CN102742143A - Edge sealant composition with reactive or unsaturated polyolefins - Google Patents

Edge sealant composition with reactive or unsaturated polyolefins Download PDF

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CN102742143A
CN102742143A CN2010800568607A CN201080056860A CN102742143A CN 102742143 A CN102742143 A CN 102742143A CN 2010800568607 A CN2010800568607 A CN 2010800568607A CN 201080056860 A CN201080056860 A CN 201080056860A CN 102742143 A CN102742143 A CN 102742143A
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weight
amount
styrene
edge
total compsn
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J.伍德
R.拉萨尔
K.莱姆
H.贝克
H.布吕赫
N.肖特
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Adco Products Inc
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Adco Products Inc
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    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/042—PV modules or arrays of single PV cells
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Abstract

A solar module includes a photovoltaic device that has an edge seal. The sealant composition of the edge seal includes an unsaturated or reactive polyolefin, an olefinic polymer, a silane modified polyolefin, inert fillers, a water scavenger or desiccant, an antioxidant, and a UV stabilizer. These components are balanced to produce a sealant having desirable sealing characteristics, high weatherability, desired rheology, low conductivity, and good thermal stability.

Description

Edge sealant composition with reactivity or unsaturated polyolefin
CROSS-REFERENCE TO RELATED PATENT
The U.S. Provisional Patent Application that present patent application requires to submit on October 14th, 2009 number 61/251; 542 senior interest; And be the Patent Application No. 12/679 of the common pending trial of submission on March 19th, 2010; 250 continuation application, said Patent Application No. 12,679; 250 require the priority of the international application no PCT/DE/2008/001564 of submission on September 22nd, 2008, and said international application no PCT/DE/2008/001564 requires the priority of the German priority document DE/10 2,007 045 104.2 of submission on September 20th, 2007.The content of above-mentioned application is attached among this paper by reference in full.
The field
The present invention relates to have the edge sealant composition of reactivity or unsaturated polyolefin, be more especially the edge sealant that can be used for solar energy module with reactivity or unsaturated polyolefin.
Background
Photovoltaic solar cells plate or module generally comprise range upon range of and/or are clipped in the electrooptical device between a plurality of layers.Most of electrooptical devices are based on the crystal silicon cell of rigidity wafer or thin-film module, and it has deposited cadmium telluride (Cd-Te), amorphous silicon or copper-indium-diselenide (CuInSe on substrate 2).Thin-film solar module can be rigidity or flexibility.Flexible thin-film battery and module are through producing photosensitive layer and any other necessary electrodeposition substance on flexible substrate.Electrooptical device is electrically connected each other, and is electrically connected with other solar panel or module, to form integrated system.
The efficient of photovoltaic solar cells plate reduces because of the intrusion of moisture.A kind of effective ways that reduce this transfer of the inside of moisture from the environment to the solar energy module, moisture-sensitive part are to use edge sealant.These edge sealant have moisture transmission rate or the low character of MVT.
Edge sealant in the solar energy module is exposed under the high temperature, for example in the range upon range of step during building solar energy module.Therefore, expect that these edge sealant have thermal stability.Most of edge sealant are actually polyolefin.Therefore, the main mechanism of degradation during high temperature exposure is a random chain scission.In case these free radicals form (because random chain scission), degraded spreads.In addition, be exposed at sealant in the application of heat/light trigger (like encapsulant, for example the EVA in the solar energy module), those initators tend to make the sealant degraded.For the integral body and the surface nature of sealant, this can cause harmful consequence (for example loss of strength, to the loss of the adhesiveness of glass).Therefore, there is the space in this area to edge sealant, and said edge sealant shows anti-degradability (long-time stability in the open air) when under hot conditions, showing good thermal stability and being exposed to the initator (encapsulant) in the solar energy module.
Summary
Solar energy module comprises the electrooptical device with edge sealing.The encapsulant composition of edge sealing comprises unsaturated or reactive polyolefin, olefin polymer, silane-modified polyolefin, inert filler, deicer or drier, oxidation inhibitor and UV stabilizer.These components of balance to be producing sealant, and said sealant has seal feature, the high weather resistance of expectation, rheology, low conductivity and the good thermal stability of expectation.
