Polyolefin-polydiorganosiloxane block copolymers and hydrosilylation reaction methods for their synthesis
阅读说明：本技术 聚烯烃-聚二有机硅氧烷嵌段共聚物及用于其合成的氢化硅烷化反应方法 (Polyolefin-polydiorganosiloxane block copolymers and hydrosilylation reaction methods for their synthesis ) 是由 S·斯威尔 P·赫士德 D·德沃尔 Z·基恩 L·斯潘塞 J·雷德尔 B·尼尔逊 J· 于 2019-02-22 设计创作，主要内容包括：一种聚烯烃-聚二有机硅氧烷嵌段共聚物可以通过氢化硅烷化反应制备。(A polyolefin-polydiorganosiloxane block copolymer can be prepared by a hydrosilylation reaction.)
1. A polyolefin-polydiorganosiloxane block copolymer comprising the unit formula:
2. The copolymer of claim 1, wherein subscript w ═ 1, subscript x ═ 0, subscript y ═ 0, and subscript z ═ 1, and the copolymer has formula (IV):
3. the copolymer of claim 1, wherein subscript w ═ 2, subscript z ═ 0, subscript x ≧ 1, subscript y ≧ 0, and the copolymer has formula (V):
wherein subscript c is 0 or more.
4. The copolymer of claim 1 or claim 3, wherein subscript w ═ 2, subscript x ═ 1, subscript y ═ 0, subscript z ═ 0, and subscript c ═ 0, and the copolymer has formula (VI):
5. the copolymer of claim 1, wherein subscript z ═ 2, subscript w ═ 0, subscript x ≧ 0, and subscript y ≧ 1, and the copolymer has formula (VII):
wherein subscript d is 0 or more.
6. The copolymer of claim 1 or claim 5, wherein subscript w ═ 0, subscript x ═ 1, subscript y ═ 0 and subscript z ═ 2, subscript d ═ 0, and the copolymer has formula (VIII): .
7. The copolymer of any of the preceding claims, wherein
(i) Each R3Having the unit formula H [ (CH)2CH2)t(CHR7CH2)u]g，
(ii) Each R6Having the formula of a unit [ (CH)2CH2)t(CHR7CH2)u]g(ii) a Or
(iii) (ii) both (i) and (ii), wherein subscripts t and u have relative values such that 0 < t ≦ 1,0 ≦ u ≦ 1, subscript g ≦ 1, and each R7Is an independently selected monovalent hydrocarbon group of 1 to 20 carbon atoms.
8. The copolymer of claim 7, wherein each R7Is hexyl.
9. The copolymer of any of the preceding claims, wherein each R1Is methyl, each R3Is methyl, and each RLIs selected from-C2H4-and-C3H6-。
10. The copolymer of any of the preceding claims, wherein R10Represents an alkoxysilyl-functional hydrocarbylene-containing group having a formula selected from:
one or both of; and
(R3 2SiO2/2)E(R3RLSiO2/2)F
11. A method for preparing a polyolefin-polydiorganosiloxane block copolymer, wherein the method comprises:
optionally, pre-1) preparing a silyl terminated polyolefin having 1 to 2 terminal silyl groups per molecule by a process comprisingWherein each R1Is an independently selected monovalent hydrocarbon group, and each subscript a is independently 1 or 2:
i) combining starting materials comprising
a) A metal of a polymer base,
optionally b) a nitrogen-containing heterocycle, and
c) a halosilane, and
optionally d) a solvent; thereby forming a product comprising the silyl terminated polyolefin;
optionally ii) washing the product with water, thereby removing unwanted substances comprising the starting material b); and
optionally iii) recovering the silyl terminated polyolefin; and
1) combining starting materials comprising
A) The silyl terminated polyolefin;
B) a substantially linear, alternatively linear, polydiorganosiloxane having from 1 to 2 terminal silicon-bonded terminal aliphatically unsaturated organic groups capable of undergoing a hydrosilylation reaction;
C) a hydrosilylation reaction catalyst;
optionally D) a solvent;
optionally E) an inhibitor of the hydrosilylation reaction; and
optionally F) an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom.
