CN103724785B - A kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material and preparation method thereof - Google Patents
A kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material, mainly formed following raw material by quality to make: photovoltaic encapsulation matrix material 100 parts, microcapsule intumescent flame retardant 10～23 parts, through the inorganic nano fire retardant 2 of coupling agent treatment～15 parts, peroxide cross-linking agent 0.1～10 parts, phenols or phosphite ester kind antioxidant 0.05～5 parts, hindered amine light stabilizer 0.01～5 parts, UV absorbers 0.01～2 parts, viscosifier 0.01～3 parts；Direct solid phase polycondensation process and microcapsule technology is used to prepare micro encapsulation polyphosphoric acid melamine borate fire retardant, the synergistic effect of recycling inorganic nano fire retardant, effectively reducing the loading of fire retardant, the achieving of low cost ensures that its mechanical property and insulating properties are not remarkably decreased while improving encapsulating material fire resistance；The addition of other auxiliary agents can ensure that the performances such as the insulating properties of photovoltaic encapsulation material, wet-heat resisting, ultraviolet ageing performance meet the requirement in photovoltaic encapsulation field.
Description
(1) technical field
The present invention relates to a kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material and preparation method thereof.
(2) background technology
Photovoltaic, as a kind of cleaning, noise-less pollution regenerative resource, has simultaneously and does not discharge temperature
The advantage of room effect gas.Day by day serious, more along with the growing of energy demand and environmental pollution
The good solar energy that utilizes is considered as one of a kind of best solution.In actual applications, mostly
Number solar cell package becomes " sandwich " structure, the most such as: glass
/ EVA/ARC-Si/EVA/TPT structure.And the oxygen index (OI) of EVA is only 19 in said structure, belong to
Combustible material, and it is easily generated the black smoke with poisonous gas during burning.
Being usually used in flame-retardant system fire-retardant for EVA at present is phosphorus system, nitrogen system, silicon system, inorganic or compound
Type fire retardant.Wherein, the inorganic combustion inhibitor with magnesium aluminum compounds as representative exists because addition is led greatly
Cause the problems such as materials processing difficulty, mechanical properties decrease.Environmental protection expansion type flame retardant then generally require by
Carry out compositional flame-retardant after multiple fire retardant physical blendings such as " carbon source ", " acid source ", " source of the gas ", just can obtain
Obtain preferable flame retardant effect, the easy problems such as disperseing migration uneven, easy and the compatibility that produces.
In view of above-mentioned condition, one is presently required existing EVA equipment can be utilized to produce continuously simultaneously
There is the fire-retardant photovoltaic encapsulation material of highly effective flame-retardant effect.
(3) summary of the invention
The object of the invention be i.e. to provide a kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material and
Preparation method.
The technical solution used in the present invention is:
A kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material, is mainly made up of following quality
Raw material is made:
Described photovoltaic encapsulation matrix material is one of following or more than two of which mixture: ethylene-
Vinyl acetate co-polymer (EVA), metallocene catalysed polyethylene, POE, ethylene
Pentene copolymer；
Described microcapsule intumescent flame retardant is micro encapsulation polyphosphoric acid melamine borate
(MPB-S)；By polyphosphoric acid melamine borate (MPB) through ultra fine, then use melamine
Resin-coating prepare, polyphosphoric acid melamine borate (MPB) can with phosphate compound, three
Poly cyanamid compounds and boric acid are raw material, use direct solid phase polycondensation process to synthesize.
The described inorganic nano fire retardant through coupling agent treatment is the nanometer hydroxide through coupling agent treatment
One in aluminum, nano-sized magnesium hydroxide, nano silicon, nano zine oxide and nano titanium oxide
Or multiple, it is preferably the nano-sized magnesium hydroxide through coupling agent treatment and/or nano zine oxide, particle diameter is
10nm～100nm；Described coupling agent is this area conventional coupling agents, preferably silane coupler.
Above-mentioned raw materials is to prepare the master used by described low filling halogen-free expansion type flame-proof photovoltaic encapsulation material
Want raw material, do not include solvent used in preparation process.Described peroxide cross-linking agent, phenols or
Phosphite kind antioxidant, hindered amine light stabilizer, UV absorbers, viscosifier are this area
Conven-tional adjuvants.
Concrete, described peroxide cross-linking agent can be one of following or more than two of which mixing
Thing: 1,1-bis-(tert-butyl hydroperoxide)-3,3,5-trimethyl-cyclohexanes, 2,5-dimethylhexane
-2,5-di-tert-butyl peroxide, 2,5-dimethyl-2,5-double (benzoyl peroxide)-hexane, mistake
Oxidation diisopropylbenzene (DIPB), double (2-t-butylperoxyisopropyl) benzene, t-butylcumylperoxide,
Di-tert-butyl peroxide, benzylhydroperoxide tert-pentyl ester, 2, double (the t-amyl peroxy)-butane of 2-, two
T-amyl peroxy compound, tert butyl peroxy benzoate, dibenzoyl peroxide, two (4-
Chlorobenzene formacyl) peroxide, two (2,4-dichlorobenzoic acid base) peroxide, two (4-first
Base benzoyl) peroxide, normal-butyl-4,4-bis-(tert-butyl hydroperoxide) valerate, ethyl
-3,3-bis-(tert-butyl hydroperoxide)-butyrate, tert-butyl hydroperoxide-butylperoxyisopropyl carbonate, tertiary fourth
Base peroxidating-2-ethylhexyl carbonate, neighbour, the o-tert-butyl group-o-isopropyl-mono--peroxycarbonates,
Tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite, neighbour, o-tertiary pentyl-o-(2-ethylhexyl)-mono--mistake
Carbonoxide acid esters；It is preferably neighbour, o-tertiary pentyl-o-(2-ethylhexyl)-mono--peroxycarbonates.