Further characteristic, advantage and application are obvious in the description that this paper provides.Should understand said description and specific embodiment and be intended to only be used for illustration purpose, and not be intended to limit the scope of the present disclosure.
Accompanying drawing
Accompanying drawing described herein only is used for illustration purpose and is not intended to limit by any way the scope of the present disclosure.Component among the figure needn't be in proportion, but focus on explaining principle of the present invention.In the accompanying drawings:
Fig. 1 has the top view of the solar energy module embodiment of edge sealing compositions in accordance with the principles of the present invention;
Fig. 2 is the sectional view that has according to the part of the solar energy module embodiment of edge of the present invention sealing compositions;
Fig. 3 is incubated the bar chart of the loss in weight after seven days for showing unsaturated or reactive polymer in 180 ℃ of air circulating ovens; And
Fig. 4 is incubated the bar chart of the loss in weight after seven days for showing non-reacted polyisobutene (PIB) in 180 ℃ of air circulating ovens.
Detail
Below describe and be merely exemplary character, and be not intended to limit the disclosure, application or purposes.
With reference to Fig. 1 and 2, adopt in accordance with the principles of the present invention the total reference number 10 that passes through of exemplary solar energy module of encapsulant composition to point out.Said solar energy module 10 can adopt and variously not break away from the form of the scope of the invention and generally comprise at least one photoelectric cell that is positioned at chamber 13 12, and said chamber 13 is through first substrate 14 and 16 qualifications of second substrate.Although a plurality of photoelectric cells 12 have been described, should understand the photoelectric cell 12 that can adopt any number.
Can operate said photoelectric cell 12 and produce electric current with daylight from irradiation photoelectric cell 12.Correspondingly, said photoelectric cell 12 can adopt the various forms that do not break away from the scope of the invention.For example, said photoelectric cell 12 can be have cadmium telluride (Cd-Te), amorphous silicon or copper-indium-diselenide (CuInSe 2) layer hull cell.Perhaps, said photoelectric cell 12 can be the crystal silicon wafer that embeds stacked film or is deposited on germanium or another on-chip GaAs.The electrooptical device 12 of adoptable other kinds comprises organic semi-conductor cell, and said organic semiconductor battery has conjugated polymer and dyestuff-sensitization metal oxide, comprises wet metal oxide and solid metal oxide.Said electrooptical device 12 can be rigidity or flexibility.Said photoelectric cell 12 connects with serial or parallel connection or its combination.The electric current that electrooptical device 12 produces is sent to electric wire or the lead 15 that leaves solar energy module 10 through converging lines or other electric conducting material or layer.Said lead 15 links with terminal box 17 so that the electric current that produces solar energy module 10 is assigned to power circuit.
Said first substrate 14 or the panel forms by operating the material that therefrom passes with the wavelength that allows daylight.For example, said first substrate 14 is glass or plastic film such as polyvinyl fluoride.Select second substrate 16 or backboard to think that solar energy module 10 provides other intensity.For example, second substrate 16 for plastics such as fluorinated ethylene-propylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), gather (tetrafluoroethene) (PTFE) with the combination of these plastics and other polymeric material.
Said photoelectric cell 12 is by layer laminate 19 encapsulation, and said layer laminate 19 is preferably crosslinkable ethyl vinyl acetate (EVA).Yet, should understand and can adopt other sandwich that does not break away from the scope of the invention or thermoplasticity encapsulant.Said layer laminate 19 is used for the local encapsulation of electrooptical device 12 to protect said electrooptical device 12 and avoid pollution, mechanical stress and away from environment.
The edge that edge or edge sealing 18 are positioned near solar energy module 10 is between first substrate 14 and second substrate 16.Said edge sealing 18 can have various width.In addition, also can comprise second edge sealing (not shown).The sealing of second edge can be made up of for example silicone, MS polymer, silylated polyurethane, butyl rubber or polysulfide.Can operate said edge sealing 18 so that said layer laminate 19 and electrooptical device 12 are sealed.Said edge sealing 18 must have the ultra-violet radiation exposure that enough weatherabilitys comprise prolongation to bear the exposure of environment to external world, has low moisture and vapor transmission (MVT), and has low conductivity.Said edge sealing 20 is made up of encapsulant composition, and said encapsulant composition has following specific characteristic: high weather resistance and low conductivity and MVT (will in following more detailed description), and good thermal stability and oxidation stability.