12. The method of claim 11, wherein a) the silyl terminated polyolefin has the unit formula (a 1):
13. The method of claim 11 or claim 12, wherein starting material B) comprises a polydiorganosiloxane of formula (B1):
14. The method according to any one of claims 11 to 13, wherein any one of conditions a) to D) is satisfied, wherein:
with the proviso that A) the silyl terminated polyolefin has one terminal silyl group per molecule,
with the proviso that B) the silyl terminated polyolefin has two terminal silyl groups per molecule,
condition C) is that the polyorganosiloxane has one terminal organic group per molecule having a terminal aliphatic unsaturation, and.
Condition D) is that the polyorganosiloxane has two terminal organic groups per molecule having terminal aliphatic unsaturation.
15. The method of claim 14, wherein one of conditions E) through I) is satisfied, wherein
Condition E) represents both condition a) and condition C),
condition F) represents both condition a) and condition D),
condition G) represents both condition B) and condition C),
condition H) represents all three of A), B) and D), and
condition I) represents all three of B), C) and D).
Technical Field
Described herein are polyolefin (a) -polyorganosiloxane (B) block copolymers and methods for their synthesis. More specifically, block copolymers having the structure polyolefin-polyorganosiloxane (AB), polyolefin-polyorganosiloxane-polyolefin (ABA), polyorganosiloxane-polyolefin-polyorganosiloxane (BAB), and copolymers comprising the structure (AB) n are described herein, where the subscript n denotes the number of repeating polyolefin-polyorganosiloxane segments.
Background
Block copolymers of polyolefins and polyorganosiloxanes have a wide range of applications due to the combination of properties with block structures, including the ability to modify the surface of finished plastic parts for friction management, improved scratch and abrasion resistance, and as processing aids to increase melt flow to reduce cycle times. In addition, these block copolymers can be used as thermoplastic elastomers, especially those having ABA triblock and (AB) n structures.
The chain shuttling technique of The Dow Chemical Company provides a useful mechanism for forming multi-block Olefin Block Copolymers (OBCs) as well as OBCs with controlled block sequence distribution. In addition, chain shuttling techniques can enable the synthesis of relatively exotic, end-functional polyolefins. This technique involves polymerizing olefins in the presence of a metal alkyl Chain Shuttling Agent (CSA), such as diethylzinc. If a large excess of chain shuttling agent is used, the majority of the chains initiated by the alkyl groups of the CSA result in the majority of the chains being functionalized by the CSA at one end and bound to the metal cation at the other end. These metal polymeryls can be further functionalized to produce chain end functional polyolefins derived from the metal cationic chain ends, or can be prepared by hydrolyzing the complex to leave functional groups on the opposite end that grow out of the CSA.
It is desirable to attach these silicon-containing functional groups to the polyorganosiloxane via a linking group. The linking group can be a symmetrical chain end, an inert chain end, or a chain end combined with an orthogonal reactive functional group. The polyorganosiloxanes and polyolefins may be (mono-) or di-terminal functional. Thus, the resulting product may be a diblock (AB) polymer, triblock (ABA or BAB) polymer, multiblock (AB) n polymer, or mixtures thereof.
In previously reported attempts to react Si-H functional polyorganosiloxanes with alkenyl-terminated polyolefins, the catalyst causes unwanted isomerization of the double bond to an internal position, deactivating it to the hydrosilylation reaction and limiting the conversion. This results in copolymers containing unreacted homopolymer, limiting their industrial applicability.
