Polyolefin composition for photovoltaic encapsulation films
阅读说明：本技术 用于光伏封装膜的聚烯烃组合物 (Polyolefin composition for photovoltaic encapsulation films ) 是由 何超 仰云峰 马伟明 陈红宇 孙亚斌 张楷男 J·M·柯吉恩 T·J·珀森 李宇岩 于 2017-10-31 设计创作，主要内容包括：本公开涉及由可固化组合物制成的封装膜,所述可固化组合物包含：(A)聚烯烃聚合物；(B)有机过氧化物；(C)硅烷偶联剂；以及(D)包含式(I)单环有机硅氧烷的助剂。(The present disclosure relates to an encapsulant film made from a curable composition comprising: (A) a polyolefin polymer; (B) an organic peroxide; (C) a silane coupling agent; and (D) an adjuvant comprising a monocyclic organosiloxane of formula (I).)
1. A curable composition for forming an encapsulating film, wherein the composition comprises:
(a) a polyolefin polymer;
(b) an organic peroxide;
(c) a silane coupling agent; and
(d) an adjuvant comprising a monocyclic organosiloxane of formula (I):
[R1，R2SiO2/2]n(I)，
wherein subscript n is an integer greater than or equal to 3; each R1Independently is (C)2-C4) An alkenyl group; and each R2Independently H, (C)1-C4) Alkyl, phenyl, or R1。
2. The composition of claim 1, comprising:
(a)80 to 99.88 wt% of the polyolefin polymer;
(b)0.1 to 5 wt% of the organic peroxide;
(c)0.01 to 2 wt% of the silane coupling agent; and
(d)0.01 to 5 wt% of the adjuvant comprising the monocyclic organosiloxane of the formula (I).
3. The composition of claim 1 or 2, wherein the polyolefin polymer is an ethylene/α -olefin copolymer comprising a density (ASTM D792) from 0.850g/cc to 0.890g/cc and a melt index (ASTM D1238, 190 ℃/2.16kg) from 1.0g/10min to 50.0g/10 min.
4. The composition according to any one of claims 1 to 3, wherein the monocyclic organosiloxane of formula (I) is further described by limiting any one of (I) to (vi): (i) subscript n is 3; (ii) each R1Independently is (C)2-C3) Alkenyl, and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is vinyl, and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is vinyl, and each R2Is methyl; (v) each R1Is allyl, and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is allyl, and each R2Is methyl.
5. The composition according to any one of claims 1 to 3, wherein the monocyclic organosiloxane of formula (I) is further described by limiting any one of (I) to (vi): (i) subscript n is 4; (ii) each R1Independently is (C)2-C3) Alkenyl, and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is vinyl, and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is vinyl, and each R2Is methyl; (v) each R1Is allyl, and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is allyl, and each R2Is methyl.
6. The composition according to any one of claims 1 to 3, wherein the monocyclic organosiloxane of formula (I) is further described by limiting any one of (I) to (vi): (i) subscript n is 5 or 6; (ii) each R1Independently is (C)2-C3) Alkenyl, and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is vinyl, and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is vinyl, and each R2Is methyl; (v) each R1Is allyl, and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is allyl, and each R2Is methyl.
7. The composition according to any one of the preceding claims, wherein the monocyclic organosiloxane of formula (I) is selected from the group consisting of: 1, 3, 5, 7-tetravinyl-1, 3, 5, 7-tetramethylcyclotetrasiloxane; 1, 3, 5-trivinyl-1, 3, 5-trimethylcyclotrisiloxane; 1, 3, 5, 7, 9-pentavinyl-1, 3, 5, 7, 9-pentamethylcyclopentasiloxane; and combinations thereof.
8. An encapsulation film comprising a crosslinked polymer composition comprising the reaction product of:
(a) a polyolefin polymer;
(b) an organic peroxide;
(c) a silane coupling agent; and
(d) an adjuvant comprising a monocyclic organosiloxane of formula (I):
[R1，R2SiO2/2]n(I)，
wherein subscript n is an integer greater than or equal to 3; each R1Independently is (C)2-C4) An alkenyl group; and each R2Independently H, (C)1-C4) Alkyl, phenyl, or R1。
9. The encapsulation film of claim 8, comprising a crosslinked polymer composition comprising the reaction product of:
(a)80 to 99.88 wt% of the polyolefin polymer;
(b)0.1 to 5 wt% of the organic peroxide;
(c)0.01 to 2 wt% of the silane coupling agent; and
(d)0.01 to 5 wt% of the adjuvant comprising the monocyclic organosiloxane of the formula (I).
10. The encapsulating film of claim 8 or 9, wherein the polyolefin polymer is an ethylene/α -olefin copolymer comprising a density (ASTM D792) from 0.850g/cc to 0.890g/cc and a melt index (ASTM D1238, 190 ℃/2.16kg) from 1.0g/10min to 50.0g/10 min.
11. The encapsulating film of any one of claims 8 to 10, wherein the formula (I) monocyclic organosiloxane is further described by any one of limitations (I) to (vi): (i) subscript n is 3; (ii) each R1Independently is (C)2-C3) Alkenyl, and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is vinyl, and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is vinyl, and each R2Is methyl; (v) each R1Is allyl, and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is allyl, and each R2Is methyl.
12. The encapsulating film of any one of claims 8 to 10, wherein the formula (I) monocyclic organosiloxane is further described by any one of limitations (I) to (vi): (i) subscript n is 4; (ii) each R1Independently is (C)2-C3) Alkenyl, and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is vinyl, and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is vinyl, and each R2Is methyl; (v) each R1Is allyl, and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is allyl, and each R2Is methyl.
13. The encapsulating film of any one of claims 8 to 10, wherein the formula (I) monocyclic organosiloxane is further described by any one of limitations (I) to (vi): (i) subscript n is 5 or 6; (ii) each R1Independently is (C)2-C3) Alkenyl, and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is vinyl, and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is vinyl, and each R2Is methyl; (v) each R1Is allyl, and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is allylAnd each R is2Is methyl.
14. The encapsulating film according to any one of claims 8 to 13, wherein the monocyclic organosiloxane of formula (I) is selected from the group consisting of: 1, 3, 5, 7-tetravinyl-1, 3, 5, 7-tetramethylcyclotetrasiloxane; 1, 3, 5-trivinyl-1, 3, 5-trimethylcyclotrisiloxane; 1, 3, 5, 7, 9-pentavinyl-1, 3, 5, 7, 9-pentamethylcyclopentasiloxane; and combinations thereof.
15. The encapsulating film according to any one of claims 8 to 14, further comprising greater than 1.0 x 10 at room temperature14Volume resistivity in ohm-cm.
16. The encapsulating film according to any one of claims 8 to 15, further comprising greater than 1.0 x 10 at 60 ℃14Volume resistivity in ohm-cm.
17. The encapsulating film of any of claims 8 to 16, further comprising an average initial glass adhesion of greater than 60N/cm.
18. An electronic device module, comprising:
in the electronic device, the electronic device is provided with a plurality of electronic components,
a cover plate, and
the encapsulation film according to any one of claims 8 to 17.
Technical Field
The present disclosure relates to polyolefin polymer compositions for use in Photovoltaic (PV) encapsulation films. In one aspect, the present disclosure relates to polyolefin polymer compositions that allow for shorter processing times to form encapsulation films. In another aspect, the present disclosure relates to PV encapsulant films comprising polyolefin polymer compositions and electronic devices comprising the same.
Background
Over the past decade, global demand for alternative energy has resulted in a dramatic increase in solar panel and PV module production. Solar cells that convert solar energy into electrical energy (also referred to as PV cells) are very fragile and must be surrounded by a durable encapsulant film. The two primary functions of the encapsulant film are (1) to adhere the solar cells to the glass cover and back sheets, and (2) to protect the PV module from environmental stresses (e.g., moisture, temperature, shock, vibration, electrical insulation, etc.). Current encapsulation films are made primarily from Ethylene Vinyl Acetate (EVA) because EVA exhibits a good balance of properties required for encapsulation films. EVA is an ethylene/unsaturated carboxylic acid ester copolymer in which the unsaturated carboxylic acid ester comonomer is a vinyl carboxylate ester.
Certain polyolefin polymers, such as polyolefin elastomers (POE) that are not ethylene/unsaturated carboxylic acid ester copolymers, have been identified as alternatives to EVA for forming encapsulation films and have advantages over EVA such as electrical resistivity, moisture and heat stability, and weatherability. However, conventional POE-based compositions have a longer processing time for forming encapsulation films than EVA-based compositions. Accordingly, the art recognizes the need for new POE-based compositions that allow for reduced processing times to form encapsulating films while maintaining good cure properties, adhesion, volume resistivity, and the like.