The encapsulant composition of edge sealing 18 comprises unsaturated or reactive polyolefin, olefin polymer, silane-modified polyolefin, inert filler, deicer, oxidation inhibitor and UV stabilizer.These components of balance to be producing sealant, and said sealant has seal feature, the high weather resistance of expectation, rheology, low conductivity and the good thermal stability of expectation.
In some embodiments of sealant, said unsaturated or reactive polyolefin is selected from EPDM, polyolefin acrylic acid ester and halogenated butyl rubber.Said olefin polymer is selected from the amorphous copolymer and/or the terpolymer (APAO) of polyisobutene, polybutene, butyl rubber (polyisobutene-isoprene), styrene block copolymer, especially SBS, SIS, SEBS, SEPS, SIBS, SPIBS and modified form and alpha-olefin.
Scope of the present invention provides polymer-modified; It is selected from polyisobutene, polybutene, butyl rubber (polyisobutene-isoprene), styrene block copolymer; Especially the amorphous copolymer of SBS, SIS, SEBS, SEPS, SIBS, SPIBS and modified form and alpha-olefin and/or terpolymer (APAO); Said polymer is group modified with at least one formula (1), and said group is that end group or statistical distribution are in chain
Figure 2010800568607100002DEST_PATH_IMAGE002
Wherein-A-does
-(CH 2) m- (2)，
-S-(CH 2) m-(3) or
Figure 2010800568607100002DEST_PATH_IMAGE004
(4)
And R 1And R 2Identical or different, and for alkyl with 1 to 20 carbon atom, have the aryl of 6 to 20 carbon atoms or have the aralkyl of 7 to 20 carbon atoms,
X is hydroxyl or hydrolyzable group,
A be 0,1,2 or 3 and b be 0,1 or 2, the summation of a and b is more than or equal to 1, and wherein n is the integer between 0 and 18, m is integer and the R between 0 and 4 3For
Figure 2010800568607100002DEST_PATH_IMAGE006
In addition, within the scope of the present invention filler is selected from powdered whiting and winnofil, silicate, lime, silica and carbon black.
In this, the present invention also provides calcium carbonate through surface treatment.
Yet, also can use not surface treated calcium carbonate.
The present invention provides silicate to be selected from talcum powder, kaolin, mica, silica, silica and calcium silicates or magnesium silicate in addition.
In addition, within the scope of the present invention drier or deicer is selected from 3A to 10A type molecular sieve (zeolite).
Certainly, also can use other chemically or physically to combine the material of water.
Can sealed compound be formulated as a part of sealed compound or two parts sealed compound.Under the situation of a part of sealed compound, all components mix during production process.Under the situation of two parts sealed compound, some components form a part and other component formation another part.At once two of said compound are together partially mixed before application subsequently.
The present invention also provides antiaging agent to be selected from sterically hindered phenol, thioether, sulfhydryl compound, phosphide, BTA, benzophenone, HALS and antiozonant.
In various enforcements; Said sealed compound can be used to make the insulating glass that is used for window, greenhouse, structure and roof glass window; Be used to be limited to land (land-bound) automobile, boats and ships and aircraft windowpane and be used to make solar energy module, comprise thermoelectric solar energy module.Except that silane is polymer-modified, has unsaturated or reactive polyolefinic sealed compound and be designed to during cascade solidifying so that other structural strength to be provided.