Disclosure of Invention
The polyolefin-polydiorganosiloxane block copolymer (copolymer) comprises the unit formula:
wherein each RLIs an independently selected divalent hydrocarbon radical, each R1Is an independently selected monovalent hydrocarbon radical, each R3Independently selected from hydrogen atoms and monovalent hydrocarbon groups free of terminal aliphatic unsaturation, each R5Is an independently selected hydrogen terminated polyolefin, each R6Is an independently selected divalent polyolefin block, each R10Independently selected from R3And an alkoxysilyl-functional hydrocarbylene-containing group, each subscript a is independently 1 or 2, and each subscript b is independently 0 or a positive number; subscript w is 0 to 2, subscript x is 0 or a positive number, subscript y is 0 or a positive number, subscript z is 0 to 2, amount (w + y) ≥ 1, amount (x + z) ≥ 1, provided that when subscript w ≥ 0, subscript z > 0, and when subscript z ≥ 0, subscript w > 0.
A method for preparing a polyolefin-polydiorganosiloxane block copolymer comprises:
1) combining starting materials, the starting materials comprising:
A) a polyolefin having 1 to 2 terminal silyl groups per molecule, wherein the terminal silyl groups have the formula
B) a substantially linear polydiorganosiloxane having from 1 to 2 terminal silicon-bonded terminal aliphatically unsaturated organic groups capable of undergoing a hydrosilylation reaction; and
C) a hydrosilylation reaction catalyst.
Detailed Description
A method for preparing a polyolefin-polydiorganosiloxane block copolymer comprises:
1) combining starting materials, the starting materials comprising:
A) a polyolefin having 1 to 2 terminal silyl groups per molecule,
B) a polydiorganosiloxane having 1 to 2 terminal organic groups having terminal aliphatic unsaturation, and
C) a hydrosilylation reaction catalyst.
The starting material may optionally further comprise one or more additional starting materials selected from the group consisting of: D) a solvent, E) a hydrosilylation reaction inhibitor, F) an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom, and a combination of two or more of D), E), and F).
Step 1) may be carried out by any convenient means, such as mixing at a temperature of from 50 ℃ to 200 ℃, alternatively from 100 ℃ to 120 ℃, at ambient pressure. Step 1) may be carried out by any convenient means, such as solution processing (i.e. dissolving and/or dispersing the other starting materials in D) solvent and heating) or melt extrusion (e.g. when no solvent is used or solvent is removed during processing).
The method may optionally further comprise one or more additional steps. For example, the method may further comprise: 2) recovering the polyolefin-polydiorganosiloxane block copolymer after step 1). Recovery may be carried out by any convenient means, such as stripping and/or distillation to undesired species, such as catalyst, inhibitors (if used), by-products and/or unreacted starting materials. Alternatively, recovery can be carried out by precipitating the polyolefin-polydiorganosiloxane block copolymer in a non-solvent, thereby removing unwanted materials, optionally washing with water.
A) Silyl terminated polyolefins
The starting material a) is a polyolefin having from 1 to 2 terminal silyl groups per molecule (silyl-terminated polyolefin). The terminal silyl group has the formula (A1):
Alternatively, the silyl terminated polyolefin may have the unit formula (a 2):
wherein the subscripts a and R1As described above, subscript f is 0 to 1, subscripts t and u have relative values such that 0 < t ≦ 1,0 ≦ u ≦ 1, subscript g is 1 or more, and each R isetRepresents an ethylene unit, and each ROIndicating olefin units other than ethylene. ROExamples of α -olefins, which may be α -olefins or cyclic olefins, are described below and include ethylene, propylene and octene cyclic olefins are described below and include ethylidene norbornene, vinyl norbornene, cyclohexene and cyclopentene alternatively subscript g may be from 1 to 500Alternatively 10 to 400, and alternatively 18 to 360. Alternatively, the subscript g may have a value sufficient to provide the silyl terminated polyolefin with an Mn of from 500 to 50,000g/mol, alternatively from 500 to 10,000 g/mol.
