resin special chemical structure.
Summary of the invention
One of object of the present invention is to provide the composition of the organic halogen-free flame-retardant organosilane cross-linked poly-ethylene of preparation.
Another object of the present invention is to provide a kind of preparation method of organic halogen-free organosilane crosslinked polyethylene, by the agent of hydroxyl organic halogen-free is incorporated in sub polyethylene minor structure, realizes organic intrinsic halogen-free flameproof of organosilane crosslinked polyethylene.
A further object of the present invention is to provide organic halogen-free organosilane crosslinked polyethylene prepared by aforesaid method.Utilize the prepared cable of the method or tubing when mechanics, insulation, resistance toheat are maintained, can obtain better flame retardant properties.
Object of the present invention is achieved through the following technical solutions:
Prepare a composition for organic halogen-free flame-retardant organosilane cross-linked poly-ethylene, comprise Silane Grafted material A material and catalyst masterbatch B material, the fire retardant in described B material is the agent of hydroxyl organic halogen-free, and this fire retardant is one or more in following structure:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7for the pure alkyl of C1 ~ C13 or containing the alkyl of phenyl ring, hydroxyl, nitro, ehter bond, cyclohexyl, naphthyl or furan structure.
Preferably, above-mentioned R
1, R
2, R
3, R
4, R
5, R
6, R
7for
In any one.
Preferably, the preparation process of described B material: according to the mass fraction, by 5~20 parts of polyvinyl resins, 0.5~25 part, auxiliary agent carrier, 1~25 part of hydroxyl organic halogen-free agent, 0.01~5 part of crosslinking catalyst, 0.5~15 part, aqua of product, 0.01~3 part, oxidation inhibitor, in high-speed mixer, fully mix, mixing at 120~180 DEG C, granulation, dry, make B material.
Preferably, the preparation process of described A material: according to the mass fraction, by dry 80~95 parts of polyvinyl resins pre-treatment to moisture below 600ppm, then fully mix with 0.01~0.5 part of 0.5~5 part of silane coupling agent, peroxide initiator, mixing at 120~230 DEG C, granulation, dry, make A material.
Preferably, above-mentioned polyvinyl resin is any one or a few in Low Density Polyethylene (LDPE), linear low density of polyethylene (LLDPE), medium-density polyethylene (MDPE), high density polyethylene(HDPE) (HDPE), ethylene-propylene copolymer;
Preferably, above-mentioned auxiliary agent carrier is any one or a few in ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA).
Preferably, above-mentioned crosslinking catalyst be dibutyl tin laurate, lauric acid toxilic acid dibutyl tin, Bis(lauroyloxy)dioctyltin, dibutyltin diacetate, to any one or a few in methylphenyl acetic acid, Witco 1298 Soft Acid, dodecylbenzene sulfonation acetyl, toluenesulphonic acids, toluene sulfonation acetyl, first sulfonation acetyl, naphthene sulfonic acid, tetrapropyl Phenylsulfonic acid;
Preferably, above-mentioned product aqua is any one or a few in two water sodium formiates, Sodium acetate trihydrate, sodium dihydrogen phosphate-water, carbamide pre-polymerization resin;
Preferably, above-mentioned oxidation inhibitor is 2,6-ditertbutylparacresol, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, two (3,5-di-tert-butyl-hydroxy phenyl) thioether, 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), 4, any one or a few in 4 '-thiobis-(6-tertiary butyl meta-cresol).
Preferably, above-mentioned silane coupling agent is any one or a few in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl silane triisopropoxide, vinyltriacetoxy silane, vinylbenzene ethyl trimethoxy silane, (3-acryloyl-oxy propyl group) Trimethoxy silane, (3-methacryloxypropyl) Trimethoxy silane, (3-methacryloxypropyl) triethoxyl silane, (3-methacryloxypropyl) three isopropoxy silane;
Preferably, above-mentioned peroxide initiator is any one or a few in benzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, dicumyl peroxide, cyclohexanone peroxide, tertbutyl peroxide.