Described phenols or phosphite kind antioxidant are one of following or more than two of which mixture:
1,3,5-tri-(the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,
6-(1H, 3H, 5H)-triketone, 2,2 '-methylene-bis--(4-ethyl-6-tert-butyl phenol), 2,
2 '-methylene-bis--(4-methyl-6-tert-butylphenol), β-(4-hydroxyl-3,5-di-tert-butyl-phenyl)
The positive octadecyl ester of propanoic acid, three (2,4-di-tert-butyl-phenyl) phosphite ester, two (2,4-dicumyl benzene
Base) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, three (nonyl phenyl)
Phosphite ester.It is preferably the mixture of more than one of the most following or two of which: 1,3,5-tri-(the tertiary fourth of 4-
Base-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone,
Three (2,4 ,-di-tert-butyl-phenyl) phosphite ester, three (2,4 ,-dicumylphenyl) tetramethylolmethane two are sub-
Phosphate ester.
Described hindered amine light stabilizer is one of following or more than two of which mixture: 3,5-
Di-t-butyl-4-hydroxy-benzoic acid cetyl ester, three (1,2,2,6,6-pentamethyl-4-piperidines
Base) phosphite ester, decanedioic acid double-2,2,6,6-tetramethyl piperidine alcohol esters, double-1-decane epoxide-2,
2,6,6-tetramethyl piperidine-4-alcohol sebacates, succinic acid and 4-hydroxyl-2,2,6,6-tetramethyls
The polymer of-1-piperidine alcohols, N, N '-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-are own
Diamidogen and 2, the chloro-6-(1 of 4-bis-, 1,3,3-tetramethyl butyl) amino-1,3,5-triazines poly-
Compound, N, N '-bis-(2,2,6,6-pentamethyl-4-piperidyl)-1,6-hexamethylene diamine and morpholine-2,
The polymer of 4,6-tri-chloro-1,3,5-triazines.It is preferably the mixed of more than one of the most following or two of which
Compound: decanedioic acid double-2,2,6,6-tetramethyl piperidine alcohol ester, double (1,2,2,6,6-pentamethyl-4-piperidyls)
Expensive two acid esters, methyl isophthalic acid, expensive two acid esters of 2,2,6,6-pentamethyl-4-piperidyl.
Described UV absorbers is one of following or more than two of which mixture: 2,2 '-(1,
4-phenylene) double (4H-3,1-benzimidazole dihydrochloride-4-ketone), 2,2 '-bis-(3,1-benzimidazole dihydrochloride-4-
Ketone), 2,2 '-tetramethylene double (3,1-benzimidazole dihydrochloride-4-ketone), 2,2 '-decamethylene double (3,
1-benzimidazole dihydrochloride-4-ketone), 2,2 '-TOPOT 2,2′ p phenylenebis (3,1-benzimidazole dihydrochloride-4-ketone), 2,2 '-
Di-2-ethylhexylphosphine oxide (3,1-benzimidazole dihydrochloride-4-ketone), 1,3,5-tri-(3,1-benzimidazole dihydrochloride-4-ketone-2-
Base) benzene, 2,4,6-tri-(3,1-benzimidazole dihydrochloride-4-ketone-2-base) naphthalene, 2,8-dimethyl-4H,
6H-benzo (1,2-d；5,4-d ') double (1,3)-piperazine-4,6-diketone, 6 ', 6-sulfonyl
Double (2-methyl-4H, 3,1-benzimidazole dihydrochloride-4-ketone), 6,7 '-di-2-ethylhexylphosphine oxide (2-methyl-4H, 3,
1-benzimidazole dihydrochloride-4-ketone), ESCALOL 567,2,4-DihydroxyBenzophenone, 2-
Hydroxyl-4-n-octyloxybenzophenone, 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone, 2,2 '-two
Hydroxyl-4,4 '-dimethoxy-benzophenone, 2-hydroxyl-5-chlorobenzophenone, double-(2-methoxyl group-4-
Hydroxyl-5-benzoylphenyl) methane, 2-(2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5-
Aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxy-5-methyl base phenyl)-5-butyl's ester benzotriazole,
2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5,6-dichloro benzotriazole, 2-(2 '-hydroxy-5-methyl base phenyl)
-5-ethylsulfonic acid benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-
Hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminophenyl) benzotriazole, 2-
(2 '-hydroxyl 3 ' ,-5 '-3,5-dimethylphenyl) benzotriazole, 2-(2 '-methyl-4 '-hydroxy phenyl) benzene
And triazole, 2-(2 '-hydroxyl-5-carboxyl phenyl) benzotriazole ethyl ester, 2-(2 '-hydroxyl-3 ' methyl
-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-octadecyl epoxide-3 ', 5 '-3,5-dimethylphenyl)-5-
Methylbenzotrazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-
Hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-methoxyphenyl)
Benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl
Base-5 '-cyclohexyl phenyl) benzotriazole, 2-(2 '-hydroxyl-4 ', 5 '-3,5-dimethylphenyl)-5-carboxylic acid benzene
And triazole butyl ester, 2-(2 '-hydroxyl-3 ', 5 '-Dichlorobenzene base) benzotriazole, 2-(2 '-hydroxyl-4 ',
5 '-Dichlorobenzene base) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl)-5-ethyl sulphonyl benzene
And triazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-methoxybenzene
Base)-5-methylbenzotrazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5-carboxylate benzotriazole, 2-
(2 '-hydroxyl-5 '-t-octyl phenyl)-5-benzotriazole or 2-(2 '-acetoxyl group-5 '-aminomethyl phenyl)
Benzotriazole.It is preferably the mixture of more than one of the most following or two of which: 2,2-tetramethylene is double
(3,1-benzimidazole dihydrochloride-4-ketone), 2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole, 2,2 '-dihydroxy
-4,4 '-dimethoxy-benzophenone.