Disclosure of Invention
In certain embodiments, the present disclosure relates to a curable composition for forming an encapsulation film, the composition comprising:
(a) a polyolefin polymer;
(b) an organic peroxide;
(c) a silane coupling agent; and
(d) an adjuvant comprising a silane compound of formula (I):
[R1，R2SiO2/2]n(I)，
wherein subscript n is an integer greater than or equal to 3; each R1Independently is (C)2-C4) An alkenyl group; and each R2Independently H, (C)1-C4) Alkyl, phenyl or R1。
In other embodiments, the present invention relates to an encapsulating film comprising a crosslinked polymer composition comprising the reaction product of:
(a) a polyolefin polymer;
(b) an organic peroxide;
(c) a silane coupling agent; and
(d) an adjuvant comprising a mono-ring organosiloxane compound of formula (I):
[R1，R2SiO2/2]n(I)，
wherein subscript n is an integer greater than or equal to 3; each R1Independently is (C)2-C4) An alkenyl group; and each R2Independently H, (C)1-C4) Alkyl, phenyl or R1。
Drawings
Fig. 1 is an exploded perspective view of an exemplary photovoltaic module.
Fig. 2 is a graph of dip time versus percent dip for certain examples of the present disclosure.
Definition of
Any reference to the periodic table of elements is the periodic table of elements as published by CRC Press, inc., 1990-1991. References to groups of elements in this table are by new reference to the numbered groups.
For purposes of united states patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent us version thereof is so incorporated by reference), especially with respect to the disclosure of definitions in the art (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge.
The numerical ranges disclosed herein include all values from the lower and upper limit values, and include the lower and upper limit values. For ranges containing exact values (e.g., 1 or 2 or 3 to 5 or 6 or 7), any subrange between any two exact values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.).
Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.
Unless stated to the contrary, all test methods were current as of the filing date of this disclosure.
"blend," "polymer blend," and similar terms refer to a composition of two or more polymers. Such blends may or may not be miscible. Such blends may or may not phase separate. Such blends may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, x-ray scattering, and any other method for measuring and/or identifying domain configurations. The blend is not a laminate, but a laminate of one or more layers may comprise the blend.
As used herein, "composition" includes mixtures of materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.
The terms "comprising," "including," "having," and derivatives thereof, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may contain any additional additive, adjuvant or compound, whether polymeric or otherwise. In contrast, the term "consisting essentially of … …" excludes from any subsequently enumerated range any other component, step, or procedure other than those not important to the operation. The term "consisting of … …" excludes any components, steps or procedures not specifically recited. Unless otherwise specified, the term "or" refers to the listed members individually as well as in any combination. The use of the singular includes the use of the plural and vice versa.
"direct contact" refers to a layer structure in which a first layer is positioned immediately adjacent to a second layer, and there are no intervening layers or structures between the first and second layers.
The term "coagent" refers to a compound that enhances crosslinking, i.e., a curing coagent. The terms "adjuvant", "crosslinking adjuvant" and "crosslinking adjuvant" are used interchangeably herein. A "conventional coagent" is an acyclic or cyclic compound that enhances crosslinking and contains carbon atoms in its respective backbone or ring substructure. Thus, the main chain or ring substructure of conventional auxiliaries is based on carbon (carbon-based substructure). By contrast, a silicon-based adjuvant refers to a non-cyclic or cyclic compound that enhances crosslinking and contains silicon atoms in its respective backbone or ring substructure. The silane compounds of formula (I) are acyclic silicon-based auxiliaries. The use of conventional auxiliaries in POE-based compositions represents prior art.
The terms "cure" and "crosslinking" are used interchangeably herein to mean the formation of a crosslinked product (network polymer) without ring-opening polymerization.
As used herein, the term "ring-opening catalyst" refers to a substance that initiates and/or enhances the rate at which cyclic siloxane monomers undergo ring-opening polymerization.
As used herein, the term "ring-opening polymerization" is a type of chain growth polymerization in which the reactive end of a polymer chain opens the ring of a cyclic monomer to give a longer polymer chain.
As used herein, "polymer" refers to a polymer compound prepared by polymerizing monomers of the same or different types. The generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace impurities can be incorporated into the polymer structure) and the term interpolymer as defined herein. Trace impurities, such as catalyst residues, can be incorporated into and/or within the polymer.
As used herein, "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers (used to refer to polymers prepared from two different types of monomers), as well as polymers prepared from more than two different types of monomers.
"propylene-based," "propylene-based polymer," "polypropylene," and similar terms refer to polymers containing (based on the total amount of polymerizable monomers) from 50 weight percent (wt%) to 100 wt% polymerized propylene monomer, and optionally may contain at least one comonomer.
"ethylene," "ethylene-based polymer," "polyethylene," and similar terms refer to polymers containing (based on the total amount of polymerizable monomers) from 50 wt% to 100 wt% polymerized ethylene monomer, and optionally may contain at least one comonomer.
As used herein, an "α -olefin" is a hydrocarbon molecule having ethylenic unsaturation in the first (α) position3-C20) α -olefin "is a hydrocarbon molecule consisting of a hydrocarbon molecule that contains (i) only one ethylenic unsaturation, said unsaturation being located between said first and second carbon atoms, and (ii) at least 3 carbon atoms, or 3-20 carbon atoms3-C20) α -olefin means H2C ═ C (h) -R, where R is straight chain (C)1-C18) An alkyl group. (C)1-C18) An alkyl group is a monovalent unsubstituted saturated hydrocarbon having from 1 to 18 carbon atoms. Non-limiting examples of R are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. (C)3-C20Non-limiting examples of α -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-dodecene, and mixtures of two or more of these monomers3-C20) α -olefins may also contain cyclic structures such as cyclohexane or cyclopentane, yielding α -olefins such as 3-cyclohexyl-1-propene (allylcyclohexane) and vinylcyclohexane (C)3-C20) α -olefins may be used as comonomers with ethylene monomers.
Term "By "ethylene-containing polymer" is meant a polymer containing a monomer derived from H2C＝CH2A polymer of the repeating unit (c).
"polyolefin elastomer" or "POE" refers to an elastomeric polymer containing equal to or greater than 50 weight percent polymerized α -olefin monomer (including ethylene) "polyolefin elastomer" includes, but is not limited to, ethylene-based polymers and propylene-based polymers as described herein.
"non-polar polymer" and similar terms refer to a polymer that does not have a permanent dipole, i.e., the polymer does not have a positive and negative terminal, and is free of heteroatoms and functional groups. "functional group" and like terms refer to a moiety or radical that is responsible for giving a particular compound its characteristic response. Non-limiting examples of functional groups include heteroatom-containing moieties, oxygen-containing moieties (such as alcohol, aldehyde, ester, ether, ketone, and peroxide groups), and nitrogen-containing moieties (such as amide, amine, azo, imide, imine, nitrate, nitrile, and nitrite groups). A "heteroatom" is an atom other than carbon or hydrogen.
"photovoltaic cell", "PV cell", and like terms refer to a structure comprising one or more photovoltaic effect materials of any of several inorganic or organic types known in the art. For example, commonly used photovoltaic effect materials include one or more known photovoltaic effect materials, including but not limited to crystalline silicon, polycrystalline silicon, amorphous silicon, copper indium gallium (di), selenide (CIGS), Copper Indium Selenide (CIS), cadmium telluride, gallium arsenide, dye sensitized materials, and organic solar cell materials. As shown in fig. 1, PV cells are typically used in a laminate structure and have at least one photoreactive surface that converts incident light into electrical current. Photovoltaic cells are well known to those skilled in the art and are typically packaged into photovoltaic modules that protect the cells and allow them to be used in various application environments, typically outdoor applications. PV cells can be flexible or rigid in nature and include photovoltaic effect materials and any protective coating surface materials applied in their production as well as appropriate wiring and electronic drive circuitry.
The terms "photovoltaic module," "PV module," and the like refer to a structure that includes PV cells. The PV module can also include a cover sheet, a front encapsulant film, a back encapsulant film, and a back sheet with the PV cells sandwiched between the front and back encapsulant films.
"room temperature" means a temperature range of about 20 to about 25 ℃.
"further processing," "further processed," and similar terms refer to polyolefin manufacturing process steps including, but not limited to, compounding, blending, melt blending, extrusion (e.g., film extrusion), kneading, absorbing, injection, and molding (e.g., injection molding, compression molding, blow molding, etc.). Non-limiting examples of suitable compounding equipment include internal batch mixers (e.g., BANBURY and bold internal mixers) and continuous single or twin screw mixers (e.g., FARREL continuous mixers, BRABENDER single screw mixers, WERNER and PFLEIDERER twin screw mixers, and BUSS kneading continuous extruders). The type of mixer used and the operating conditions of the mixer can affect the properties of the composition, such as viscosity, volume resistivity, and extruded surface smoothness.