Described hydroxyl organic halogen-free agent is prepared by addition reaction by DOPO, DOPS, DPPO, DPPA, DAPO and aldehydes, and concrete preparation method does not limit.The structural formula of DOPO, DOPS, DPPO, DPPA and DAPO is as follows respectively:
Above-mentioned DOPO-R
1-OH, DOPS-R
2-OH, DPPO-R
3-OH, HO-R
4-DPPA-R
5-OH, HO-R
6-DAPO-R
7the preparation method of-OH, concrete steps are as follows:
1) under protection of inert gas, will be dissolved in organic solvent containing phosphorus heterocycle reactant, then add aldehydes and tertiary amine catalyst, 25~150 DEG C of stirring reactions 0.5~24 hour, obtain reaction solution;
2) reaction solution is first filtered or rotary evaporation, after then washing and being dried, obtain object product.Described is 9 containing phosphorus heterocycle reactant, 10-dihydro-9,10-oxa--10-phospho hetero phenanthrene-10-oxide compound (DOPO), 9,10-dihydro-9,10-oxa--10-phospho hetero phenanthrene-10-sulfide (DOPS), 2,8-dimethyl-phenoxazine phosphorus-10-oxide compound (DPPO), 5,10-dihydro-Phenylphosphine piperazine-10-oxide compound (DPPA) and/or 9,10-dihydro-9-azepine-10-phospho hetero phenanthrene-10-oxide compound (DAPO).
Described aldehydes is (1.25~1) with the molar ratio containing phosphorus heterocycle reactant: 1 (for DOPO, DOPS and DPPO), (2.5~2): 1 (for DPPA and DAPO); The mass ratio of catalyzer and phosphorus-nitrogen containing heterocycle reactant is (0.005~0.1): 1; In every gram of phosphorus-nitrogen containing heterocycle reactant, adding the volume of solvent is 0.5~15ml.
Described catalyzer is first dissolved in organic solvent, then aldehydes and catalyst solution are added drop-wise in reaction system in 0.5 ~ 2h.
Described aldehydes is formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde-n, isobutyric aldehyde, valeraldehyde, isovaleric aldehyde, special valeral, n-hexyl aldehyde, enanthaldehyde, n-octaldehyde, n-nonyl aldehyde, 3, 5, 5-trimethylammonium hexanal, n-capric aldehyde, the undecyl aldehyde, lauric aldehyde, tridecyl aldehyde, the 2-methyl undecyl aldehyde, phenyl aldehyde, phenylacetic aldehyde, phenylpropyl aldehyde, p-tolyl aldehyde, p-Hydroxybenzaldehyde, m-hydroxybenzaldehyde, salicylaldhyde, Vanillin, 2-hydroxyl-5-nitrobenzaldehyde, paranitrobenzaldehyde, m-nitrobenzaldehyde, Ortho Nitro Benzaldehyde, 4-ethylbenzene formaldehyde, 2-diphenylphosphine phenyl aldehyde, 3, 4-(methylene-dioxy) phenyl aldehyde, 3, 4, 5-TMB, furtural, 5-methyl furan aldehyde, 2-naphthaldehyde, any one or a few in hexahydrobenzaldehyde.
Described tertiary amine catalyst is trolamine, vulkacit H, Tetramethyl Ethylene Diamine, 4-methyl hexamethylene diamine, dimethylethanolamine, benzyldimethylamine, adjacent hydroxybenzyl dimethylamine, N, accelerine, N-methyl-N-ethylaniline, 2,4,6-tri-(dimethylamino methyl) phenol, triethylamine, dimethylamino ethylamine, the first and second propylamine, pyridine, N dimethylamine base benzylamine, N, any one or a few in N-lupetazin.
Described organic solvent is any one or a few in methyl alcohol, ethanol, Virahol, acetone, butanone, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, methyl acetate, propyl acetate, ethyl acetate, methylene dichloride, ethylene dichloride, chloroform, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO).
The preparation method of above-mentioned a kind of organic halogen-free organosilane crosslinked polyethylene, fully mixes A material and B material, after moulding, places 1~3 day, makes organic halogen-free organosilane crosslinked polyethylene.
Preferably, the mass ratio of described A material and B material is (3 ~ 9): 1.