Described viscosifier are one of following or more than two of which mixture: gamma-aminopropyl-triethoxy
Silane, γ-methacrylic acid acryloxypropylethoxysilane trimethoxy silane, γ-glycidyl ether oxygen propyl front three
Base silane, 3-propyl silane；It is preferably gamma-aminopropyl-triethoxy-silane.
The invention still further relates to the preparation method of described encapsulating material, described method includes:
(1) by phosphate compound, tripolycyanamide compounds and boric acid by 1.05～1.5:1:1～1.5
Mol ratio ball milling mixing 10～20min, obtains MPB mixing raw material；Described phosphoric acid class
Compound is one or more in APP, phosphoric acid, bis-phenol diphosphate, excellent
Elect APP as；Described tripolycyanamide compounds is selected from tripolycyanamide, melamine
Aminuria hydrochlorate or a combination thereof, preferably tripolycyanamide；
(2) the MPB mixing raw material obtained in step (1) is reacted 1～3h at 300～350 DEG C,
Prepare MPB9(polyphosphoric acid melamine borate)；
(3) the MPB ball milling 15～30min that will obtain in step (2), by the MPB after ball milling
Join water and alcohol by volume ratio in the solution of 1:1, be configured to containing MPB
The MPB solution of 18wt%～25wt%；Adding with MPB mass ratio is 1:15～25
Cetyl trimethylammonium bromide, stir 0.5～1h；Add melamine resin (trimerization
Cyanamide formaldehyde resin) so that it is the concentration range in MPB solution is 1wt～5wt%,
With phosphoric acid regulation MPB pH value of solution to 4～5, solution water-bath is heated to 70～90 DEG C,
Reaction 1.5～3h, cooling, sucking filtration, it is washed with deionized 3～5 times, then at 70～90 DEG C
Under be dried 18～22h, prepare MPB-S(micro encapsulation polyphosphoric acid melamine borate)；
(4) to the silane coupler ethanol solution of 0.5wt%～1.5wt%, (i.e. solute is silane
Coupling agent, solvent is dehydrated alcohol, and silane coupler mass concentration is 0.5%～1.5%)
Middle addition inorganic nano fire retardant, ultrasonic mixing 1～3h, frequency of oscillation 100～140 times
/ min, dries 10～34h, obtains modified inorganic nano-meter flame retardants at a temperature of 50～90 DEG C,
Standby.Wherein the quality consumption of silane coupler is inorganic nano fire retardant quality
0.5%～3%；Described coupling agent can be one of following: KH550, KH570.
(5) by the peroxide cross-linking agent of formula ratio, phenols or phosphite kind antioxidant, it is subject to
Hindered amine light stabilizer, UV absorbers, viscosifier are jointly the water-bath of 50～70 DEG C
Middle stirring 10～30min, obtains mixed aid, standby；
(6) first the photovoltaic encapsulation matrix material of formula ratio is joined in batch mixer, then will
The mixed aid that 1/3～2/3 step (5) obtains joins in batch mixer, stirs 1～2min；
Again remaining mixed aid is joined in batch mixer, after continuing stirring 1～2min, then
The modification nothing that the MPB-S step (3) of formula ratio obtained and step (4) prepare
Machine nano-meter flame retardants joins in batch mixer, stirs 3～5min, obtains mixture；
(7) pour the mixture that step (6) obtains into extruder, enter at a temperature of 80～100 DEG C
Row extrusion, casting film-forming, cool down, cut and rolling, obtain described low filling Halogen
Expansion type flame-retarding photovoltaic encapsulation material.
The beneficial effects are mainly as follows: the present invention uses direct solid phase polycondensation process and micro-glue
Capsule technology, prepares micro encapsulation polyphosphoric acid melamine borate fire retardant, recycling inorganic nano resistance
The synergistic effect of combustion agent, effectively reduces the loading of fire retardant, thus low cost achieve improvement
Ensure while the fire resistance of encapsulating material that its mechanical property and insulating properties are not remarkably decreased；Pass through
The addition of other auxiliary agents, it is ensured that the insulating properties of fire-retardant photovoltaic encapsulation material, wet-heat resisting, ultraviolet ageing
The performances such as performance meet the requirement in photovoltaic encapsulation field.
(4) detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention
It is not limited to that:
Embodiment 1:
A kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material, in parts by weight, it is the most former
Material composition is as follows: 100 parts of VA content is the ethylene-vinyl acetate copolymer (Dupont of 33%
Company), 10 parts of MPB-S, 15 parts of particle diameters are the zinc oxide of 10nm, and 0.1 part of hindered amines light is stable
Double-2,2,6, the 6-tetramethyl piperidine alcohol esters of agent decanedioic acid (Shanghai spark is good plastifies company limited), 0.2 part resists
Oxygen agent 1,3,5-tri-(the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H,
3H, 5H)-triketone/tri-(2,4 ,-di-tert-butyl-phenyl) phosphite ester compound (mass ratio 1:2,
Huge Tian Hai development in science and technology company limited), 0.2 part of cross-linking agent neighbour, o-tertiary pentyl-o-(2-ethyl
Hexyl)-mono--peroxycarbonates (this (giant dragon) rubber raw materials trade Co., Ltd of Guangzhou power),
0.1 part of ultraviolet absorber 2,2-tetramethylene double (3,1-benzimidazole dihydrochloride-4-ketone) (Nanjing what bright science and technology many
Company limited), 3 parts of viscosifier gamma-aminopropyl-triethoxy-silanes (Nanjing Li Pai Chemical Co., Ltd.).
Above-mentioned low filling halogen-free expansion type flame-proof photovoltaic encapsulation material is prepared as follows:
(1) ammonium phosphate, tripolycyanamide and boric acid are pressed 1.05:1:1.5 mol ratio ball milling mixing 15min,
Obtain MPB mixing raw material.