As the evidence of principle, unsaturated or reactive polyolefin: Exxpro 3433 (Exxon) below the test, Lanxess bromo butyl rubber 2030 (Lanxess), EPDM (Vistalon 5601) (Exxon) with Exxon chloro butyl rubber 1068.All samples is incubated 7 days and weighs and lose with calculated weight in 180 ℃ of air circulating ovens.The degree of the said loss in weight and thermal degradation (thermal stability is opposite) is proportional.Exposing 7 days in 180 ℃ of air circulating ovens selects to study the thermal stability of polymer as extreme condition.Under these extreme conditions, butyl rubber tends to stand thermal degradation widely, causes the significant weight loss.Mechanism of degradation main under these conditions more possibly be random chain scission, and up to the point that forms enough little molecule, said molecule can be taken away by air, causes the loss in weight.In addition, oxygen can quicken the speed of thermal degradation, because in case through random chain scission formation group, oxygen molecule can form alkoxyl and peroxy with its reaction.The reactivity of unsaturated rubber is tended to use these free radicals and is stopped further degraded.In many cases, observe unsaturated and combination group and caused molecular weight accumulation and/or crosslinked, further increased intensity.Can be clear that from Fig. 3 selected reactivity or unsaturated polyolefin show the minimum loss in weight (less than 5%) after 180 ℃ of air circulating ovens expose 7 days.The non-reacted polyolefin (from Oppanol B-100 and the B-50 of BASF) that is exposed under the condition of similarity shows that (see figure 4) surpasses 95% the loss in weight.
The radical reaction of observing reactivity and/or unsaturated position and under high temperature exposure, forming causes the degraded (if any) and the improved thermal stability of minimum degree.The sealing of said edge show low MVTR and can be crosslinked with radical reaction time the, wherein said free radical possibly be thermal degradation or thermal oxidative degradation or with the encapsulant of solar energy module in the result of the peroxide reactions that contains.In addition, after aging 7 days (a kind of accelerated aging test is as the tolerance of thermal stability and thermo oxidative stability), said edge sealant shows the loss in weight less than 10% in 180 ℃ of air circulating ovens.More preferably, aging after 7 days in 180 ℃ of air circulating ovens, said edge sealant shows the loss in weight less than 7.5%.
Special concern be the EPDM polymer, it contains unsaturated polymerization skeleton, but said polymeric skeleton is made up of at least a non-conjugated diene (like norbornadiene, bicyclopentadiene and/or 1,5-hexadiene) of ethene and propylene monomer and little significant quantity.Meaning is; There is preferential duality in various EPDM polymer: although skeleton is saturated fully; Thereby most of parts are comprised that peroxide and other oxidants are highly stable and non-reacted; But the accidental two keys permissions that exist are crosslinked in side chain, and if these side chain bond fissions, skeleton is kept perfectly.
Attention is in Fig. 1, although all goods that contain the polymer of all listing provide impressive low weight loss result, it is minimum to contain the loss in weight result that the preparation of EPDM (Vistalon) provides.In theory, in more challenging environment, expection contains the EPDM preparation and bears more rigorous environment better, makes it to distinguish mutually with other.
EPDM also provides reactive and does not comprise the saturated-backbone of halogen such as chlorine or bromine.Hydrochloric acid and hydrobromic acid toxic emission are impossible for EPDM.
For the present invention can more easily be understood, with reference to following examples, said embodiment is intended to explain principle of the present invention, but does not limit its scope.
Wherein for each embodiment, component is:
Unsaturated reactive polyolefinSuch as EPDM, polyolefin acrylic acid ester and molecular weight Mn is 100-100,000 Da, preferred 100-500, the halogenated butyl rubber of 000 Da;
Olefin polymer: polyethylene, polypropylene, polybutene, polyisobutene, butyl rubber (polyisobutene-isoprene), styrene block copolymer (and modified form): (Mn is 100-1 for all weight of otefi pi polymer; 000; 000 Da, preferred 100-300,000 Da);
Silane: DFDA-5451NT (from the silane grafting PE of Dow Chemical), DFDA-5481 NT (from the moisture-curing catalyst of Dow Chemical), amorphous poly alpha olefin (such as but be not limited to Vestoplast 206, Vestoplast 2412), alkoxy silane, amino silane;
Inert filler: powdered whiting and winnofil, silicate, silica and carbon black, CaCO 3, Ca (OH) 2, titanium dioxide,
Silicate is selected from talcum powder, kaolin, mica, silica, silica and calcium silicates or magnesium silicate;
DeicerAs CaO or DrierLike molecular sieve, silica gel and calcium sulfate;
Antiaging agent: sterically hindered phenol, bulky amine, thioether, sulfhydryl compound, phosphide, BTA, benzophenone and antiozonant.