Alternatively, the silyl terminated polyolefin may have the unit formula (a 3):wherein the subscripts a, f, g, t and u and R1As described above. Each R7Independently a monovalent hydrocarbon group of 2 to 20 carbon atoms. For R7The monovalent hydrocarbon group of (a) may be an alkyl group, an alkenyl group or an aryl group; alternatively an alkyl group. Alternatively, R7May be an alkyl group of 2 to 12 carbon atoms, and alternatively 2 to 6 carbon atoms. Alternatively, each R7Is hexyl.
Starting material a), a silyl terminated polyolefin, may have one terminal silyl group per molecule (i.e., where subscript f ═ 1). Examples of such silyl terminated polyolefins having a silyl group at one end of the polymer chain include: dimethylhydrosilyl-terminated polyethylene; dimethylhydrosilyl-terminated poly (ethylene/octene) copolymer; (ii) a methyl dihydrosilyl terminated polyethylene; a methyldihydrosilyl-terminated poly (ethylene/octene) copolymer; diphenylhydrosilyl-terminated polyethylene; diphenylhydrosilyl-terminated poly (ethylene/octene) copolymers; phenyldihydrosilyl terminated polyethylenes; a phenyldihydrosilyl terminated poly (ethylene/octene) copolymer; a chlorophenylhydrosilyl-terminated polyethylene; or a chlorophenylhydrosilyl-terminated poly (ethylene/octene) copolymer. Such silyl terminated polyolefins may be prepared by the methods described in co-pending U.S. patent application serial No. 62/644635 filed on 3/19/2018, U.S. patent application serial No. 62/644624 filed on 3/19/2018, both of which are incorporated herein by reference.
A silyl terminated polyolefin having one terminal silyl group per molecule may be prepared by a process comprising: 1) combining starting materials, the starting materials comprising: a) poly(s) are polymerizedA metal-compote, optionally b) a nitrogen-containing heterocycle, and c) a halosilane; thereby forming a product comprising a silyl terminated polyolefin. The starting material may optionally further comprise d) a solvent. The process may optionally further comprise one or more additional steps selected from: 2) washing the product with water, and 3) recovering the product. a) The metal polymeryl may be prepared by a process comprising: combining starting materials, the starting materials comprising: i) an olefin monomer, ii) a catalyst, and iii) a compound of formula RF NM, wherein M is a metal atom of group 1, 2, 12 or 13 of the periodic Table of the elements, each RFIndependently a monovalent hydrocarbon group of 1 to 20 carbon atoms, and subscript N is 1 to the maximum valence of the metal selected for M. In certain embodiments, M may be a divalent metal including, but not limited to, calcium (Ca), magnesium, and zinc (Zn), and in this embodiment, the subscript N ═ 2. In certain embodiments, M may be a trivalent metal including, but not limited to, aluminum (Al), boron (B), and gallium (Ga), and in this embodiment the subscript N ═ 3. Alternatively, M may be Zn or Al; and alternatively Zn. The monovalent hydrocarbon group of 1 to 20 carbon atoms can be an alkyl group (as defined herein), alternatively exemplified by ethyl, propyl, octyl, and combinations thereof.