(2) by step (1), the MPB mixing raw material of acquisition is at 300 DEG C, under 1 atmospheric pressure,
Reaction 3h, prepares MPB.
(3) the MPB ball milling 20min that will obtain in step (2), adds the MPB after ball milling
Enter to water and alcohol by volume ratio in the solution of 1:1, be configured to the MPB solution containing MPB20wt%；
Adding with MPB mass ratio is the cetyl trimethylammonium bromide of 1:25, stirs 0.5h；Add
Enter melamine resin (melamine resin) so that it is the concentration range in MPB solution is
1wt%, with the phosphoric acid regulation MPB solution PH of 10wt% to about 4.5, by solution heating in water bath
To 80 DEG C, react 2h, cooling, sucking filtration, be washed with deionized 3～5 times, then at 80 DEG C
It is dried 20h, prepares MPB-S.
(4) adding particle diameter in the Silane coupling agent KH550 ethanol solution of 0.5wt% is
The zinc oxide of 10nm, wherein the consumption of Silane coupling agent KH550 is the 1% of zinc oxide quality, super
Sound mixing 2h, 140 times/min of frequency of oscillation, dry 30h, obtain modified Nano at a temperature of 80 DEG C
Zinc oxide, standby.
(5) by the peroxide cross-linking agent of formula ratio, phenols or phosphite kind antioxidant, it is subject to
Hindered amine light stabilizer, UV absorbers, viscosifier jointly stirred in water bath 20min of 60 DEG C,
Obtain mixed aid, standby.
(6) first the photovoltaic encapsulation matrix material of formula ratio is joined in batch mixer, then will
The mixed aid that 1/3～2/3 step (5) obtains joins in batch mixer, stirs 1～2min；Again will
Remaining mixed aid joins in batch mixer, continues stirring 1～2min.
(7) modification that the MPB-S step (3) of formula ratio obtained and step (4) prepare
Nano zine oxide joins in batch mixer, stirs 3～5min, obtains mixture.
(8) pour the mixture that step (7) obtains into extruder, carry out at a temperature of 90 DEG C
Extrusion, casting film-forming, cool down, cut and rolling, obtain the low filling halogen-free expansible resistance of the present invention
Combustion photovoltaic encapsulation material S-1.
Embodiment 2:
A kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material, in parts by weight, its composition is such as
Under: 100 parts of VA content is in the ethylene vinyl acetate copolymer (du pont company) of 16%,
23 parts of MPB-S, 2 parts of particle diameters are the magnesium hydroxide of 20nm, 0.1 part of hindered amine light stabilizer last of the ten Heavenly stems two
Double-2,2,6, the 6-tetramethyl piperidine alcohol esters of acid (Shanghai spark is good plastifies company limited), 0.2 part of antioxidant 1,3,5-
Three (the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)
-triketone/tri-(2,4 ,-dicumylphenyl) pentaerythritol diphosphites compound (mass ratio 1:4, sky
Great Tian Hai development in science and technology company limited), 1.5 parts of cross-linking agent neighbours, o-tertiary pentyl-o-(2-ethyl hexyl
Base)-mono--peroxycarbonates (this (giant dragon) rubber raw materials trade Co., Ltd of Guangzhou power), 0.1
(Nanjing is many for part ultraviolet absorber ultraviolet absorber 2,2-tetramethylene double (3,1-benzimidazole dihydrochloride-4-ketone)
He Sheng Science and Technology Ltd.), (groupization is found in Nanjing to 0.4 part of viscosifier gamma-aminopropyl-triethoxy-silane
Work company limited).
Above-mentioned low filling halogen-free expansion type flame-proof photovoltaic encapsulation material is prepared as follows:
(1) ammonium phosphate, tripolycyanamide and boric acid are pressed 1.5:1:1 mol ratio ball milling mixing 18min,
Obtain MPB mixing raw material.
(2) by step (1), the MPB mixing raw material of acquisition is at 330 DEG C, under 1 atmospheric pressure,
Reaction 2.5h, prepares MPB.
(3) the MPB ball milling 18min that will obtain in step (2), adds the MPB after ball milling
Enter to water and alcohol by volume ratio in the solution of 1:1, be configured to the MPB solution containing MPB20wt%；
Adding with MPB mass ratio is the cetyl trimethylammonium bromide of 1:20, stirs 0.5h；Add
Enter melamine resin (melamine resin) so that it is the concentration range in MPB solution is
1wt%, with the phosphoric acid regulation MPB solution PH of 10wt% to about 4.5, by solution heating in water bath
To 80 DEG C, react 2h, cooling, sucking filtration, be washed with deionized 3～5 times, then at 80 DEG C
It is dried 20h, prepares MPB-S.
(4) adding particle diameter in the Silane coupling agent KH550 ethanol solution of 0.5wt% is
The magnesium hydroxide of 20nm, wherein the consumption of Silane coupling agent KH550 is the 0.5% of zinc oxide quality,
Ultrasonic mixing 1h, 100 times/min of frequency of oscillation, dry 15h, obtain modification and receive at a temperature of 50 DEG C
Rice magnesium hydroxide, standby.
(5) by the peroxide cross-linking agent of formula ratio, phenols or phosphite kind antioxidant, it is subject to
Hindered amine light stabilizer, UV absorbers, viscosifier, plasticizer are jointly in the water-bath of 60 DEG C
Stirring 20min, obtains mixed aid, standby.
(6) first the photovoltaic encapsulation matrix material of formula ratio is joined in batch mixer, then will
The mixed aid that 1/3-2/3 step (5) obtains joins in batch mixer, stirs 1-2min；Again will be surplus
Remaining mixed aid joins in batch mixer, continues stirring 1-2min.