The intrinsic fire retardant mechanism of organosilane crosslinked polyethylene of the present invention is: add after the organic halogen-free agent containing active group hydroxyl, grafted silane in sub polyethylene subchain is in the time of hydrolytic crosslinking and hydroxyl generation condensation reaction, by fire-retardant group grafting on sub polyethylene subchain, thereby it is fire-retardant to realize polyethylene intrinsic; The efficient cooperative flame retardant effect producing between ignition-proof element and fire-retardant group gives organosilane crosslinked polyethylene good flame retardant properties.
Compared with prior art, tool of the present invention has the following advantages and beneficial effect:
(1) the present invention adopts organic intrinsic Non-halogen Flame Retardant Technology, by add the agent of a kind of hydroxyl organic halogen-free in organosilane crosslinked polyethylene, utilize the contained active group hydroxyl of fire retardant to participate in silane hydrolyzate crosslinking reaction and form the part of sub polyethylene minor structure, by phosphorus, nitrogen, sulphur halogen-free flameproof element and aromatic nucleus, the functional group of the fire-retardant group composition such as heterocycle is incorporated in basal body structure, utilize phosphorus, nitrogen, sulphur ignition-proof element and phenyl ring, the feature of efficient cooperative flame retardant between the fire-retardant group such as heterocycle, effectively improve the flame retardant properties of material, provide a new way for improving the flame retardant properties of macromolecular material.
(2) the organosilane crosslinked polyethylene oxygen index that prepared by the present invention reaches more than 27, and fire-retardant rank reaches UL94V-0 level, and simultaneously mechanics, insulation, resistance toheat are unaffected, can be used for manufacturing cable or pipe material product.
Embodiment
Be described further of the present invention below in conjunction with specific embodiment, but content of the present invention is not limited to following embodiment.
Raw material DPPA preparation process: 169g pentanoic and 94g phosphorus trichloride are packed in the 1L tri-neck round-bottomed flasks of belt stirrer, condensation exhaust device and nitrogen protection, slowly be heated to 70 DEG C of stirring reactions 1 hour, then be heated to 220 DEG C of reactions 6 hours, reaction mixture generates red solid, cool to room temperature; Dissolve red solid with dimethyl formamide/water (volume ratio 10:1) mixing solutions of 600ml heat, solution is poured in 2L cold distilled water and violent stirring 1 hour, obtain raw product; Filter, use 300ml ethanol, after 96 hours, to be dried and to remove ethanol through Soxhlet extractor extracting, obtain final product 174g.Reference: Schafer A., Seibold S., Walter O., Doring M.Polymer Degradation and Stability, 2008,93:557-560.
Raw material DAPO preparation process: 100g 2-phenylaniline is added in the three neck round-bottomed flasks that 400g phosphorus trichloride, nitrogen protection are housed, and hydrogenchloride is emitted in adition process.Be heated to 130 DEG C and react 18 hours until hydrogenchloride is no longer emitted, be cooled to 40 DEG C, vacuum is removed phosphorus trichloride and is obtained dark brown solid.Add 8g aluminum chloride to be heated to 165 DEG C of reactions after 6 hours, be cooled to room temperature and obtain 141g brown solid.Then brown solid is joined in the band condenser round-bottomed flask that 600ml methylene dichloride is housed, 50 DEG C of stirrings after 1 hour are poured solution in the bath of 1L trash ice, precipitation generates, and stirred solution, until ice melts completely, filters vacuum-drying and obtains final product 45g purple solid.Reference: Dewar M.J.S., Kubba V.P, Journal of American Chemical Society, 1960,82:5685-5688.
Raw material DOPO is commercially available industrial goods.
The preparation process of raw material DPPO: 60g p-Xylol base ether, 105ml phosphorus trichloride, 40g aluminum chloride are packed in the 1L tri-neck round-bottomed flasks of belt stirrer, condensation exhaust device and nitrogen protection, slowly be heated to 85 DEG C of stirring reactions 24 hours, reaction mixture generates white solid, cool to room temperature; Then pouring 1kg trash ice into stirs until ice all melts; Filter, successively use 1mol/L hydrochloric acid, saturated solution of sodium bicarbonate and distilled water wash, dry after in benzene recrystallization, 120 DEG C of vacuum-drying 24h, obtain final product 66.7g.Reference: Schafer A., Seibold S., Lohstroh W., Walter O., Doring M.Journal of Applied Polymer Science, 2007,105:685-696.