Suitable olefin monomers are disclosed, for example, in U.S. Pat. No. 7,858,706 at column 16, lines 5-36 and U.S. Pat. No. 8,053,529 at column 12, lines 7-41, which are incorporated herein by reference. Examples of suitable olefin monomers include linear or branched alpha-olefins of 2 to 30 carbon atoms, alternatively 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; from 3 to 30, alternatively from 3 to 20 carbon atoms, of cycloolefins, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl-1, 4, 5, 8-dimethylbridge-1, 2,3, 4, 4a, 5, 8, 8 a-octahydronaphthalene. Alternatively, the starting material i) may comprise ethylene and optionally one or more olefin monomers other than ethylene, such as propylene or 1-octene. Alternatively, the olefin monomers may be ethylene and 1-octene. Alternatively, the olefin monomer may be ethylene. Suitable catalysts (and optional co-catalysts) are disclosed, for example, in U.S. Pat. No. 7,858,706 at column 19, line 45 to column 51, line 29, and U.S. Pat. No. 16, line 37 to column 48, line 17 of U.S. Pat. No. 8,053,529, which are incorporated herein by reference. Suitable chain shuttling agents include trialkyl aluminum and dialkyl zinc compounds such as triethyl aluminum, tri (isopropyl) aluminum, tri (isobutyl) aluminum, tri (n-hexyl) aluminum, tri (n-octyl) aluminum, triethyl gallium, and diethyl zinc. Suitable chain shuttling agents are disclosed at column 16, line 37 through column 19, line 44 of U.S. Pat. No. 7,858,706, and at column 12, line 49 through column 14, line 40 of U.S. Pat. No. 8,053,529, which are incorporated herein by reference.
Metal polymeryls suitable for use in preparing the silyl terminated polyolefins may be prepared using known process conditions and equipment, such as those disclosed in Arriola et al, U.S. Pat. No. 7,858,706 at column 52, line 2 to column 57, line 21 and Carnahan et al, U.S. Pat. No. 8,053,529.
An optional nitrogen-containing heterocycle may be added, for example, when the metal polymeryl is a polymeryl zinc and the halosilane is a chlorosilane. The optional nitrogen-containing heterocycle may have a formula selected from the group consisting of:
b1)b2)b3)
b4)b5)
b6)
When nitrogen-containing heterocycles are used, the resulting product can be recovered, for example, by water washing to remove the nitrogen-containing heterocycles prior to using the silyl-terminated polyolefin in the process for preparing the polyolefin-polydiorganosiloxane block copolymers described herein. Without wishing to be bound by theory, it is believed that the presence of nitrogen-containing heterocycles may be detrimental to the hydrosilylation reaction and, therefore, removal by water washing may increase reactivity in the process for preparing polyolefin-polydiorganosiloxane block copolymers.
The halosilane may have the formula HJR12 KSiX(4-J-K)Wherein each R is12Independently selected from hydrogen and monovalent hydrocarbon radicals of 1 to 18 carbon atoms, each X is independently a halogen atom, subscript J is 1 to 3, and subscript K is 0 to 2, provided that the amount (J + K). ltoreq.3. Examples of suitable halosilanes include, but are not limited to: dihalosilanes, such as methylhydrodichlorosilane, methylhydrodiiodosilane, methylhydrochloroiodosilane, ethylhydrodichlorosilane, ethylhydrodibromosilane, ethylhydrodiiodosilane, ethylhydrochloroiodosilane, propylhydrodichlorosilane, propylhydrodibromosilane, propylhydrodiiodosilane, propylhydrochloroiodosilane, phenylhydrodichlorosilane, phenylhydrodiiodosilane, phenylhydrodibromosilane, and mixtures thereof. Examples of suitable halosilanes further include, but are not limited to: monohalosilanes, such as dimethylhydrochlorosilane, dimethylhydrobromosilane, dimethylhydroiodosilane, diethylhydrochlorosilane, diethylhydroiodosilane, dipropylhydrochlorosilane, dipropylhydrobromosilane, dipropylhydroiodosilane, diphenylhydrochlorosilane, diphenylhydroiodosilane, diphenylhydrobromosilane and mixtures thereof. Alternatively, the halosilane may be selected from the group consisting of: c1) dimethylhydrochlorosilane, c2) diphenylhydrochlorosilane, c3) phenyldihydrochlorosilane, c4) phenylhydrodichlorosilane, c5) dimethylhydroiodosilane, and mixtures of two or more of c1), c2), c3), c4), and c 5).