(7) modification that the MPB-S step (3) of formula ratio obtained and step (4) prepare
Nano-sized magnesium hydroxide joins in batch mixer, stirs 3-5min, obtains mixture.
(8) pour the mixture that step (7) obtains into extruder, carry out at a temperature of 90 DEG C
Extrusion, casting film-forming, cool down, cut and rolling, obtain the low filling halogen-free expansible resistance of the present invention
Combustion photovoltaic encapsulation material S-2.
Embodiment 3:
A kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material, in parts by weight, its composition is as follows:
100 parts of VA content is the ethylene-vinyl acetate copolymer (du pont company) of 40%, 20 parts
MPB-S, 5 parts of particle diameters are the aluminium hydroxide of 30nm, and 0.1 part of hindered amine light stabilizer is double
(1,2,2,6,6-pentamethyl-4-piperidyl) expensive two acid esters/methyl isophthalic acid, 2,2,6,6-pentamethyl-4-piperidyl is expensive
Two acid esters compounds (mass ratio 1:1, Beijing Big Dipper Co., Ltd), 0.2 part of antioxidant 1,3,5-
Three (the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)
-triketone/tri-(2,4 ,-dicumylphenyl) pentaerythritol diphosphites compound (mass ratio 1:4, sky
Great Tian Hai development in science and technology company limited), 1.5 parts of cross-linking agent neighbours, o-tertiary pentyl-o-(2-ethylhexyl)
-mono--peroxycarbonates (this (giant dragon) rubber raw materials trade Co., Ltd of Guangzhou power), 0.5 part of purple
Outer absorbent 2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole (Nanjing Zhong Hesheng Science and Technology Ltd.),
0.4 part of viscosifier gamma-aminopropyl-triethoxy-silane (Nanjing Li Pai Chemical Co., Ltd.).
Above-mentioned low filling halogen-free expansion type flame-proof photovoltaic encapsulation material is prepared as follows:
(1) ammonium phosphate, tripolycyanamide and boric acid are pressed 1.05:1:1.2 mol ratio ball milling mixing 15min,
Obtain MPB mixing raw material.
(2) by step (1), the MPB mixing raw material of acquisition is at 330 DEG C, under 1 atmospheric pressure,
Reaction 2.5h, prepares MPB.
(3) the MPB ball milling 20min that will obtain in step (2), adds the MPB after ball milling
Enter to water and alcohol by volume ratio in the solution of 1:1, be configured to the MPB solution containing MPB20wt%；
Adding with MPB mass ratio is the cetyl trimethylammonium bromide of 1:20, stirs 0.5h；Add
Enter melamine resin (melamine resin) so that it is the concentration range in MPB solution is
1wt%, with the phosphoric acid regulation MPB solution PH of 10wt% to about 4.5, by solution heating in water bath
To 80 DEG C, react 2h, cooling, sucking filtration, be washed with deionized 3-5 time, then at 80 DEG C
It is dried 20h, prepares MPB-S.
(4) adding particle diameter in the silane coupler KH570 ethanol solution of 0.5wt% is
The aluminium hydroxide of 30nm, wherein the consumption of silane coupler KH570 is the 0.5% of zinc oxide quality,
Ultrasonic mixing 2h, 110 times/min of frequency of oscillation, dry 24h, obtain modification and receive at a temperature of 80 DEG C
Rice aluminium hydroxide, standby.
(5) by the peroxide cross-linking agent of formula ratio, phenols or phosphite kind antioxidant, it is subject to
Hindered amine light stabilizer, UV absorbers, viscosifier jointly stirred in water bath 20min of 60 DEG C,
Obtain mixed aid, standby.
(6) first the photovoltaic encapsulation matrix material of formula ratio is joined in batch mixer, then will
The mixed aid that 1/3-2/3 step (5) obtains joins in batch mixer, stirs 1-2min；Again will be surplus
Remaining mixed aid joins in batch mixer, continues stirring 1-2min.
(7) modification that the MPB-S step (3) of formula ratio obtained and step (4) prepare
Nano-aluminum hydroxide joins in batch mixer, stirs 3-5min, obtains mixture.
(8) pour the mixture that step (7) obtains into extruder, carry out at a temperature of 90 DEG C
Extrusion, casting film-forming, cool down, cut and rolling, obtain the low filling halogen-free expansible resistance of the present invention
Combustion photovoltaic encapsulation material S-3.
Embodiment 4:
A kind of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material, in parts by weight, its composition is as follows:
100 parts of metallocene catalysed polyethylene (PEKN, Mitsubishi Chemical Ind) resin raw materials, 18 parts of MPB-S,
7 parts of particle diameters are the silicon dioxide of 50m, 0.1 part of hindered amine light stabilizer decanedioic acid double-2,2,6,6-
Tetramethyl piperidine alcohol ester (Shanghai spark is good plastifies company limited), 0.2 part of antioxidant 1,3,5-tri-(uncle 4-
Butyl-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone/
Three (2,4 ,-di-tert-butyl-phenyl) phosphite ester compound (mass ratio 1:2, send out by sea, huge sky science and technology
Exhibition company limited), 0.2 part of cross-linking agent neighbour, o-tertiary pentyl-o-(2-ethylhexyl)-mono--peroxidating
Carbonic ester (this (giant dragon) rubber raw materials trade Co., Ltd of Guangzhou power), 0.1 part of ultraviolet absorber
2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone (Nanjing Zhong Hesheng Science and Technology Ltd.), 3 parts of increasings
Stick gamma-aminopropyl-triethoxy-silane (Nanjing Li Pai Chemical Co., Ltd.).
Above-mentioned low filling halogen-free expansion type flame-proof photovoltaic encapsulation material is prepared as follows:
(1) ammonium phosphate, tripolycyanamide and boric acid are pressed 1.1:1:1.2 mol ratio ball milling mixing 15min,
Obtain MPB mixing raw material.