The preparation process of raw material DOPS: 54g DOPO, 150ml toluene are packed in the 500ml tri-neck round-bottomed flasks of belt stirrer, thermometer and argon shield, be heated to 55 DEG C, add 14g P
4s
10after stirring reaction 2h, then add 14gP
4s
10cool to 40 DEG C of stirring reaction 15h, reaction mixture is removed toluene, 100ml chloroform washing and filtering through thin layer filtered through silica gel, vacuum.Filtrate is poured in 100ml sodium bicarbonate and stir 20min under argon shield, after after filtration with 50 DEG C of vacuum-drying 24h, obtain final product 43.5g.Reference: Rakotomalala M., Wagner S., Zevaco T., Ciesielski M., Walter O., Doering M.Heterocycles, 2011,83,743-753.
HO-CH
2-DPPA-CH
2the preparation process of-OH: 21.5g DPPA and 100ml dimethylbenzene are added in the 500ml flask with prolong, mechanical stirring, constant pressure funnel and nitrogen protection; be warming up to 90 DEG C; after dissolving completely, DPPA dripped the formalin of 16.5ml 37% and the 10ml xylene solution containing 0.15g trolamine in 1 hour; continue reaction 0.5 hour; then by reaction mixture through vacuum-drying 12h at filtration, washing with alcohol, 60 DEG C, finally obtain the organic halogen-free agent HO-CH containing phosphorus heterocycle
2-DPPA-CH
2-OH, productive rate is 91.8%.Organic halogen-free agent HO-CH
2-DPPA-CH
2in-OH, each element quality percentage composition is respectively: C 69.14%, H 5.76%, O 6.58%, P 12.76%, N 5.76%; Nuclear magnetic spectrogram data are:
1h NMR (DMSO-d6): 7.00-7.88ppm (8H, Ph-H), 4.00-4.30ppm (4H, P-CH
2-, N-CH
2-), 5.58-5.64ppm (2H, O-H);
31p NMR (DMSO-d6): 15.41ppm (s).The impact of fire retardant F-1 on macromolecular material thermostability and flame retardant effect are in table 1.
HO-R
4-DPPA-R
5-OH (R
4for
r
5for
) preparation process: 21.5g DPPA and 200ml ethanol/dimethyl sulfoxide (DMSO) (volume ratio 1/1) are added to band prolong, mechanical stirring, in the 500ml flask of constant pressure funnel and nitrogen protection, be warming up to 80 DEG C, after DPPA dissolves completely, in 0.5 hour, drip 50ml containing the ethanolic soln of 4.5g acetaldehyde and 10.6g phenyl aldehyde and 10ml the ethanolic soln containing 0.5g triethylamine, continue reaction 4 hours, then by reaction mixture process rotary evaporation, filter, washing with alcohol, vacuum-drying 12h at 60 DEG C, finally obtain the organic halogen-free agent 35.3g containing phosphorus heterocycle, productive rate is 96.4%.The impact of fire retardant F-2 on macromolecular material thermostability and flame retardant effect are in table 1.
HO-CH
2-DAPO-CH
2the preparation method of-OH: 21.5g DAPO and 120ml ethyl acetate/Virahol (volume ratio 1/1) are added to band prolong, mechanical stirring, in the 500ml flask of constant pressure funnel and nitrogen protection, be warming up to 75 DEG C, after dissolving completely, DAPO dripped the formalin of 16ml 37% and the 10ml chloroformic solution containing 0.2g vulkacit H in 2 hours, continue reaction 1 hour, then by reaction mixture process rotary evaporation, filter, washing with alcohol, vacuum-drying 12h at 60 DEG C, finally obtain the organic halogen-free agent 26.1g containing phosphorus heterocycle, productive rate is 93.6%.The impact of fire retardant F-3 on macromolecular material thermostability and flame retardant effect are in table 1.
DOPO-CH
2the preparation process of-OH: 21.6g DOPO and 100ml dimethylbenzene are added in the 500ml flask with prolong, mechanical stirring, constant pressure funnel and nitrogen protection; be warming up to 90 DEG C; after dissolving completely, DOPO dripped the formalin of 8ml 37% and the 10ml xylene solution containing 0.15g trolamine in 1 hour; continue reaction 0.5 hour; then by reaction mixture through vacuum-drying 12h at filtration, washing with alcohol, 60 DEG C; finally obtain the organic halogen-free agent 22.9g containing phosphorus heterocycle, productive rate is 92.3%.The impact of fire retardant F-4 on macromolecular material thermostability and flame retardant effect are in table 1.