The starting material (d) solvent may optionally be used in step 1) of the process to prepare the silyl terminated polyolefin. The solvent may be a hydrocarbon solvent, such as an aromatic solvent or an isoparaffinic solvent. Suitable solvents include, but are not limited to: a non-polar aliphatic or aromatic hydrocarbon solvent selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, decalin, benzene, toluene, xylene; isoparaffinic fluids, including but not limited to IsoparTME、IsoparTMG、IsoparTMH、IsoparTML、IsoparTMM; non-aromatizing fluids, including but not limited to ExxsolTMD or isomers and mixtures of two or more thereof. Alternatively, the solvent may be toluene and/or IsoparTME。
Alternatively, the starting material a), the silyl-terminated polyolefin, may have two silyl end groups per molecule (i.e., in formulae (a2) and (A3) where subscript f ═ 0, the silyl-terminated polyolefin is telechelic. Such telechelic silyl terminated polyolefins may be prepared by processes such as those disclosed in co-pending U.S. patent application serial No. 62/644808 filed on 3/19/2018, which is incorporated herein by reference.
Telechelic silyl terminated polyolefins may be prepared, for example, by a process comprising: 1) combining starting materials comprising a') a silicon-terminated organometallic and c) a halosilane (as described above) to obtain a product comprising a silyl-terminated polyolefin. In a further embodiment, the starting material for the process may further comprise b) a nitrogen-containing heterocycle (as described above). The starting materials for this process may optionally further comprise d) a solvent (as described above).
The process may optionally further comprise one or more additional steps. For example, the process may further comprise: 2) recovering the telechelic silyl terminated polyolefin. Recovery may be carried out by any suitable means, such as precipitation and filtration, optionally with washing with water, to remove unwanted materials.
The amount of each starting material depends on various factors, including the specific selection of each starting material. However, in certain embodiments, a molar excess of starting material c) may be used per molar equivalent of starting material a'). For example, the amount of starting material c) may be 2 to 3 molar equivalents per molar equivalent of starting material a'). If starting material b) is used, the amount of starting material b) may be 2 molar equivalents per molar equivalent of starting material a').
d) The amount of solvent will depend on various factors including the choice of starting materials a'), c) and, if present, b). However, the amount of d) solvent may be from 65% to 95% by weight of the combined weight of all starting materials used in step 1).
The starting material a') may be a silicon-terminated organometallic having the formula (II) or (III):
wherein
MA is a divalent metal selected from the group consisting of Zn, Mg, and Ca;
MB is a trivalent metal selected from the group consisting of Al, B, and Ga;
each Z is an independently selected divalent hydrocarbon group of 1 to 20 carbon atoms;
subscript m is a number of from 1 to 100,000;
each J is independently a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms;
each RA、RBAnd RCIndependently selected from the group consisting of: a hydrogen atom, a monovalent hydrocarbon group of 1 to 10 carbon atoms, a vinyl group, an alkoxy group, or one or more siloxy units selected from M, D and T units:
when R isA、RBAnd RCWhen two or all three of (A) are each independently one or more siloxy units selected from D and T units, R isA、RBAnd RCTwo or all three of which may optionally be joined together to form a ring structure.
In certain embodiments, subscript m of formulae (II) and (III) is a number of 1 to 75,000, 1 to 50,000, 1 to 25,000, 1 to 10,000, 1 to 5,000, 1 to 2,500, and/or 1 to 1,000.
In certain embodiments of formula (II), MA is Zn. In certain embodiments of formula (III), MB is Al. In further embodiments of formula (II), J is ethyl. In further embodiments of formula (III), J is a hydrogen atom.
Prior to this process, silicon-terminated organometallic compounds may be prepared according to the disclosures of co-pending U.S. patent application nos. 62/644654 and 62/644664, both filed on 3/19/2018, both of which are incorporated herein by reference.