Detailed Description
Currently, encapsulation films are mainly made of EVA. However, it is of great interest to replace EVA-based compositions with polyolefin polymer compositions that do not comprise EVA (e.g., polyolefin elastomers (POE) as defined herein), as they may provide certain advantages for encapsulation films, including but not limited to resistivity, moisture and heat stability, and weatherability. However, a challenge with forming POE-based encapsulation films is longer processing times relative to the formation of EVA-based encapsulation films. Specifically, in the process of forming the EVA-based or POE-based encapsulating film, the initial step may be to impregnate the EVA or POE with a curing package (which includes a peroxide, a silane coupling agent, and a crosslinking coagent). For POE, the initial impregnation step may be much longer (e.g., up to 16 hours) when using conventional cure packs, as compared to EVA (e.g., about 1 hour). Therefore, a longer impregnation time of POE may severely limit productivity and increase manufacturing costs for forming the POE-based encapsulating film. For this reason, the present disclosure provides a surprising and unexpected reduction in the time required to impregnate POE with cured packages when replacing conventional crosslinking coagents, such as Triallylisocyanurate (TAIC), with coagents comprising the mono-ring organosiloxane compound of formula (I).
Composition comprising a metal oxide and a metal oxide
The composition of the present disclosure ("the present composition") is a curable composition for forming an encapsulating film, the composition comprising: (A) a polyolefin polymer; (B) an organic peroxide; (C) a silane coupling agent; and (D) an adjuvant comprising a monocyclic siloxane compound of formula (I).
(A) Polyolefin polymers
The composition of the present invention comprises a polyolefin polymer. In certain embodiments, the inventive compositions comprise 80 to 99.99 wt% of the polyolefin polymer (e.g., 80 to 99.88 wt%, 85 to 99.88 wt%, 88 to 99.88 wt%, 90 to 99 wt%, 95 to 99 wt%, 97 to 99 wt%, 97.50 to 98.50 wt%, 97.75 to 98.25 wt%, etc.). In other words, in certain embodiments, the inventive compositions comprise 80 wt%, or 85 wt%, or 88 wt%, or 90 wt%, or 95 wt%, or 97 wt%, or 97.50 wt%, or 97.75 wt% to 98.25 wt%, or 98.5 wt%, or 99 wt%, or 99.88 wt%, or 99.99 wt% of the polyolefin polymer.
In certain embodiments, the polyolefin polymer is a polyolefin elastomer as defined herein. In a further embodiment, the polyolefin polymer is a non-polar polyolefin elastomer.
In some embodiments, the polyolefin polymer is an ethylene-based polymer comprising 50 to 100 wt% ethylene monomer units, 50 to 0 wt% (C)3-C20α -olefin derived comonomer units and optionally 20 to 0 wt% of a diene comonomer, wherein the total weight percentage is 100 wt%. the diene used to prepare the diene comonomer can be 1, 3-butadiene, 1, 5-hexadiene, 1, 7-octadiene, ethylidene norbornene, dicyclopentadiene or vinyl norbornene.
In some embodiments, the polyolefin polymer is a propylene-based polymer comprising 50 to 100 wt% propylene monomer units, 50 to 0 wt% ethylene or (C)4-C20) α -olefin derived copolymerizationMonomer units and optionally 20 to 0 wt% of a diene comonomer, wherein the total weight percentage is 100 wt%. The diene used to prepare the diene comonomer may be 1, 3-butadiene, 1, 5-hexadiene, 1, 7-octadiene, ethylidene norbornene, dicyclopentadiene or vinyl norbornene.
In some embodiments, the polyolefin polymer is poly ((C)3-C20) α -olefin) homopolymer comprising 99 to 100 wt% of (C3-C20) α -olefin monomer units, or is poly ((C)3-C20) α -olefin) copolymer containing 99 to 100% by weight of at least two different (C)3-C20) α -olefin monomer/comonomer units.
In certain embodiments, the polyolefin polymer is an ethylene/α -olefin interpolymer the ethylene/α -olefin interpolymer can be a random or block interpolymer the block interpolymer includes multi-block and diblock copolymers non-limiting examples of suitable ethylene/α -olefin interpolymers include ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/1-octene, ethylene/propylene/1-butene, and ethylene/butene/1-octene interpolymers in some embodiments, ethylene/α -olefin interpolymers are ethylene/α -olefin copolymers non-limiting examples of suitable ethylene/α -olefin copolymers include ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/1-hexene copolymers, and ethylene/1-octene copolymers.
In certain embodiments, the polyolefin polymer is a propylene/α -olefin interpolymer, wherein the "α -olefin" includes ethylene in some embodiments, the propylene/α -olefin interpolymer is a propylene/α -olefin copolymer.
In certain embodiments, the polyolefin polymer has a density from 0.850g/cc to 0.900g/cc (e.g., from 0.855g/cc to 0.900g/cc, from 0.860g/cc to 0.900g/cc, from 0.865g/cc to 0.900g/cc, from 0.870g/cc to 0.890g/cc, from 0.875g/cc to 0.885g/cc, and/or from 0.880g/cc to 0.885g/cc) according to ASTM D792. In other words, the polyolefin polymer has a density of 0.850g/cc, or 0.855g/cc, or 0.860g/cc, or 0.865g/cc, or 0.870g/cc, or 0.875g/cc, or 0.880g/cc to 0.885g/cc, or 0.890g/cc, or 0.900g/cc, according to ASTM D792.
In certain embodiments, the polyolefin polymer has a Melt Index (MI) of 1g/10min to 100g/10min (e.g., 1g/10min to 75g/10min, 1g/10min to 50g/10min, 1g/10min to 45g/10min, 1g/10min to 40g/10min, 1g/10min to 35g/10min, 1g/10min to 30g/10min, 5g/10min to 25g/10min, 10g/10min to 25g/10min, 15g/10min to 20g/10min, and/or 18g/10min to 20g/10min) at 190 ℃/2.16kg according to ASTM D1238. In other words, in certain embodiments, the polyolefin polymer has a melt index of 1g/10min, or 5g/10min, or 10g/10min, or 15g/10min, or 18g/10min to 20g/10min, or 25g/10min, or 30g/10min, or 35g/10min, or 40g/10min, or 45g/10min, or 50g/10min, or 75g/10min, or 100g/10min at 190 ℃/2.16kg according to ASTM D1238.
In some embodiments, the polyolefin polymer has a melting point of 40 ℃ to 125 ℃. In other words, in some embodiments, the melting point of the polyolefin polymer is 40 ℃, or 45 ℃, or 50 ℃, or 55 ℃ to 60 ℃, or 65 ℃, or 70 ℃, or 80 ℃, or 90 ℃, or 95 ℃, or 100 ℃, or 110 ℃, or 120 ℃, or 125 ℃.
In some embodiments, the polyolefin polymer has a glass transition temperature (Tg) of from-35 ℃ to-100 ℃. In other words, in some embodiments, the polyolefin polymer has a glass transition temperature (Tg) of-35 ℃, or-40 ℃, or-45 ℃, or-50 ℃ to-80 ℃, or-85 ℃, or-90 ℃, or-95 ℃, or-100 ℃.
In other embodiments, the polyolefin polymer of the present disclosure is an ethylene/α -olefin interpolymer, excluding ethylene/propylene copolymers (e.g., ethylene-propylene rubber and/or ethylene-propylene terpolymers).
In certain embodiments, the polyolefin polymer is an ethylene/α -olefin interpolymer having one, some, or all of the following properties:
(i) a density of 0.850g/cc, or 0.855g/cc, or 0.860g/cc, or 0.865g/cc, or 0.870g/cc, or 0.875g/cc, or 0.880g/cc to 0.885g/cc, or 0.890g/cc, or 0.900 g/cc;
(ii) a melt index of 1g/10min, or 5g/10min, or 10g/10min, or 15g/10min, or 18g/10min to 20g/10min, or 25g/10min, or 30g/10min, or 35g/10min, or 40g/10min, or 45g/10min, or 50g/10min, or 75g/10min, or 100g/10 min; and/or
(iii) The melting point (Tm) is from 40 ℃, or 45 ℃, or 50 ℃, or 55 ℃ to 60 ℃, or 65 ℃, or 70 ℃, or 80 ℃, or 90 ℃, or 95 ℃, or 100 ℃, or 110 ℃, or 120 ℃, or 125 ℃.
The polyolefin polymer may be a blend or combination of two or more of the foregoing embodiments. The polyolefin polymer may also be blended or diluted with one or more other polymers.