DOPO-R
1-OH (R
1for
) preparation process: 21.6g DOPO and 200ml methanol/toluene (volume ratio 1/2) are added to band prolong, mechanical stirring, in the 500ml flask of constant pressure funnel and nitrogen protection, be warming up to 65 DEG C, after DOPO dissolves completely, in 0.5 hour, drip 50ml containing the ethanolic soln of 12.2g p-Hydroxybenzaldehyde and 10ml the ethanolic soln containing 0.6g benzyldimethylamine, continue reaction 16 hours, then reaction mixture process is filtered, washing with alcohol, vacuum-drying 12h at 60 DEG C, finally obtain the organic halogen-free agent 32.7g containing phosphorus heterocycle, productive rate is 96.7%.The impact of fire retardant F-5 on macromolecular material thermostability and flame retardant effect are in table 1.
DPPO-CH
2the preparation process of-OH: 24.4g DPPO and 120ml dimethylbenzene are added in the 500ml flask with prolong, mechanical stirring, constant pressure funnel and nitrogen protection; be warming up to 90 DEG C; after dissolving completely, DPPO dripped the formalin of 8ml 37% and the 10ml xylene solution containing 0.15g trolamine in 1 hour; continue reaction 0.5 hour; then by reaction mixture through vacuum-drying 12h at filtration, washing with alcohol, 60 DEG C; finally obtain the organic halogen-free agent 26.1g containing phosphorus heterocycle, productive rate is 94.6%.The impact of fire retardant F-6 on macromolecular material thermostability and flame retardant effect are in table 1.
DOPS-CH
2the preparation process of-OH: 23.2g DOPS and 150ml dimethylbenzene are added in the 500ml flask with prolong, mechanical stirring, constant pressure funnel and nitrogen protection; be warming up to 90 DEG C; after dissolving completely, DOPS dripped the formalin of 8ml 37% and the 10ml xylene solution containing 0.15g trolamine in 1 hour; continue reaction 0.5 hour; then by reaction mixture through vacuum-drying 12h at filtration, washing with alcohol, 60 DEG C; finally obtain the organic halogen-free agent 24.7g containing phosphorus heterocycle, productive rate is 93.6%.The impact of fire retardant F-7 on macromolecular material thermostability and flame retardant effect are in table 1.
The agent of table 1 organic halogen-free is on the impact of macromolecular material thermostability and flame retardant effect
Embodiment 1
The LDPE that is 2.3g/10min by quality 9kg melt flow rate (MFR) is dried to moisture below 600ppm, then fully mix with 0.5kg vinyltrimethoxy silane, 50g benzoyl peroxide, mixing at 150 DEG C, granulation, dry, vacuum packaging, obtains A material; The LDPE, the 0.5kgEVA that are 2.3g/10min by 1kg melt flow rate (MFR), 1kg DOPO-CH
2-OH, 0.3kg dibutyl tin laurate, 0.5kg carbamide pre-polymerization resin, 5g tetra-(β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester fully mixing in high-speed mixer, mixing at 130 DEG C, granulation, dry, vacuum packaging, obtains B material; By 9kgA material and the fully mixing of 1kgB material, enter forcing machine and injection moulding machine is made test bars, at room temperature place 2 days, complete crosslinked with silicane process.Oxygen index and vertical combustion are tested by GB/T2406.2-2009 and ASTM D 5207 standards respectively, and oxygen index is 27.3, and fire-retardant rank reaches UL94V-0 (3.2mm) level.Tensile strength and elongation at break are tested by GB/T 1040-2006 standard, and tensile strength is 14.6MPa, and elongation at break is 485%.Volume specific resistance is tested by GB/T1410-2006 standard, is 2.3 × 10
17Ω cm.5% heat decomposition temperature (N
2atmosphere, 10 DEG C/min of temperature rise rate) be 491 DEG C.