For example, in certain embodiments, the silicon-terminated organometallic may be prepared by a process comprising combining starting materials comprising: (a) a vinyl-terminated silicon-based compound, (b) a chain shuttling agent, (c) a procatalyst, (d) an activator, (e) an optional solvent, and (f) an optional scavenger, thereby obtaining a product comprising a silicon-terminated organometallic.
Alternatively, the silicon-terminated organometallic may be prepared by a process comprising combining at elevated temperature starting materials comprising: (a) a vinyl terminated silicon based compound, (b) a chain shuttling agent, and optionally (e) a solvent. The process may be carried out at a temperature of from 60 ℃ to 200 ℃, alternatively from 80 ℃ to 180 ℃, and alternatively from 100 ℃ to 150 ℃. The process may be carried out for a duration of 30 minutes to 200 hours.
In certain embodiments, (a) the vinyl-terminated silicon-based compound may have the formula (IV):
wherein Z, RA、RBAnd RCAs described above.
In certain embodiments, (b) the chain shuttling agent can be of the formula RF NM, wherein RFM and subscript N are as described above.
In certain embodiments, the (c) procatalyst may be any compound or combination of compounds capable of polymerizing unsaturated monomers when combined with an activator. Suitable procatalysts include those disclosed in: WO 2005/090426, WO 2005/090427, WO 2007/035485, WO 2009/012215, WO 2014/105411, WO 2017/173080, U.S. patent publication nos. 2006/0199930, 2007/0167578, 2008/0311812 and us patent nos. 7,355,089B 2, 8,058,373B 2 and 8,785,554B 2. The nitrogen-containing heterocycle and the halosilane are as described above for starting materials b) and c) for preparing the silyl-terminated polyolefin having one terminal silyl group per molecule.
In certain embodiments, the (d) activator can be any compound or combination of compounds capable of activating the procatalyst to form an active catalyst composition or system. Suitable activators include, but are not limited to, bronsted acids, lewis acids, carbocationic species, or any activator known in the art, including but not limited to those disclosed in WO 2005/090427 and U.S. patent No. 8,501,885B 2. In exemplary embodiments, the cocatalyst is [ (C)16-18H33-37)2CH3NH]Tetrakis (pentafluorophenyl) borate.
In certain embodiments, the (e) optional solvent may be any of the solvents disclosed above as starting material (d) or as described below.
In further embodiments, the silicon-terminated organometallic prepared by the above process may be followed by a subsequent polymerization step. Specifically, the silicon-terminated organometallic prepared by the above process can be combined with at least one olefin monomer, a procatalyst as defined herein, an activator as defined herein and optional materials such as solvents and/or scavengers under polymerization process conditions known in the art, including but not limited to those disclosed in U.S. Pat. No. 7,858,706 and U.S. Pat. No. 8,053,529. Such polymerization steps substantially increase the subscript n in formula (I) and the subscripts m in formulae (II) and (III). Examples of suitable olefin monomers for the polymerization step are described above.
As described below, the silicon-terminated organometallic may also be prepared by: combined comprising 6-bromo-1-hexene, THF and chlorodimethylsilane (Me)2HSiCl) to form hex-5-en-1-yldimethylsilane, followed by combining hexa-5-en-1-yldimethylsilane,Triethylborane, borane-dimethyl sulfide complex, and diethyl zinc to form a silicon-terminated organometallic.
Alternatively, the silicon-terminated organometallic may be prepared in a batch reactor using a process as described below with reference to example 10 by varying the appropriate starting materials, i.e., olefin monomer, catalyst, chain shuttling agent, catalyst, procatalyst, activator, and solvent, suitable examples of which are described herein. Step 1) of combining the starting materials may be carried out by any suitable means, such as mixing at a temperature of 50 ℃ to 200 ℃, alternatively 100 ℃ to 120 ℃, at ambient pressure. The heating may be carried out under inert drying conditions. In certain embodiments, step 1) of combining the starting materials may be performed for a duration of 30 minutes to 20 hours, alternatively 1 hour to 10 hours. In further embodiments, step 1) of combining the starting materials may be performed by solution processing (i.e., dissolving and/or dispersing the starting materials in (d) solvent and heating) or melt extrusion (e.g., when (d) solvent is not used or is removed during processing).