(2) by step (1), the MPB mixing raw material of acquisition is at 330 DEG C, under 1 atmospheric pressure,
Reaction 2.5h, prepares MPB.
(3) the MPB ball milling 20min that will obtain in step (2), adds the MPB after ball milling
Enter to water and alcohol by volume ratio in the solution of 1:1, be configured to the MPB solution containing MPB20wt%；
Adding with MPB mass ratio is the cetyl trimethylammonium bromide of 1:20, stirs 0.5h；Add
Enter melamine resin (melamine resin) so that it is the concentration range in MPB solution is
1wt%, with the phosphoric acid regulation MPB solution PH of 10wt% to about 4.5, by solution heating in water bath
To 80 DEG C, react 2h, cooling, sucking filtration, be washed with deionized 3-5 time, then at 80 DEG C
It is dried 20h, prepares MPB-S.
(4) adding particle diameter in the silane coupler KH570 ethanol solution of 0.5wt% is 50m
Silicon dioxide, wherein the consumption of silane coupler KH570 is the 0.5% of zinc oxide quality, ultrasonic
Mixing 2h, 120 times/min of frequency of oscillation, dry 24h, obtain modified Nano two at a temperature of 80 DEG C
Silicon oxide, standby.
(5) by the peroxide cross-linking agent of formula ratio, phenols or phosphite kind antioxidant, it is subject to
Hindered amine light stabilizer, UV absorbers, viscosifier jointly stirred in water bath 20min of 60 DEG C,
Obtain mixed aid, standby.
(6) first the photovoltaic encapsulation matrix material of formula ratio is joined in batch mixer, then will
The mixed aid that 1/3～2/3 step (5) obtains joins in batch mixer, stirs 1～2min；Again will
Remaining mixed aid joins in batch mixer, continues stirring 1～2min.
(7) modification that the MPB-S step (3) of formula ratio obtained and step (4) prepare
Nano silicon joins in batch mixer, stirs 3～5min, obtains mixture.
(8) pour the mixture that step (7) obtains into extruder, carry out at a temperature of 90 DEG C
Extrusion, casting film-forming, cool down, cut and rolling, obtain the low filling halogen-free expansible resistance of the present invention
Combustion photovoltaic encapsulation material S-4.
Comparative example:
In the ethylene-vinyl acetate copolymer that 90 parts of VA content is 33%, add 10 parts of cyclopentadienyls
The ethylene-pentene copolymers of metal catalytic, 3 parts of light stabilizer N, N '-bis-(2,2,6,6-tetramethyl-4-
Piperidyl)-1,6-hexamethylene diamine and 2,4-bis-chloro-6-(1,1,3,3-tetramethoxy) amino-1,3,5-triazine
Polymer, 2 parts of antioxidant 1,3,5-tri-(the 4-tert-butyl group-3-hydroxyl-2,6-dimethyl benzyl)-1,3,5-
Triazine-2,4,6-(1H, 3H, 5H)-triketone/tri-(2,4-di-tert-butyl-phenyl) phosphite ester compounds
Thing, 5 parts of cross-linking agent neighbours, the o-tert-butyl group-o-(2-ethylhexyl)-mono--peroxycarbonates, and
Mix homogeneously.
Mixture carries out blending extrusion in an extruder, and temperature controls at 90 DEG C, and extrudate passes through
Be cast, cool down, cut, coiling process, prepare packaging adhesive film, be designated as C-1.
Performance test:
The property indices of low filling halogen-free expansion type flame-proof photovoltaic encapsulation material is by following side
Method is measured:
1, fire resistance
Fire resistance is tested according to UL94Test standard.
2, oxygen index (OI)
Oxygen index (OI) is tested according to standard ISO4589-1984.
The adhesive strength of 3 and TPT
Test according to standard GB/T2790-1995.
4, ultraviolet resistance irradiation behaviour
Require to carry out the aging survey of ultraviolet irradiation according to IEC IEC61345 regulation
Examination.
Experimental condition: specimen surface temperature 60 ± 5 DEG C；Wavelength is 280-400nm scope, and irradiation is strong
Degree is 15KW h/m2.Yellowness index (Δ YI) is to be analyzed by by GB2409-80.
5, wet and heat ageing resistant performance
Hydrothermal aging test is carried out by GB/T2423.3 test method.
Experimental condition :+85 DEG C, relative humidity 85%, 2000h.
Yellowness index (Δ YI) is analyzed by GB2409-80.
6, specific insulation
It is measured according to standard GB/T1410.
The low filling halogen-free expansion type flame-proof photovoltaic encapsulation material obtained by above-described embodiment, through above-mentioned
Method of testing is evaluated, shown in its evaluation result following table:
The invention is not limited in described embodiment, those skilled in the art is without departing from this
In the range of bright spirit is i.e. open, still can make some and revise or change, therefore the rights protection model of the present invention
Enclose and limit in the range of standard with claims.
Claims (7)
1. a low filling halogen-free expansion type flame-proof photovoltaic encapsulation material, is mainly formed following raw material by quality and makes:
Described photovoltaic encapsulation matrix material is one of following or more than two of which mixture: ethylene-vinyl acetate copolymer, metallocene catalysed polyethylene, POE, ethylene pentene copolymer；
Described microcapsule intumescent flame retardant is micro encapsulation polyphosphoric acid melamine borate；
The described inorganic nano fire retardant through coupling agent treatment is one or more in the nano-aluminum hydroxide through coupling agent treatment, nano-sized magnesium hydroxide, nano silicon, nano zine oxide and nano titanium oxide.