The polyolefin polymer may be prepared by any suitable method known in the art. Any conventional or later-discovered production method for producing polyolefin polymers may be used to prepare the polyolefin polymers of the present invention. Exemplary non-limiting preparation methods include one or more polymerization reactions, such as high pressure polymerization methods or coordination polymerization methods using one or more polymerization catalysts, including but not limited to ziegler-natta, chromium oxide, metallocene, constrained geometry, or post-metallocene catalysts. Suitable temperatures are from 0 ° to 250 ℃, or from 30 ° to 200 ℃. Suitable pressures are from atmospheric (101kPa) to 10,000 atmospheres (about 1, 013 megapascals ("MPa")). In most polymerizations, a catalyst is used in a molar ratio to polymerizable olefin (monomer/comonomer) of 10-121 to 10-11, or 10-91 to 10-5∶1。
Non-limiting examples of polyolefin polymers include ENGAGE from Dow chemical companyTMPolyolefin elastomers, AFFINITY from the Dow chemical companyTMPolyolefin elastomers, INFUSE from the Dow chemical companyTMOlefin block copolymers, INTUNE from Dow chemical companyTMPP olefin block copolymer, EXACT from Exxon chemicalTMResin, TAFMER from Mitsui ChemicalsTMResin, LUCENE from LG chemistryTMResin fromEASTOFLEX of Islam Chemical Company (Eastman Chemical Company)TMResin, and FLEXOMER from the Dow chemical companyTMAnd (3) resin.
(B) Organic peroxides
The compositions of the present invention comprise an organic peroxide. In certain embodiments, the inventive compositions comprise 0.1 wt% to 3 wt% of the organic peroxide (e.g., 0.1 wt% to 2.5 wt%, 0.1 wt% to 2 wt%, 0.5 wt% to 1.5 wt%, and/or 1 wt% to 1.5 wt%). In other words, the present composition comprises 0.1 wt%, or 0.5 wt%, or 1 wt% to 1.5 wt%, or 2 wt%, or 2.5 wt%, or 3 wt% of the organic peroxide.
In certain embodiments, the organic peroxide is a molecule containing carbon atoms, hydrogen atoms, and two or more oxygen atoms and having at least one-O-group, with the proviso that when there is more than one-O-group, each-O-group is indirectly bonded to another-O-through one or more carbon atoms, or a collection of such molecules.
The organic peroxide may be a monoperoxide of the formula: rO-O-O-ROWherein each R is0Independently is (C)1-C20) Alkyl or (C)6-C20) And (4) an aryl group. Each (C)1-C20) Alkyl is independently unsubstituted or substituted by 1 or 2 (C)6-C12) Aryl substitution. Each (C)6-C20) Aryl being unsubstituted or substituted by 1 to 4 (C)1-C10) Alkyl substitution. Alternatively, the organic peroxide may be a diperoxide of the formula: rO-O-O-R-O-O-ROWherein R is a divalent hydrocarbon group, such as (C)2-C10) Alkylene, (C)3-C10) Cycloalkylene or phenylene, and each ROAs defined above.
Non-limiting examples of suitable organic peroxides include dicumyl peroxide, dodecyl peroxide, benzoyl peroxide, t-butyl perbenzoate, di (t-butyl) peroxide, cumene hydroperoxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 2, -5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butyl hydroperoxide, isopropyl percarbonate, α '-bis (t-butylperoxy) diisopropylbenzene, t-butylperoxy-2-ethylhexyl monocarbonate, 1, 1-bis (t-butylperoxy) -3, 5, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-dihydroxyperoxide, t-butyl cumyl peroxide, α' -bis (t-butylperoxy) -p-diisopropylbenzene, bis (1, 1-dimethylethyl) peroxide, bis (1, 1-dimethylpropyl) peroxide, 2, 5-dimethyl-2, 5-bis (1, 1-dimethylethyl) hexane, 2, 5-bis (1, 1-dimethylethyl) peroxy) hexane, 2, 5-dimethyl-2, 5-bis (1, 1-dimethylethyl) hexane, 2, 5-di (t-butyl peroxy) -3, 5-dimethyl-2, 5-butyl peroxy) -3, 5-dimethyl-3, 5-isopropyl peroxybutyl-3, 5-dimethyl-butyl peroxyethyl peroxybutyl-3, 5-dimethyl-isopropyl peroxybutyl-3, 5-isopropyl peroxybutyl-2, 5-dimethyl-isopropyl peroxybutyl-2, bis (1, 5-dimethyl-isopropyl) peroxybutyl-isopropyl peroxybutyl-2, bis (1, 5-dimethyl-isopropyl) peroxybutyl-isopropyl peroxybutyl-2, bis (1, 5-isopropyl peroxybutyl) peroxybutyl-isopropyl peroxybutyl-4, 5, bis (4, bis (.
Non-limiting examples of suitable commercially available organic peroxides include TRIGONOX (R) from Akzo Nobel and LUPEROX (R) from ARKEMA.
(C) Silane coupling agent
The present composition comprises a silane coupling agent. In certain embodiments, the compositions of the present disclosure comprise 0.01 wt% to 2 wt% of the silane coupling agent (e.g., 0.05 wt% to 1.5 wt%, 0.10 wt% to 1 wt%, 0.15 wt% to 0.5 wt%, 0.2 wt% to 0.4 wt%, and/or 0.25 wt% to 0.3 wt%). In other words, the composition of the present invention comprises 0.01 wt%, or 0.05 wt%, or 0.10 wt%, or 0.15 wt%, or 0.20 wt% to 0.3 wt%, or 0.4 wt%, or 0.5 wt%, or 1 wt%, or 1.5 wt%, or 2 wt% of the silane coupling agent.
Non-limiting examples of suitable silane coupling agents include gamma chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris (β -methoxy) silane, allyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, β - (3, 4-ethoxy-cyclohexyl) ethyltrimethoxysilane, gamma-glycidylpropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, and 3- (trimethoxysilyl) propylmethacrylate.
In some embodiments, the silane coupling agent is vinyltrimethoxysilane or 3- (trimethoxysilyl) propyl methacrylate or 3-allyltrimethoxysilane.
(D) Auxiliary agent
The compositions of the present invention comprise an adjuvant comprising a monocyclic organosiloxane of formula (I): [ R ]1，R2SiO2/2]n(I) Wherein subscript n is an integer greater than or equal to 3; each R1Independently is (C)2-C4) An alkenyl group; and each R2Independently H, (C)1-C4) Alkyl, phenyl or R1。
In certain embodiments, the monocyclic organosiloxane of formula (I) is further described by any of the following limitations: (i) subscript n is 3; (ii) each R1Independently is (C)2-C3) An alkenyl group; and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is a vinyl group; and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is a vinyl group; and each R2Is methyl; (v) each R1Is an allyl group; and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is an allyl group; and each R2Is methyl.
In certain embodiments, the monocyclic organosiloxane of formula (I) is further described by any of the following limitations: (i) subscript n is 4; (ii) each R1Independently is (C)2-C3) An alkenyl group; and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is a vinyl group; and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is a vinyl group; and each R2Is methyl; (v) each R1Is an allyl group; and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is an allyl group; and each R2Is methyl.
In certain embodiments, the monocyclic organosiloxane of formula (I) is further described by any of the following limitations: (i) subscript n is 5 or 6; (ii) each R1Independently is (C)2-C3) An alkenyl group; and each R2Independently H, (C)1-C2) Alkyl or (C)2-C3) An alkenyl group; (iii) each R1Is a vinyl group; and each R2Independently is (C)1-C2) An alkyl group; (iv) each R1Is a vinyl group; and each R2Is methyl; (v) each R1Is an allyl group; and each R2Independently is (C)1-C2) An alkyl group; (vi) each R1Is an allyl group; and each R2Is methyl.
In certain embodiments, the mono-cyclic organosiloxane of formula (I) is an alkenyl-functional mono-cyclic organosiloxane. In certain embodiments, the mono-cyclic organosiloxane of formula (I) is a cyclic molecule that does not contain carbon or nitrogen in its ring.
In certain embodiments, the mono-cyclic organosiloxane of formula (I) is a molecule comprising a single cyclic substructure of silicon and oxygen atoms arranged in an alternating arrangement; and an unsaturated organic group; and optionally H, saturated or aromatic substituents; wherein at least two unsaturated organic groups are present and at least two silicon atoms in the ring sub-structure are each bonded to at least one unsaturated organic group and wherein any remaining valences of the silicon atoms are bonded to H, a saturated or aromatic substituent after the unsaturated organic group and the oxygen atom are occupied; a collection of such molecules.
The monocyclic organosiloxane of formula (I) may be a monocyclic organosiloxane consisting of a 6-membered ring (n ═ 3), an 8-membered ring (n ═ 4), a 10-membered ring (n ═ 5), or a 12-membered ring (n ═ 6). The ring substructure is composed of units of formula (I): [ R ]1，R2SiO2/2]n(I) Wherein the subscripts n, R1And R2As defined earlier. At each [ R ]1，R2SiO2/2]nIn the unit (a), R thereof1And R2The group is bonded to its silicon atom. The units may be simply represented as D using the conventional organosiloxane shorthand notationR1，R2Whereby formula (I) becomes [ D ]R1，R2]n is the same as the formula (I). In this regard, superscripts R1 and R2 may be separately from R1And R2And (4) interchanging. In some aspects, R1And R2Are the same or different.