Description of the invention is merely exemplary character, and the variation that does not break away from main idea of the present invention is intended to belong in the scope of the present invention.These variations are not regarded as and are departed from the spirit and scope of the present invention.

Claims (20)

1. edge sealing that is used to make two sides or multiaspect insulating glass or solar energy module, the sealing of said edge comprises that sealant and bond, wherein said sealant contain the group modified polymer of useful particular reactive and have following main assembly:
A) unsaturated or reactive polyolefin or its combination, its amount is about 10 weight %-80 weight % of total compsn;
B) olefin polymer or its combination, it amount of comprising is the about 80 weight % of about 5 weight %-of total compsn;
C) at least a filler, it amount of comprising are the about 60 weight % of about 10 weight %-of total compsn;
D) at least a in drier or the deicer, it amount of comprising is the about 25 weight % of about 2.5 weight %-of total compsn; With
E) at least a antiaging agent that comprises oxidation inhibitor or UV stabilizer, it amount of comprising are the about 3 weight % of about 0.1 weight %-of total compsn.
2. the edge of claim 1 sealing, wherein the amount of comprising of olefin polymer is the about 50 weight % of about 5 weight %-of total compsn, and the amount of comprising of silane modified polymer is the about 30 weight % of about 5 weight %-of total compsn.
3. the edge of claim 2 sealing, wherein said filler also comprises particulate filler, its amount is the about 50 weight % of about 5 weight %-of total compsn.
4. the edge of claim 2 sealing, wherein said olefin polymer is selected from the amorphous copolymer and/or the terpolymer (APAO) of polyisobutene, polybutene, butyl rubber (polyisobutene-isoprene), styrene block copolymer, SBS (s-B-S), SIS (styrene-isoprene-phenylethene), SEBS (styrene-ethylene-butylene-styrene), SEPS (styrene-ethylene-propylene-styrene), SIBS (styrene-isoprene-butadiene-styrene), SPIBS (styrene-polyisobutene-styrene) and modified form and alpha-olefin.
5. the edge of claim 2 sealing, wherein said silane modified polymer is selected from the amorphous copolymer and/or the terpolymer (APAO) of polyisobutene, polybutene, butyl rubber (polyisobutene-isoprene), styrene block copolymer, SBS (s-B-S), SIS (styrene-isoprene-phenylethene), SEBS (styrene-ethylene-butylene-styrene), SEPS (styrene-ethylene-propylene-styrene), SIBS (styrene-isoprene-butadiene-styrene), SPIBS (styrene-polyisobutene-styrene) and alpha-olefin.
6. the edge of claim 5 sealing, wherein said APAO polymer is group modified with at least one formula (1), and said group is that end group or statistical distribution are in chain
，
Wherein-A-does
-(CH 2) m- (2)，
-S-(CH 2) m-(3) or
(4)
And R 1And R 2Identical or different, and for alkyl with 1 to 20 carbon atom, have the aryl of 6 to 20 carbon atoms or have the aralkyl of 7 to 20 carbon atoms,
X is hydroxyl or hydrolyzable group,
A be 0,1,2 or 3 and b be 0,1 or 2, the summation of a and b is more than or equal to 1, and wherein n is the integer between 0 and 18, m is integer and the R between 0 and 4 3For
。
7. the edge of claim 3 sealing, the particulate filler of wherein said sealant is selected from powdered whiting and winnofil, silicate, lime, silica and carbon black.
8. the edge of claim 7 sealing, the calcium carbonate of wherein said sealant is surface treated calcium carbonate.
9. the edge of claim 7 sealing, the silicate of wherein said sealant is selected from talcum powder, kaolin, mica, silica, silica and calcium silicates or magnesium silicate.
10. the edge of claim 1 sealing, the drier of wherein said sealant or deicer are selected from molecular sieve, phosphorus pentoxide, calcium oxide, anhydrous salt, epoxidized vegetable oil, carbodiimide, tolysulfonyl based isocyanate or their combination.