null2. encapsulating material as claimed in claim 1，It is characterized in that described peroxide cross-linking agent is one of following or more than two of which mixture: 1，1-bis-(tert-butyl hydroperoxide)-3，3，5-trimethyl-cyclohexane、2，5-dimethylhexane-2，5-di-tert-butyl peroxide、2，5-dimethyl-2，Double (benzoyl the peroxide)-hexane of 5-、Cumyl peroxide、Double (2-t-butylperoxyisopropyl) benzene、T-butylcumylperoxide、Di-tert-butyl peroxide、Peroxide acid tert-amyl acetate、2，Double (the t-amyl peroxy)-butane of 2-、Two t-amyl peroxy compounds、Tert butyl peroxy benzoate、Dibenzoyl peroxide、Two (4-chlorobenzene formacyl) peroxide、Two (2，4-dichlorobenzoic acid base) peroxide、Two (4-methyl benzoyl) peroxide、Normal-butyl-4，4-bis-(tert-butyl hydroperoxide) valerate、Ethyl-3，3-bis-(tert-butyl hydroperoxide)-butyrate、Tert-butyl hydroperoxide-butylperoxyisopropyl carbonate、Tert-butyl hydroperoxide-2-ethylhexyl carbonate、Adjacent，The o-tert-butyl group-o-isopropyl-mono--peroxycarbonates、Tert-butyl hydroperoxide carbonic acid-2-Octyl Nitrite、Adjacent，O-tertiary pentyl-o-(2-ethylhexyl)-mono--peroxycarbonates.
3. encapsulating material as claimed in claim 1, it is characterized in that described phenols or phosphite ester kind antioxidant are one of following or more than two of which mixture: 1, 3, 5-tri-(the 4-tert-butyl group-3-hydroxyl-2, 6-dimethyl benzyl)-1, 3, 5-triazine-2, 4, 6-(1H, 3H, 5H)-triketone, 2, 2 '-methylene-bis--(4-ethyl-6-tert-butyl phenol), 2, 2 '-methylene-bis--(4-methyl-6-tert-butylphenol), β-(4-hydroxyl-3, 5-di-tert-butyl-phenyl) the positive octadecyl ester of propanoic acid, three (2, 4-di-tert-butyl-phenyl) phosphite ester, two (2, 4-dicumylphenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, three (nonyl phenyl) phosphite ester.
null4. encapsulating material as claimed in claim 1，It is characterized in that described hindered amine light stabilizer is one of following or more than two of which mixture: 3，5-di-t-butyl-4-hydroxy-benzoic acid cetyl ester、Three (1，2，2，6，6-pentamethyl-4-piperidyl) phosphite ester、Decanedioic acid double-2，2，6，6-tetramethyl piperidine alcohol ester、Double-1-decane epoxides-2，2，6，6-tetramethyl piperidine-4-alcohol sebacate、Succinic acid and 4-hydroxyl-2，2，6，The polymer of 6-tetramethyl-1-piperidine alcohols、N，N '-bis-(2，2，6，6-tetramethyl-4-piperidyl)-1，6-hexamethylene diamine and 2，The chloro-6-of 4-bis-(1，1，3，3-tetramethyl butyl) amino-1，3，The polymer of 5-triazine、N，N '-bis-(2，2，6，6-tetramethyl-4-piperidyl)-1，6-hexamethylene diamine and morpholine-2，4，6-tri-chloro-1，3，The polymer of 5-triazine.
null5. encapsulating material as claimed in claim 1，It is characterized in that described UV absorbers is one of following or more than two of which mixture: 2，2’-(1，4-phenylene) double (4H-3，1-benzimidazole dihydrochloride-4-ketone)、2，2 '-bis-(3，1-benzimidazole dihydrochloride-4-ketone)、2，2 '-tetramethylene double (3，1-benzimidazole dihydrochloride-4-ketone)、2，2 '-decamethylene double (3，1-benzimidazole dihydrochloride-4-ketone)、2，2 '-TOPOT 2,2′ p phenylenebis (3，1-benzimidazole dihydrochloride-4-ketone)、2，2 '-di-2-ethylhexylphosphine oxide (3，1-benzimidazole dihydrochloride-4-ketone)、1，3，5-tri-(3，1-benzimidazole dihydrochloride-4-ketone-2-base) benzene、2，4，6-tri-(3，1-benzimidazole dihydrochloride-4-ketone-2-base) naphthalene、2，8-dimethyl-4H，6H-benzo (1，2-d；null5，4-d ') double (1，3)-piperazine-4，6-diketone、6’，Double (2-methyl-the 4H of 6-sulfonyl，3，1-benzimidazole dihydrochloride-4-ketone)、6，7 '-di-2-ethylhexylphosphine oxide (2-methyl-4H，3，1-benzimidazole dihydrochloride-4-ketone)、ESCALOL 567、2，4-dihydroxy benaophenonel、2-hydroxyl-4-n-octyloxybenzophenone、2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone、2，2 '-dihydroxy-4，4 '-dimethoxy-benzophenone、2-hydroxyl-5-chlorobenzophenone、Double-(2-methoxyl group-4-hydroxyl-5-benzoylphenyl) methane、2-(2 '-hydroxy phenyl) benzotriazole、2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole、2-(2 '-hydroxy-5-methyl base phenyl)-5-butyl's ester benzotriazole、2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5，6-dichloro benzotriazole、2-(2 '-hydroxy-5-methyl base phenyl)-5-ethylsulfonic acid benzotriazole、2-(2 '-hydroxyl-5 '-tert-butyl-phenyl)-5-chlorobenzotriazole、2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole、2-(2 '-hydroxyl-5 '-aminophenyl) benzotriazole、2-(2 '-methyl-4 '-hydroxy phenyl) benzotriazole、2-(2 '-hydroxyl-5-carboxyl phenyl) benzotriazole ethyl ester、2-(2 '-octadecyl epoxide-3 '，5 '-3,5-dimethylphenyl)-5-methylbenzotrazole、2-(2 '-hydroxyl-3 '，5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole、2-(2 '-hydroxyl-3 '-the tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole、2-(2 '-hydroxyl-5 '-methoxyphenyl) benzotriazole、2-(2 '-hydroxyl-3 '，5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole、2-(2 '-hydroxyl-5 '-cyclohexyl phenyl) benzotriazole、2-(2 '-hydroxyl-4 '，5 '-3,5-dimethylphenyl)-5-carboxylic acid benzotriazole butyl ester、2-(2 '-hydroxyl-3 '，5 '-Dichlorobenzene base) benzotriazole、2-(2 '-hydroxyl-4 '，5 '-Dichlorobenzene base) benzotriazole、2-(2 '-hydroxyl-3 '，5 '-3,5-dimethylphenyl)-5-ethyl sulphonyl benzotriazole、2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole、2-(2 '-hydroxyl-5 '-methoxyphenyl)-5-methylbenzotrazole、2-(2 '-hydroxyl-5 '-aminomethyl phenyl)-5-carboxylate benzotriazole、2-(2 '-hydroxyl-5 '-t-octyl phenyl)-5-benzotriazole or 2-(2 '-acetoxyl group-5 '-aminomethyl phenyl) benzotriazole.