In certain embodiments of the monocyclic organosiloxanes of formula (I), R1Is vinyl and R2Is ethyl and the mono-cyclic organosiloxane of the formula (I) is DVi，EtWherein Vi is vinyl and Et is ethyl; or, R1Is allyl and R2Is ethyl and the mono-cyclic organosiloxane of the formula (I) is DAllyl group, Et(ii) a Or, R1Is butenyl (H)2C＝C(H)CH2CH2-) and R2Is ethyl and the mono-cyclic organosiloxane of the formula (I) is DButenyl radical, Et. In some aspects, R1Is vinyl and R2Is vinyl and the monocyclic organosiloxane of the formula (I) is DVi，Vi(ii) a Or, R1Is allyl and R2Is allyl and the mono-cyclic organosiloxane of the formula (I) is DAllyl, allyl(ii) a Or, R1Is butenyl (H)2C＝C(H)CH2CH2-) and R2Is butenyl and the mono-cyclic organosiloxane of the formula (I) is DButenyl, butenyl. In some aspects, R1Is vinyl and R2Is phenyl and the monocyclic organosiloxane of the formula (I) is DVi，PhWherein Ph is phenyl; or, R1Is allyl and R2Is phenyl and the monocyclic organosiloxane of the formula (I) is DAllyl group, Ph(ii) a Or, R1Is butenyl (H)2C＝C(H)CH2CH2-) and R2Is phenyl and the monocyclic organosiloxane of the formula (I) is DButenyl group, Ph. When R is2Is methyl (CH)3) When said cell can be more simply denoted as DR1Whereby formula (I) becomes [ D ]R1]n. In some aspects, R1Is vinyl and R2Is methyl and the monocyclic organosiloxane of the formula (I) is DVi(ii) a Or, R1Is allyl and R2Is methyl and the monocyclic organosiloxane of the formula (I) is DAllyl radical(ii) a Or, R1Is butenyl (H)2C＝C(H)CH2CH2-) and R2Is methyl and the monocyclic organosiloxane of the formula (I) is DButenyl radical. In some embodiments, the monocyclic organosiloxane of formula (I) is 2, 4, 6-trimethyl-2, 4, 6-trivinyl-cyclotrisiloxane, "(D)Vi)3"(CAS No. 3901-77-7); 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetravinyl-cyclotetrasiloxane, "(D)Vi)4"(CAS No. 2554-06-5); or a combination thereof.
In certain embodiments, the adjuvant in the compositions of the present invention consists only of the mono-ring organosiloxane compound of formula (I).
The amount of the mono-ring organosiloxane compound of formula (I) in the composition of the invention may be a crosslinking effective amount. The term "crosslinking effective amount" refers to an amount (e.g., wt%) sufficient to enable crosslinking of the polyolefin macromolecules by the multivalent crosslinker groups derived from the mono-ring organosiloxane compound of formula (I). The conditions may include the loading level (wt%) of the mono-cyclic organosiloxane compound of formula (I), the loading level (wt%) of the organic peroxide in the peroxide cure example, or the radiation dose in the radiation cure example. The crosslinking effective amount of the mono-cyclic organosiloxane compound of formula (I) provides a greater degree of crosslinking at a particular loading level (wt%) of organic peroxide or at a particular dosage level of radiation than a control composition without the mono-cyclic organosiloxane compound of formula (I). The situation may also depend on the total amount of other components or any optional additives, if any, present in the polyolefin composition.
With respect to determining the crosslinking effective amount of the adjuvant of the compositions of the present invention, the presence of crosslinking can be detected by increasing the torque using a Moving Die Rheometer (MDR). In some aspects, the presence of cross-linking can be detected as a percent solvent extraction (Ext%). Ext% ═ W1/Wo 100%, where W1 is the weight after extraction, Wo is the original weight before extraction,/denotes division,/denotes multiplication. Crosslinking polyolefin products unsaturated organic groups (e.g. R) of the monocyclic organosiloxane compound of formula (I)1) The absence or reduced level of carbon-carbon double bonds (due to coupling with (a) the polyolefin polymer) can be detected by carbon-13 or silicon-29 nuclear magnetic resonance (13C-NMR spectroscopy and/or 29Si-NMR spectroscopy).
In certain embodiments, the compositions of the present disclosure comprise 0.01 wt% to 5 wt% (e.g., 0.05 wt% to 4.5 wt%, 0.1 wt% to 4 wt%, 0.15 wt% to 3.5 wt%, 0.2 wt% to 3 wt%, 0.25 wt% to 2.5 wt%, 0.3 wt% to 2 wt%, 0.35 wt% to 1.5 wt%, 0.4 wt% to 1.25 wt%, 0.45 wt% to 1 wt%, 0.5 wt% to 1 wt%, etc.) of an adjuvant comprising a monocyclic organosiloxane of formula (I). In other words, the composition of the invention comprises from 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.15 wt%, or 0.2 wt%, or 0.25 wt%, or 0.3 wt%, or 0.35 wt%, or 0.4 wt%, or 0.45 wt%, or 0.5 wt% to 1 wt%, or 1.25 wt%, or 1.5 wt%, or 2 wt%, or 2.5 wt%, or 3 wt%, or 3.5 wt%, or 4 wt%, or 4.5 wt%, or 5 wt% of the adjuvant comprising a monocyclic organosiloxane of formula (I).
In certain embodiments, the compositions of the present invention comprise an adjuvant comprising a monocyclic organosiloxane of formula (I), with the proviso that the composition does not contain (i.e., lacks) a phosphazene base. In certain embodiments, the compositions of the present invention do not contain any ring-opening catalyst. In other embodiments, when the polyolefin polymer is an ethylene-containing polymer and the subscript n (formula (I) monocyclic organosiloxane) is 4, the inventive composition contains no inorganic filler at 24 wt% or more, or no inorganic filler at 22 wt% or more, or no inorganic filler at 20.0 wt% or more, or no inorganic filler at 15 wt% or more, or no inorganic filler at 10 wt% or more, selected from the group consisting of: alumina, aluminum silicate, calcium silicate, magnesium silicate, silicon dioxide, titanium dioxide, and mixtures thereof. In other embodiments, the inventive composition is free of 20 wt% or more inorganic filler, or free of 15 wt% or more inorganic filler, or free of 10 wt% or more inorganic filler, or free of any inorganic filler selected from the group consisting of: al-containing solids, Ca-containing solids, Mg-containing solids, Si-containing solids, Ti-containing solids, and mixtures thereof. In other embodiments, the compositions of the present invention do not contain a silsesquioxane, or any siloxane other than the mono-ring organosiloxane of formula (I). In some aspects, the compositions of the present invention are free of silsesquioxanes and any of the above groups of inorganic fillers.
In certain embodiments, the formula (I) monocyclic organosiloxanes overcome certain limitations of conventional adjuvants. For example, conventional adjuvants are often limited in solubility or miscibility in polyolefin compositions. This limits the maximum loading level of adjuvant in the composition. It also allows the adjuvant to migrate improperly to the surface of the composition (e.g., the surface of the pellet), thereby limiting the shelf life of the composition. Conventional adjuvants also pose other problems. For example, it may produce a crosslinked product that is insufficiently crosslinked after curing. Alternatively, the composition may cure too slowly for certain manufacturing operations. Alternatively, the composition may cure prematurely (i.e., scorch easily during injection molding and film extrusion). Not surprisingly, these problems have limited the structure of conventional auxiliaries that have been used for polyolefins.
Typically, conventional adjuvants comprise a conventional substructure group bonded to two or more ethylenic crosslinking groups. Conventional substructural groups are acyclic or cyclic multivalent groups comprising a backbone or a ring, respectively, which contain carbon atoms and optionally nitrogen and/or oxygen atoms in the backbone or ring, but not silicon atoms.
(E) Optionally present additives
In certain embodiments, the present compositions comprise one or more optional additives. Non-limiting examples of suitable additives include antioxidants, antiblock agents, stabilizers, colorants, Ultraviolet (UV) absorbers or stabilizers, flame retardants, compatibilizers, fillers, hindered amine stabilizers, tree retardants, methyl radical scavengers, scorch retarders, nucleating agents, carbon black, and processing aids.
The optional additives are present in an amount of greater than 0, or 0.01 wt%, or 0.1 wt% to 1 wt%, or 2 wt%, or 3 wt%, or 5 wt%, based on the total weight of the composition of the present invention.