Embodiment 2
The LDPE that is 0.6g/10min by quality 9.5kg melt flow rate (MFR) is dried to moisture below 600ppm, then fully mix with 0.3kg vinyltriethoxysilane, 40g dicumyl peroxide, mixing at 160 DEG C, granulation, dry, vacuum packaging, obtains A material; The LDPE that is 2.3g/10min by 0.5kg melt flow rate (MFR), 1.5kg EAA, 1.5kg DPPO-CH
2-OH, 0.2kg lauric acid toxilic acid dibutyl tin, 1kg bis-water sodium formiates, 10g 2,6 ditertiary butyl p cresol are fully mixed in high-speed mixer, and mixing at 150 DEG C, granulation are dry, and vacuum packaging obtains B material; By 8kg A material and the fully mixing of 2kgB material, enter forcing machine and injection moulding machine is made test bars, at room temperature place 3 days, complete crosslinked with silicane process.Oxygen index is 28.8, and fire-retardant rank reaches UL94V-0 (1.6mm) level, and tensile strength is 15.7MPa, and elongation at break is 422%.Volume specific resistance is 3.7 × 10
17Ω cm, 5% heat decomposition temperature is 495 DEG C.
Embodiment 3
The LDPE that is 2.3g/10min by quality 9kg melt flow rate (MFR) is dried to moisture below 600ppm, then fully mix with 0.2kg vinyl three (2-methoxy ethoxy) silane, 10g peroxidized t-butyl perbenzoate, mixing at 180 DEG C, granulation, dry, vacuum packaging, obtains A material; The LLDPE that is 1.2g/10min by 1kg melt flow rate (MFR), 2kg EMA, 2.5kg DOPS-CH
2-OH, 5g Bis(lauroyloxy)dioctyltin, 50g Sodium acetate trihydrate, two (3, the 5-di-tert-butyl-hydroxy phenyl) thioethers of 0.1kg fully mix in high-speed mixer, and mixing at 140 DEG C, granulation are dry, and vacuum packaging, obtains B material; By 8.5kg A material and the fully mixing of 1.5kg B material, enter forcing machine and injection moulding machine is made test bars, at room temperature place 2 days, complete crosslinked with silicane process.Oxygen index is 29.9, and fire-retardant rank reaches UL94V-0 (1.6mm) level, and tensile strength is 14.1MPa, and elongation at break is 357%.Volume specific resistance is 2.9 × 10
17Ω cm, 5% heat decomposition temperature is 487 DEG C.
Embodiment 4
The LLDPE that the LDPE that is 2.3g/10min by quality 7kg melt flow rate (MFR) and 2kg melt flow rate (MFR) are 1.2g/10min is dried to moisture below 600ppm, then fully mix with 0.1kg vinyl silane triisopropoxide, 5g cyclohexanone peroxide, mixing at 200 DEG C, granulation, dry, vacuum packaging, obtains A material; The LDPE that is 2.3g/10min by 1kg melt flow rate (MFR), 0.25kg EEA, 1.5kgHO-CH
2-DPPA-CH
2-OH, 50g dibutyltin diacetate, 0.5kg sodium dihydrogen phosphate-water, 0.3kg4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol) fully mixes in high-speed mixer, and mixing at 160 DEG C, granulation are dry, and vacuum packaging obtains B material; By 8kg A material and the fully mixing of 2kg B material, enter forcing machine and injection moulding machine is made test bars, at room temperature place 1 day, complete crosslinked with silicane process.Oxygen index is 29.6, and fire-retardant rank reaches UL94V-0 (1.6mm) level, and tensile strength is 15.4MPa, and elongation at break is 451%.Volume specific resistance is 3.1 × 10
17Ω cm, 5% heat decomposition temperature is 496 DEG C.