11. the sealing of the edge of claim 1, the drier of wherein said sealant or deicer are selected from the molecular sieve (zeolite) of 3A to 10A type.
12. the sealing of the edge of claim 1, the antiaging agent of wherein said sealant is selected from sterically hindered phenol, thioether, sulfhydryl compound, phosphide, BTA, benzophenone, HALS (hindered amine light stabilizer) and oxidation inhibitor.
13. the sealing of the edge of claim 1, wherein said unsaturated or reactive polyolefin is selected from EPDM, polyolefin acrylic acid ester and halogenated butyl rubber.
14. the edge of claim 2 sealing; Wherein the amount of comprising of olefin polymer is the about 50 weight % of about 30 weight %-, and its Mn is that about 5,000 D are to about 1; 000; 000 D, the amount of comprising of silane modified polymer is about 5 weight %-25 weight %, and the amount of comprising of drier or deicer is at most about 15 weight % of total compsn.
15. a solar energy module, it comprises:
First substrate;
Second substrate;
At least one is arranged at the photoelectric cell between first and second substrates;
Sealant, said sealant contact with first and second substrates and form the water vapour barrier layer, arrive at least one photoelectric cell to hinder water vapour, and wherein said sealant comprises:
Unsaturated or reactive polyolefin;
Olefin polymer;
At least a in silane-modified APAO and the silane-modified polyisobutene;
At least a filler;
At least a in deicer or the drier; With
At least a antiaging agent, and
Wherein said sealant makes the photoelectric cell electric insulation.
16. the solar energy module of claim 15, wherein at least a in first and second substrates is at least a in glass, polymer and the metal.
17. the solar energy module of claim 15; The wherein said unsaturated or reactive polyolefinic amount of comprising is the about 80 weight % of about 10 weight %-of total compsn; Said olefin polymer comprises the polyisobutene of amount of the about 50 weight % of about 5 weight %-of total compsn; At least a amount of comprising in said silane-modified APAO and the silane-modified polyisobutene is the about 30 weight % of about 5 weight %-of total compsn; The amount of comprising of said filler is the about 60 weight % of about 10 weight %-of total compsn; At least a amount of comprising in said deicer or the drier is the about 25 weight % of about 2.5 weight %-of total compsn, and the amount of comprising of said antiaging agent is the about 3 weight % of 0.1 weight %-of total compsn.
18. a compound that is used to have the solar energy module of photoelectric cell, said compound comprises:
Unsaturated or reactive polyolefin;
Olefin polymer;
At least a in silane-modified APAO and the silane-modified polyisobutene;
At least a filler;
At least a in deicer or the drier; With
At least a antiaging agent, and
Wherein said compound makes the photoelectric cell electric insulation.
19. the compound of claim 18; The wherein said unsaturated or reactive polyolefinic amount of comprising is the about 80 weight % of about 10 weight %-of total compsn; Said olefin polymer comprises the polyisobutene of amount of the about 50 weight % of about 5 weight %-of total compsn; At least a amount of comprising in said silane-modified APAO and the silane-modified polyisobutene is the about 30 weight % of about 5 weight %-of total compsn; The amount of comprising of said filler is the about 60 weight % of about 10 weight %-of total compsn; At least a amount of comprising in said deicer or the drier is the about 25 weight % of about 2.5 weight %-of total compsn, and the amount of comprising of said antiaging agent is the about 3 weight % of 0.1 weight %-of total compsn.
20. a sealed compound that is used to have the solar energy module of first substrate and second substrate, wherein said sealed compound is arranged between first substrate and second substrate, and said sealed compound comprises:
Unsaturated or reactive polyolefin;
Olefin polymer greater than the amount of about 30 weight % of total compsn;
At least a in silane-modified APAO and the silane modified polymer, its amount is less than 35 weight % of total compsn;
Filler;
Primary particle diameter is less than the carbon black of about 60nm;
At least a in deicer or the drier; With
Antiaging agent.
CN2010800568607A 2009-10-14 2010-10-14 Edge sealant composition with reactive or unsaturated polyolefins Pending CN102742143A (en)

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