Packaging film
In certain embodiments, the present disclosure relates to an encapsulant film comprising a curable composition comprising: (A) a polyolefin polymer, (B) an organic peroxide, (C) a silane coupling agent, and (D) an adjuvant comprising a monocyclic organosiloxane of formula (I). In some embodiments, the curable composition forms the entire encapsulation film.
In certain embodiments, the present disclosure relates to an encapsulation film comprising a crosslinked polymer composition comprising the reaction product of: (A) a polyolefin polymer, (B) an organic peroxide, (C) a silane coupling agent, and (D) an adjuvant comprising a monocyclic organosiloxane of formula (I). In some embodiments, the crosslinked polymer composition forms the entire encapsulation film.
In certain embodiments, the present disclosure relates to methods for forming an encapsulation film comprising a curable composition or a crosslinked polymer composition. In certain embodiments, (a) the polyolefin polymer, (B) the organic peroxide, (C) the silane coupling agent, (D) the coagent comprising the mono-cyclic organosiloxane of formula (I) and any optional additives may be added in any order or simultaneously or in combination with each other and by any method known in the art (e.g., impregnation, compounding, etc.). In some embodiments, (B) an organic peroxide, (C) a silane coupling agent, (D) an adjuvant comprising the mono-cyclic organosiloxane of formula (I), and any optional additives are pre-mixed, and the pre-mixture is added to (a) the polyolefin polymer before or during further processing (e.g., compounding, extrusion, molding, etc.) by any method known in the art. In some embodiments, the dried pellets of (a) polyolefin polymer are impregnated with a pre-mix (i.e., a cure package consisting of (B) an organic peroxide, (C) a silane coupling agent, (D) a coagent comprising the mono-cyclic organosiloxane compound of formula (I), and any optional additives), and then the impregnated pellets are further processed (e.g., compounded, extruded, shaped, etc.). In certain embodiments, the crosslinked polymer compositions and encapsulating films of the present invention are formed by film extrusion or compression molding.
In some embodiments, the present disclosure relates to a method of forming an encapsulation film, the method comprising (a) impregnating a polyolefin polymer with a premix to form the impregnated polyolefin polymer, wherein the premix comprises an organic peroxide, a silane coupling agent, and a coagent comprising a mono-cyclic organosiloxane compound of formula (I). In other embodiments, step (a) is performed at a temperature of 0 ℃ to 100 ℃ (e.g., 5 ℃ to 75 ℃, 10 ℃ to 50 ℃, 15 ℃ to 45 ℃, 20 ℃ to 40 ℃, etc.). In other embodiments, step (a) is performed for a duration (i.e., immersion time) of 0 minutes to 250 minutes (e.g., 0 minutes to 225 minutes, 25 minutes to 200 minutes, 50 minutes to 175 minutes, 60 minutes to 160 minutes, etc.).
Dry pellets of polyolefin polymers impregnated with a curing package containing conventional auxiliaries, such as Triallylisocyanurate (TAIC), require long impregnation times (up to 16 hours) to fully saturate the pellets, resulting in limited productivity and increased manufacturing costs. As defined herein, "fully impregnated" means a percent impregnation of greater than 90% to 100% (e.g., greater than or equal to 93%, greater than or equal to 95%, greater than or equal to 97%, greater than or equal to 98%, etc.). "percent impregnation" as defined herein refers to the following: (X3-X2)/
Surprisingly, when the conventional coagent is replaced by a coagent comprising a monocyclic siloxane of formula (I), the impregnation time required for complete impregnation of the (a) polyolefin polymer is significantly reduced. For example, in some embodiments, a percentage of impregnation greater than or equal to 90% may be achieved when step (a) of the method is performed at room temperature for a duration of less than or equal to 155 minutes. In other embodiments, a percent impregnation of greater than or equal to 95% may be achieved when step (a) of the method is performed at room temperature for a duration of less than or equal to 186 minutes. In other embodiments, a percentage of impregnation greater than 96% may be achieved when step (a) of the method is performed at room temperature for a duration of less than or equal to 155 minutes. In other embodiments, a percent impregnation of greater than or equal to 97% may be achieved when step (a) of the method is performed at room temperature for a duration of less than or equal to 175 minutes. In other embodiments, a percentage of impregnation greater than or equal to 99% may be achieved when step (a) of the method is performed at room temperature for a duration of less than or equal to 225 minutes.
In other embodiments, a percentage of impregnation greater than 90% may be achieved when step (a) of the method is performed at a temperature of 40 ℃ for a duration of less than or equal to 60 minutes. In other embodiments, when step (a) of the method is performed at a temperature of 40 ℃ for a duration of less than or equal to 35 minutes, a percentage of impregnation greater than or equal to 93% may be achieved. In other embodiments, a percentage of impregnation greater than 95% may be achieved when step (a) of the method is performed at a temperature of 40 ℃ for a duration of less than or equal to 75 minutes. In other embodiments, a percentage of impregnation greater than 97% may be achieved when step (a) of the method is performed at a temperature of 40 ℃ for a duration of less than or equal to 75 minutes. In other embodiments, a percentage of impregnation greater than 98% may be achieved when step (a) of the method is performed at a temperature of 40 ℃ for a duration of less than or equal to 75 minutes. In other embodiments, when step (a) of the method is performed at a temperature of 40 ℃ for a duration of less than 90 minutes, a percentage of impregnation of 100% may be achieved. In other embodiments, a percentage of impregnation greater than or equal to 96% may be achieved when step (a) of the method is performed at a temperature of 40 ℃ for a duration of less than or equal to 45 minutes. In other embodiments, a percentage of impregnation greater than or equal to 97% may be achieved when step (a) of the method is performed at a temperature of 40 ℃ for a duration of less than or equal to 60 minutes.
Furthermore, unexpectedly, other properties (e.g., curing properties, adhesion, volume resistivity, etc.) required to form an encapsulation film are maintained or improved when conventional adjuvants are replaced with adjuvants comprising a monocyclic organosiloxane of formula (I).
In certain embodiments, (a) the impregnated pellets of polyolefin polymer are cured during further processing (e.g., compounding, extrusion, molding, etc.). Accordingly, in some embodiments, the method of forming an encapsulation film further comprises: (2) the impregnated polyolefin polymer is cured and further processed to form an encapsulation film. In this regard, the temperature during further processing of the impregnated polyolefin polymer is 80 ℃, or 90 ℃ to 100 ℃, or 110 ℃, or 120 ℃, or 130 ℃, or 140 ℃, or 150 ℃, or 160 ℃, or 170 ℃.
In other embodiments, it is desirable to avoid or limit curing until other steps, such as lamination, as described below. Premature crosslinking and/or premature decomposition of the organic peroxide can result in encapsulation films having reduced glass adhesion. In other words, the encapsulation film comprising the curable composition remains reactive until lamination, at which point crosslinking is complete and the crosslinked polymer composition of the encapsulation film becomes the reaction product of the polyolefin polymer, the organic peroxide, the silane coupling agent, and the coagent comprising the monocyclic organosiloxane of formula (I). Thus, in a further embodiment, a method for further forming an encapsulation film comprises: (2) the impregnated polyolefin polymer is further processed to form a curable film. Subsequent steps include, but are not limited to: curing the curable film to form an encapsulation film, or curing the curable film during the laminating step to form an encapsulation film.
Thus, the temperature at which the impregnated polyolefin polymer is further processed may be below the decomposition temperature of the organic peroxide. In this regard, in some embodiments, the temperature during further processing of the impregnated polyolefin polymer is 80 ℃, or 90 ℃ to 100 ℃, or 110 ℃, or 120 ℃.
Curing as discussed herein can be free radical curing by irradiating the inventive composition with a curing effective dose of radiation and/or heating the inventive composition at a curing effect temperature with an organic peroxide in a manner that reacts (a) the polyolefin polymer with (D) the coagent to form a crosslinked product. The combination of a crosslinking effective amount of an adjuvant comprising a monocyclic organosiloxane of formula (I) with a curing effective amount of radiation or a curing effective temperature and any other desired reaction conditions (e.g., pressure or inert gas atmosphere) is sufficient to cure the composition of the invention and prepare a crosslinked polymer composition of the encapsulating film. The illumination source may be an electron beam, gamma radiation, ultraviolet light, or any combination thereof.