6. encapsulating material as claimed in claim 1, it is characterised in that described viscosifier are one of following or more than two of which mixture: gamma-aminopropyl-triethoxy-silane, γ-methacrylic acid acryloxypropylethoxysilane trimethoxy silane, γ-glycidyl ether oxygen propyl trimethyl silane, 3-propyl silane.
7. the preparation method of encapsulating material as claimed in claim 1, described method includes:
(1) by phosphate compound, tripolycyanamide compounds and boric acid by 1.05～1.5:1:1～1.5 mol ratio ball milling mixing 10～20min, polyphosphoric acid melamine borate mixing raw material is obtained；Described phosphate compound is one or more in APP, phosphoric acid, bis-phenol diphosphate, and described tripolycyanamide compounds is selected from tripolycyanamide, melamine cyanurate or a combination thereof；
(2) the polyphosphoric acid melamine borate mixing raw material obtained in step (1) is reacted 1～3h at 300～350 DEG C, prepare polyphosphoric acid melamine borate；
(3) the polyphosphoric acid melamine borate ball milling 15～30min that will obtain in step (2), polyphosphoric acid melamine borate after ball milling is joined water and alcohol by volume ratio in the solution of 1:1, be configured to the polyphosphoric acid melamine borate solution containing polyphosphoric acid melamine borate 18wt%～25wt%；Add and the cetyl trimethylammonium bromide that polyphosphoric acid melamine borate mass ratio is 1:15～25, stir 0.5～1h；Add melamine resin, making its concentration range in polyphosphoric acid melamine borate solution is 1wt～5wt%, polyphosphoric acid melamine borate solution pH to 4～5 is regulated with phosphoric acid, solution water-bath is heated to 70～90 DEG C, reacts 1.5～3h, cooling, sucking filtration, it is washed with deionized 3～5 times, at 70～90 DEG C, is then dried 18～22h, prepares micro encapsulation polyphosphoric acid melamine borate；
(4) in the coupling agent ethanol solution of 0.5wt%～1.5wt%, inorganic nano fire retardant is added, ultrasonic mixing 1～3h, frequency of oscillation 100～140 times/min, dry 10～34h at a temperature of 50～90 DEG C, obtain the inorganic nano fire retardant through coupling agent treatment, standby；
(5) by peroxide cross-linking agent, phenols or phosphite ester kind antioxidant, hindered amine light stabilizer, UV absorbers, viscosifier jointly the stirred in water bath 10～30min of 50～70 DEG C, mixed aid is obtained, standby；
(6) first photovoltaic encapsulation matrix material is joined in batch mixer, then the mixed aid that 1/3～2/3 step (5) obtains is joined in batch mixer, stir 1～2min；Again remaining mixed aid is joined in batch mixer, after continuing stirring 1～2min, the inorganic nano fire retardant through coupling agent treatment that micro encapsulation polyphosphoric acid melamine borate step (3) obtained again and step (4) prepare joins in batch mixer, stirring 3～5min, obtains mixture；
(7) pour the mixture that step (6) obtains into extruder, carry out extruding at a temperature of 80～100 DEG C, casting film-forming, cool down, cut and rolling, obtain described low filling halogen-free expansion type flame-proof photovoltaic encapsulation material.
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| CN104530548B (en) * | 2014-12-25 | 2017-02-22 | 杭州福斯特光伏材料股份有限公司 | Halogen-free transparent flame-retardant photovoltaic encapsulating material and preparation method of halogen-free transparent flame-retardant photovoltaic encapsulating material |
| CN107266777A (en) * | 2017-07-25 | 2017-10-20 | 合肥华盖光伏科技有限公司 | A kind of photovoltaic encapsulation material and preparation method thereof |
| CN107345035A (en) * | 2017-08-02 | 2017-11-14 | 合肥同佑电子科技有限公司 | A kind of Flame-retardant Wire and Cable Compounds for being used to communicate and preparation method thereof |
| CN107501706B (en) * | 2017-09-01 | 2020-07-28 | 泰州隆基乐叶光伏科技有限公司 | P-type double-sided battery packaging adhesive film |
| CN108084545A (en) * | 2018-01-02 | 2018-05-29 | 马鞍山佳夫尼电气科技有限公司 | A kind of preparation method of photovoltaic apparatus encapsulating material |
| CN108998974A (en) * | 2018-09-11 | 2018-12-14 | 宁波叮叮家居科技有限公司 | A kind of preparation method of ultraviolet protection curtain fabric |
| CN112409391B (en) * | 2020-11-20 | 2023-06-06 | 云南江磷集团股份有限公司 | Melamine borate salt thermal polycondensate anti-dripping agent and application thereof in PA6 |
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