Embodiment 5
The HDPE that the LDPE that is 2.3g/10min by quality 7kg melt flow rate (MFR) and 1kg melt flow rate (MFR) are 6.5g/10min is dried to moisture below 600ppm, then fully mix with 0.3kg vinylbenzene ethyl trimethoxy silane, 3g benzoyl peroxide, 1g dicumyl peroxide, mixing at 140 DEG C, granulation, dry, vacuum packaging, obtains A material; The LLDPE that is 1.2g/10min by 2kg melt flow rate (MFR), 0.5kg EBA, 2kg HO-CH
2-DAPO-CH
2-OH, 0.1kg Bis(lauroyloxy)dioctyltin, 50g Witco 1298 Soft Acid, 1kg carbamide pre-polymerization resin, 0.1kg 4,4 '-thiobis-(6-tertiary butyl meta-cresol) fully mixes in high-speed mixer, mixing at 180 DEG C, granulation, dry, vacuum packaging, obtains B material; By 7.5kgA material and the fully mixing of 2.5kgB material, enter forcing machine and injection moulding machine is made test bars, at room temperature place 2 days, complete crosslinked with silicane process.Oxygen index is 30.5, and fire-retardant rank reaches UL94V-0 (1.6mm) level, and tensile strength is 16.8MPa, and elongation at break is 416%.Volume specific resistance is 3.8 × 10
17Ω cm, 5% heat decomposition temperature is 484 DEG C.
Embodiment 6
The MDPE that the LDPE that is 2.3g/10min by quality 6kg melt flow rate (MFR) and 2kg melt flow rate (MFR) are 5.4g/10min is dried to moisture below 600ppm, then fully mix with 0.2kg (3-acryloyl-oxy propyl group) Trimethoxy silane, 20g tertbutyl peroxide, mixing at 170 DEG C, granulation, dry, vacuum packaging, obtains A material; LLDPE, 0.25kg EVA, 0.25kg EAA, 0.5kgDOPO-CH that the LDPE that is 2.3g/10min by 1kg melt flow rate (MFR) and 1kg melt flow rate (MFR) are 1.2g/10min
2-OH, 0.5kgHO-CH
2-DPPA-CH
2-OH, 0.1kg dibutyl tin laurate, 0.2kg toluene sulfonation acetyl, 1kg carbamide pre-polymerization resin, 50g tetra-(β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester fully mixing in high-speed mixer, mixing at 160 DEG C, granulation, dry, vacuum packaging, obtains B material; By 8kg A material and the fully mixing of 2kg B material, enter forcing machine and injection moulding machine is made test bars, at room temperature place 2 days, complete crosslinked with silicane process.Oxygen index is 27.8, and fire-retardant rank reaches UL94V-0 (3.2mm) level, and tensile strength is 16.3MPa, and elongation at break is 435%.Volume specific resistance is 3.5 × 10
17Ω cm, 5% heat decomposition temperature is 498 DEG C.
Embodiment 7
The HDPE that the LDPE that is 2.3g/10min by quality 7kg melt flow rate (MFR) and 2kg melt flow rate (MFR) are 11.6g/10min is dried to moisture below 600ppm, then fully mix with 0.25kg vinyltriethoxysilane, 50g vinyl silane triisopropoxide, 10g dicumyl peroxide, mixing at 160 DEG C, granulation, dry, vacuum packaging, obtains A material; The LDPE, the 1kgEVA that are 2.3g/10min by 1kg melt flow rate (MFR), 1.5kg DOPO-R
1-OH (R
1for
), 0.2kg dibutyl tin laurate, 0.5kg Sodium acetate trihydrate, 50g 2,6 ditertiary butyl p cresol fully mix in high-speed mixer, mixing at 130 DEG C, granulation, dry, vacuum packaging, obtains B material; By 8.5kg A material and the fully mixing of 1.5kg B material, enter forcing machine and injection moulding machine is made test bars, at room temperature place 2 days, complete crosslinked with silicane process.Oxygen index is 29.2, and fire-retardant rank reaches UL94V-0 (3.2mm) level, and tensile strength is 15.7MPa, and elongation at break is 451%.Volume specific resistance is 3.3 × 10
17Ω cm, 5% heat decomposition temperature is 487 DEG C.