The compositions of the present invention can be cured (crosslinked) by irradiation or organic peroxides without ring opening of the mono-cyclic organosiloxane of the formula (I). The curing reaction is carried out in such a way that the mono-cyclic organosiloxane of formula (I) does not give rise to polymerized siloxanes (silicone polymers). Without being bound by theory, it is believed that the ingredients of the composition of the present invention are selected such that during curing, the monocyclic organosiloxane of formula (I) does not ring open to ring-opened silanol (S-OH) functional organosiloxane oligomers (linear or branched) and thus the polymerized siloxane (silicone polymer) is not formed in situ within the polyolefin polymer. The mono-cyclic organosiloxane of formula (I) is not capable of undergoing ring opening at least in part because the composition of the invention does not contain a ring opening catalyst and thus because the curing reaction is carried out in the absence of a ring opening catalyst. Excluded ring-opening catalysts are known and include phosphazene bases. Phosphazene bases have a core structure P ═ N, wherein the free N valency is linked to hydrogen, a hydrocarbyl group, -P ═ N or ═ P-N, and the free P valency is linked to ═ N or-N. Examples of phosphazene bases are found in US 8,426,519B 2 at column 9, line 29 to
In other embodiments, crosslinking of the inventive composition occurs in the absence of a platinum-based catalyst.
It could not have been predicted that the compositions of the present invention containing a monocyclic organosiloxane of formula (I) or a crosslinked polyolefin product of the present invention prepared therefrom have at least one improved property relative to a comparative polyolefin composition that does not contain a monocyclic organosiloxane of formula (I) or contains a linear vinylmethoxysiloxane homopolymer (oligomer), a vinyl, methylsiloxane homopolymer (oligomer), or a cage-like vinyl functional silsesquioxane, or a product prepared therefrom, respectively. The improved property may be a reduction in the time period ("T90") for the crosslinked polyolefin product to achieve 90% crosslinking, which indicates that a faster cure rate is beneficial; a greater maximum torque value ("MH"), which indicates a greater degree of crosslinking in the crosslinked polyolefin product is beneficial; increased scorch time ("tsl"), which represents a benefit to increased resistance to premature curing of the inventive compositions during extrusion (e.g., curing in an extruder rather than in a post-extrusion operation); and/or the monocyclic organosiloxanes of formula (I) can be supported in polyolefin polymers in greater concentrations without the occurrence of "sweating" of the monocyclic organosiloxanes of formula (I) compared to the possible support of conventional auxiliaries in polyolefin polymers. Less "sweating" during storage of the inventive composition for a certain period of time indicates greater compatibility and/or solubility of the monocyclic organosiloxane of formula (I) as silicon-based adjuvant in the polyolefin polymer of the inventive composition.
In aspects where the inventive composition further comprises an organic peroxide as a curing agent, the resulting inventive crosslinked polyolefin product prepared by curing may be characterized by a degree of crosslinking that is greater (greater in the number of crosslinks) than that achievable by a comparative crosslinked polyolefin product prepared by curing a comparative polyolefin composition comprising a polyolefin and an organic peroxide, but not comprising a monocyclic organosiloxane of formula (I). The resulting crosslinked polyolefin product of the present invention may be crosslinked to a greater degree than can be achieved using conventional coagents instead of the mono-ring organosiloxane of formula (I). The compositions of the present invention may have a longer shelf life without experiencing "sweating", possibly due to the fact that the solubility of the monocyclic organosiloxanes of formula (I) in the polyolefin polymer is higher than the solubility of conventional adjuvants in the polyolefin polymer. The T90 crosslinking time of the composition of the invention is shorter (faster crosslinking) than can be achieved using conventional coagents instead of the mono-ring organosiloxane of the formula (I). When the comparative crosslinked polyolefin product is formulated to have the same number of crosslinks as the forming agent, the crosslinked polyolefin product of the present invention has greater scorch resistance (e.g., tsl) than the comparative crosslinked polyolefin product.
Packaging film 1: in one embodiment, the encapsulating film is comprised of a curable composition (or a crosslinked polymer composition comprising the reaction product of) comprising: (A) a polyolefin polymer, (B) an organic peroxide, (C) a silane coupling agent, and (D) an adjuvant comprising a monocyclic organosiloxane of formula (I).
And (3) packaging film 2: in one embodiment, the encapsulating film is comprised of a curable composition (or a crosslinked polymer composition comprising the reaction product of) comprising: (A)80 wt%, or 85 wt%, or 88 wt%, or 90 wt%, or 95 wt%, or 97 wt%, or 97.50 wt%, or 97.75 wt% to 98.25 wt%, or 98.5 wt%, or 99 wt%, or 99.88 wt%, or 99.99 wt% of a polyolefin polymer, (B)0.1 wt%, or 0.5 wt%, or 1 wt% to 1.5 wt%, or 2 wt%, or 2.5 wt% or 3 wt% of an organic peroxide, (C)0.01 wt% or 0.05 wt%, or 0.10 wt%, or 0.15 wt%, 0.20 wt%, or 0.25 wt% to 0.3 wt%, or 0.4 wt%, or 0.5 wt%, or 1 wt%, or 1.5 wt%, or 2 wt% of a silane coupling agent, (D)0.01 wt%, or 0.05 wt%, or 0.10 wt%, or 0.15 wt%, or 0.20 wt%, or 0.25 wt%, or 0.30 wt%, or 0.35 wt%, or 0.5 wt%, or 1.5 wt%, or 0.5 wt%, or 1 wt%, or 1.5 wt% of a silane coupling agent, (D)0.01 wt%, or 0.05 wt%, or 0.10 wt%, or 0.15 wt%, or 0.20wt, Or 3 wt%, or 3.5 wt%, or 4 wt%, or 4.5 wt%, or 5 wt% of an adjuvant comprising a monocyclic organosiloxane of formula (I). It is understood that the total amount of components (a), (B), (C), (D) and any optional additives results in a 100 wt% composition.
And (3) packaging film: in one embodiment, the encapsulating film is comprised of a curable composition (or a crosslinked polymer composition comprising the reaction product of) comprising: (A) 95 to 99 wt% of a polyolefin polymer, (B)0.5 to 2 wt% of an organic peroxide, (C)0.1 to 0.5 wt% of a silane coupling agent, (D)0.2 to 1 wt% of an adjuvant comprising a monocyclic organosiloxane of formula (I), based on the total weight of the composition. It is to be understood that the total amount of components (a), (B), (C), (D) and any optionally present additives results in a 100 wt% composition.
In certain embodiments, the encapsulation film of the present disclosure is in accordance with
In certain embodiments, the encapsulation film is according to
In certain embodiments, the encapsulation film is according to
In certain embodiments, the encapsulating film is according to encapsulating
The encapsulation film of the present invention can have any thickness.
In one embodiment, the encapsulating film is a layer wherein a single layer is comprised of the composition of the present invention. In one embodiment, the encapsulating film has two or more layers, wherein at least one layer is comprised of the composition of the present invention.
Electronic device
The encapsulation film of the present invention is used for constructing an electronic device module. The encapsulation film serves as one or more "skins" for the electronic device, i.e., is applied to one or both facial surfaces of the electronic device, e.g., as a front encapsulation film or a back encapsulation film, or as both a front encapsulation film and a back encapsulation film, e.g., where the device is completely enclosed within a material.
In one embodiment, an electronics module includes (i) at least one electronic device, which is a plurality of such devices arranged in a generally linear or planar pattern, (ii) at least one cover sheet, and (iii) at least one encapsulation film according to any embodiment of the present disclosure. The encapsulation film is located between the cover plate and the electronic device, and the encapsulation film exhibits good adhesion to both the electronic device and the cover plate.
In one embodiment, an electronics module includes (i) at least one electronic device that is a plurality of such devices arranged in a generally linear or planar pattern, (ii) a front cover sheet, (iii) a front encapsulation film, (iv) a rear encapsulation film, and (v) a back sheet, wherein at least one of the (iii) front encapsulation film and the (iv) rear encapsulation film is an encapsulation film of the present invention. The electronic device is sandwiched between the front and rear encapsulation films, and the cover plate and the back plate enclose the front encapsulation film/electronic device/rear encapsulation film unit.
In one embodiment, the cover plate is glass, acrylic, polycarbonate, polyester, or a fluorine-containing resin. In another embodiment, the cover plate is glass.
In one embodiment, the backsheet is a single or multilayer film composed of glass, metal, or polymer resin. The back sheet is a film composed of glass or polymer resin. In another embodiment, the backsheet is a multilayer film comprised of a fluoropolymer layer and a polyethylene terephthalate layer.
In one embodiment, the electronic device is a solar cell or a Photovoltaic (PV) cell.
In one embodiment, the electronics module is a PV module.
Fig. 1 shows an exemplary PV module. The
The encapsulation film of the present invention may be a front encapsulation film, a rear encapsulation film, or both a front encapsulation film and a rear encapsulation film. In one embodiment, the encapsulation film of the present invention is a front encapsulation film. In another embodiment, the encapsulation film of the present invention is both a front encapsulation film and a back encapsulation film.
In one embodiment, the encapsulation film of the present invention is applied to an electronic device by one or more lamination techniques. The cover sheet is brought into direct contact with the first facial surface of the encapsulation film and the electronic device is brought into direct contact with the second facial surface of the encapsulation film by lamination. The cover sheet is brought into direct contact with the first face surface of the front encapsulation film, the back sheet is brought into direct contact with the second face surface of the back encapsulation film, and the electronic device is fixed therebetween and is brought into direct contact with the second face surface of the front encapsulation film and the first face surface of the back encapsulation film.