Embodiment 8
The HDPE that the LDPE that is 2.3g/10min by quality 8kg melt flow rate (MFR) and 1kg melt flow rate (MFR) are 1.1g/10min is dried to moisture below 600ppm, then fully mix with 50g vinyltriethoxysilane, 0.1kg (3-methacryloxypropyl) three isopropoxy silane, 3g benzoyl peroxide, 5g dicumyl peroxide, mixing at 180 DEG C, granulation, dry, vacuum packaging, obtains A material; The LDPE that is 2.3g/10min by 1kg melt flow rate (MFR), 0.5kg EAA, 1kgHO-R
4-DPPA-R
5-OH (R
4for
r
5for
), 0.2kg Bis(lauroyloxy)dioctyltin, 1kg bis-water sodium formiates, 80g tetra-(β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester fully mixing in high-speed mixer, mixing at 150 DEG C, granulation, dry, vacuum packaging, obtains B material; By 8.5kgA material and the fully mixing of 1.5kg B material, enter forcing machine and injection moulding machine is made test bars, at room temperature place 2 days, complete crosslinked with silicane process.Oxygen index is 29.5, and fire-retardant rank reaches UL94V-0 (3.2mm) level, and tensile strength is 16.5MPa, and elongation at break is 472%.Volume specific resistance is 2.7 × 10
17Ω cm, 5% heat decomposition temperature is 502 DEG C.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. for the preparation of a composition for organic halogen-free organosilane crosslinked polyethylene, comprise Silane Grafted material A material and catalyst masterbatch B material, it is characterized in that, the fire retardant in described B material is one or both in following structure:
Wherein, R
4, R
5, R
6, R
7for
in any one.
2. composition according to claim 1, it is characterized in that, the preparation process of described B material: according to the mass fraction, by 5~20 parts of polyvinyl resins, 0.5~25 part, auxiliary agent carrier, 1~25 part of hydroxyl organic halogen-free agent, 0.01~5 part of crosslinking catalyst, 0.5~15 part, aqua of product, 0.01~3 part, oxidation inhibitor, in high-speed mixer, fully mix, mixing at 120~180 DEG C, granulation, dry, make B material; Described auxiliary agent carrier is any one or a few in ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer.
3. composition according to claim 1, it is characterized in that, the preparation process of described A material: according to the mass fraction, by dry 80~95 parts of polyvinyl resins pre-treatment to moisture below 600ppm, then fully mix with 0.01~0.5 part of 0.5~5 part of silane coupling agent, peroxide initiator, mixing at 120~230 DEG C, granulation, dry, make A material.
4. composition according to claim 2, is characterized in that, described polyvinyl resin is any one or a few in Low Density Polyethylene, linear low density of polyethylene, medium-density polyethylene, high density polyethylene(HDPE), ethylene-propylene copolymer.
5. composition according to claim 2, it is characterized in that, described crosslinking catalyst is dibutyl tin laurate, lauric acid toxilic acid dibutyl tin, Bis(lauroyloxy)dioctyltin, dibutyltin diacetate, to any one or a few in methylphenyl acetic acid, Witco 1298 Soft Acid, dodecylbenzene sulfonation acetyl, toluenesulphonic acids, toluene sulfonation acetyl, first sulfonation acetyl, naphthene sulfonic acid, tetrapropyl Phenylsulfonic acid;
Described product aqua is any one or a few in two water sodium formiates, Sodium acetate trihydrate, sodium dihydrogen phosphate-water, carbamide pre-polymerization resin;
Described oxidation inhibitor is 2,6-ditertbutylparacresol, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, two (3,5-di-tert-butyl-hydroxy phenyl) thioether, 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), 4, any one or a few in 4 '-thiobis-(6-tertiary butyl meta-cresol).
6. composition according to claim 3, it is characterized in that, described silane coupling agent is vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl silane triisopropoxide, vinyltriacetoxy silane, vinylbenzene ethyl trimethoxy silane, (3-acryloyl-oxy propyl group) Trimethoxy silane, (3-methacryloxypropyl) Trimethoxy silane, (3-methacryloxypropyl) triethoxyl silane, any one or a few in (3-methacryloxypropyl) three isopropoxy silane,
Described peroxide initiator is any one or a few in benzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, dicumyl peroxide, cyclohexanone peroxide, tertbutyl peroxide.
7. a preparation method for organic halogen-free organosilane crosslinked polyethylene, is characterized in that, the A material in composition described in claim 1~6 any one and B material are fully mixed, and after moulding, places 1~3 day, makes organic halogen-free organosilane crosslinked polyethylene.
8. preparation method according to claim 7, is characterized in that, the mass ratio of described A material and B material is (3~9): 1.
9. the organic halogen-free organosilane crosslinked polyethylene of preparing according to method described in claim 7 or 8.
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