In one embodiment, the lamination temperature is sufficient to activate the organic peroxide and crosslink the inventive composition, i.e., a curable composition comprising the polyolefin polymer, the organic peroxide, the silane coupling agent, and the coagent comprising the monocyclic organosiloxane of formula (I) remains reactive while crosslinking occurs until lamination. During the crosslinking process, the silane coupling agent forms chemical bonds between two or more molecular chains of the polyolefin polymer through silane bonds. "silane bonds" have the structure-Si-O-Si-. Each silane linkage may link two or more, or three or more, molecular chains of the polyolefin polymer. The silane coupling agent also interacts with the surface of the cover sheet to increase the adhesion between the encapsulation film and the cover sheet. After lamination, the composition is the reaction product of a polyolefin polymer, an organic peroxide, a silane coupling agent, and an adjuvant.
In one embodiment, the lamination temperature used to prepare the electronic device is 130 ℃, or 135 ℃, or 140 ℃, or 145 ℃ to 150 ℃, or 155 ℃, or 160 ℃. In one embodiment, the lamination time is 8 minutes, or 10 minutes, or 12 minutes, or 15 minutes to 18 minutes, or 20 minutes, or 22 minutes, or 25 minutes.
In one embodiment, the electronic device of the present invention comprises an encapsulating film comprised of a crosslinked polymer composition that is the reaction product of (a) a polyolefin polymer, (B) an organic peroxide, (C) a silane coupling agent, and (D) a co-agent comprising a monocyclic organosiloxane of formula (I), and the encapsulating film has an initial glass adhesion greater than 60N/cm (e.g., greater than 70N/cm, greater than 80N/cm, greater than 90N/cm, greater than 100N/cm, etc.).
In one embodiment, the electronic device of the present disclosure comprises an encapsulation film according to
Some embodiments of the present invention will now be described in detail in the following examples.
Examples of the invention
Test method
Density is measured according to ASTM D792. Results are in grams (g)/cubic centimeter (g/cc or g/cm)3) And (6) recording.
Glass transition temperature (Tg) was measured according to ASTM D7028.
Melt Index (MI) was measured according to ASTM D1238 at 190 ℃, 2.16kg and reported in grams per 10 minutes (g/10 min).
Melting points were measured according to ASTM D3418.
Crosslinking or curing was tested according to ASTM D5289 using a moving die rheometer. A Moving Die Rheometer (MDR) was loaded with 4 grams of each sample. The MDR was run at 150 ℃ for 25 minutes and provided time versus torque curves for the samples over the given intervals. The temperature of 150 ℃ represents the module lamination temperature. The maximum torque applied by the MDR during the 25 minute test interval (MH) is reported in dNm. MH generally corresponds to the torque applied at 25 minutes. Report torque in minutesTime required to X% of MH (t)x)。txIs a standardized measure for understanding the cure kinetics of each resin. Up to 90% of MH (T)90) Time of (d) is reported in minutes.
The glass bond strength was measured by 180 ° peel test (average
The volume resistivity was tested according to the following, which is based on ASTM D257. Measurements were performed using a Keithley 6517B electrometer in combination with a Keithley 8009 test fixture. The test chamber, Keithley 8009, is located inside a forced-air oven, capable of operating at high temperatures (
where ρ is the volume resistivity (ohm-cm), V is the applied voltage (volts), A is the electrode contact area (cm)2) I is the leakage current (amperes) and t is the average thickness of the sample. To obtain the average thickness of the samples, the thickness of each sample was measured before the test, and five points of the sample were measured to obtain the average thickness. Volume resistivity testing was performed at 1000 volts at Room Temperature (RT) and 60 ℃. Two compression molded encapsulation films were tested to obtain an average value.
Material
The following materials were used to prepare examples of the present disclosure.
POE: an ethylene/octene copolymer having a density of 0.880g/cc (ASTM D782) and a melt index of 18.0g/10min (ASTM D1238, 2.16kg at 190 ℃) was purchased from the Dow chemical company.
TBEC: t-butyl peroxy 2-ethylhexyl carbonate, an organic peroxide, available from J & K scientific ltd.
VMMS: 3- (trimethoxysilyl) propyl methacrylate, a silane coupling agent available from Dow Corning.
TAIC: triallyl isocyanurate, a conventional adjuvant available from fangruda chemical co., Ltd., has the following structure:
vinyl-D4: 1, 3, 5, 7-tetravinyl-1, 3, 5, 7-tetramethylcyclotetrasiloxane, an adjuvant obtained from Alfa Aser and having the structure:
vinyl-D3: 1, 3, 5-trivinyl-1, 3, 5-trimethylcyclotrisiloxane, an adjuvant obtained from J & K science, Inc. and having the following structure:
sample preparation
Dipping:the compositions were prepared according to the formulations of table 1 below by first premixing the desired weight percentages of organic peroxide, silane coupling agent and adjuvant shown in table 1 in a sealable bottle. The total weight of organic peroxide, silane coupling agent and coagent for each composition was recorded as X1. Depending on the examples (see table 1), the dry pellets of POE were weighed (the weight of the dry pellets of each composition was recorded as X2) and then placed in a bottle for impregnation. To ensure uniform distribution and complete impregnation of the cure package (i.e., organic peroxide, silane coupling agent and coagent) into the pellets, the bottles were tumbled for 1 minute and then placed on a roller at Room Temperature (RT) or 40 ℃ for a certain impregnation time (seeTables 2 and 3). After a certain immersion time (see tables 2 and 3), the pellets were removed from the bottle and the surface of the pellets was wiped thoroughly with paper until no wetting was found on the used paper. The scraped pellets were then weighed and recorded as X3. The percent impregnation is then determined by the following equation discussed above: (X3-X2)/X1 × 100%.
Tables 2 and 3 provide the percent impregnation determined according to the above equation using the specific impregnation times at room temperature and 40 c, respectively, for each example. This percentage of impregnation is also provided in the impregnation curve of fig. 2.
TABLE 1
TABLE 2
TABLE 3
As shown in tables 2 and 3 and fig. 2, the composition comprising the conventional adjuvant required a long impregnation time to completely impregnate POE. These compositions represent the prior art. Surprisingly, the impregnation times (at room temperature) for the vinyl-D4 or vinyl-D3 based formulations (with the same amount of coagent and the same organic peroxide and silane coupling agent) were much shorter than those for the TAIC based formulations representative of the prior art. Furthermore, the immersion time was further shortened at 40 ℃ for the inventive examples. Accordingly, it has been found that replacing conventional adjuvants with the mono-ring organosiloxanes of formula (I), such as vinyl-D3 and vinyl-D4, significantly reduces the immersion time, thereby allowing the overall process time for forming the encapsulation film to be shortened. In addition, the inventive examples maintained other important performance characteristics, as shown in table 1.
Compression molding:after impregnation, the impregnated particles were cured and compression molded into 0.5mm packagesAnd (3) a membrane. Compression molding was performed using a hydraulic press. The composition was preheated at 120 ℃ for 5 minutes without applying pressure and then degassed. Subsequently, the composition was pressed at 10MPa and a temperature of 150 ℃ for 15 minutes to ensure complete curing. Finally, the temperature was cooled to room temperature and the pressure was released. The cured compression molded encapsulation film was then tested for volume resistivity.
Film extrusion: unlike compression molding, the impregnated pellets are also formed into an encapsulating film by a film extrusion method. The impregnated pellets were fed into a Brabender single screw mixer at 100 ℃ at a rotor speed of 40rpm to form a film (or sheet) of about 0.5mm thickness. The film was then stored in aluminum foil bags for subsequent testing or processing. During film extrusion, no curing was performed. Instead, curing is delayed until the lamination step discussed below.
Lamination of: the glass plate was cut into 4x6 square inch samples and cleaned with water and then dried before use. The backing sheet was also cut into 4x6 square inch samples. The film extruded encapsulation film was then cut into pieces that fit the glass panel and backsheet sample sizes. The backsheet samples, film extruded encapsulation films, and glass samples were then laminated together and laminated through a PENERGY L036 laminator. The samples were laminated under the following conditions: 150 ℃ for 20 minutes (4 minutes vacuum process and 16 minutes press). Glass adhesion testing was performed using the laminated samples.
As shown in table 1, the inventive examples provide similar or improved properties with respect to glass adhesion, volume resistivity and cure performance compared to TAIC-based compositions (representative of the prior art). Accordingly, the present disclosure provides novel POE-based compositions that significantly reduce the impregnation time of the cured pack in POE while maintaining good curing properties, glass adhesion, volume resistivity, and the like.
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