The silicon-terminated organometallic prepared as described above for the starting material (a') can then be combined with (c) a halosilane and optionally (b) a nitrogen-containing heterocycle and/or (d) a solvent, as described above, to produce a telechelic silyl-terminated polyolefin.
Alternatively, the silyl-terminated polyolefin suitable for use as starting material a) may be prepared in a solution polymerization process, wherein the polyolefin polymer is prepared by a process comprising: a) combining i) an olefin monomer, ii) a catalyst, and iii) the above-described chain shuttling agent to produce iv) a metal polymeryl; b) combining iv) a metal polymeryl, v) a halosilane, and optionally v) a nitrogen-containing heterocycle; wherein steps a) and b) are carried out in solution. In solution, the resulting silyl terminated polyolefin may comprise from 10% to 20% by weight of the total reaction mixture. The remainder generally comprises unreacted olefin monomer and non-reactive solvent. Commercial processes are typically carried out in continuous reactors, where fresh olefin monomer and catalyst are continuously fed to achieve steady state conversion to polyolefin, and polyolefin is removed at a rate commensurate with these feeds and conversion to polyolefin. In these systems, the olefin monomer is not completely converted to polyolefin. For example, in the case of copolymerization of ethylene and alpha-olefins, the effluent from the reactor typically contains unreacted monomer, 10% ethylene and > 50% alpha-olefins. After polymerization, the solvent and unreacted monomers can be removed by a devolatilization process to leave the silyl terminated polyolefin as a solid. After devolatilization of the silyl terminated polyolefin, the starting materials comprising the silyl terminated polyolefin, polydiorganosiloxane and catalyst can be combined in step 1) of the process described above for preparing the polyolefin-polydiorganosiloxane block copolymer.
The starting material a) may be one silyl terminated polyolefin or may comprise two or more silyl terminated polyolefins that differ in at least one of the following properties: structure, viscosity, average molecular weight, olefin block and sequence. Alternatively, the starting material a) may comprise a mixture of silyl terminated polyolefins, wherein a silyl terminated polyolefin mono-terminated with a silyl group having one terminal silyl group per molecule is used in the mixture) and a telechelic silyl terminated polyolefin are both used for the starting material a).
The amount of starting material a) used in step 1 of the process for preparing the copolymers described herein will depend on various factors including whether a mixture of mono-and telechelic silyl-terminated polyolefins is used, the desired structure of the polyolefin-polydiorganosiloxane block copolymer to be formed, and the choice of starting material B), but the amount of starting material a) can be from 5% to 95% of the combined weight of all starting materials combined in step 1). Alternatively, the amount of starting material a) may be from 10% to 60%, and alternatively from 10% to 40%, on the same basis.
B) Polydiorganosiloxane
In the process for preparing the copolymers, the starting materials B) are polydiorganosiloxanes having from 1 to 2 terminal silicon-bonded terminal aliphatically unsaturated organic groups which are capable of undergoing hydrosilylation reactions. The polydiorganosiloxane is substantially linear, alternatively linear.
The starting material B) may comprise a polydiorganosiloxane of formula (B1):
in the formula (B1), each R2Is an independently selected monovalent organic group having a terminal aliphatic unsaturation. Each R3Independently a hydrogen atom or a monovalent organic group free of terminal aliphatic unsaturation. Each R4Independently selected from R2And R3. Subscript b may be 0 or a positive number. Alternatively, subscript b has an average value of at least 2. Alternatively, subscript b may be from 2 to 2000. Alternatively, subscript b may be 10 to 1,000. Alternatively, subscript b may be 30 to 500.
For R2The group having a terminal aliphatic unsaturation of (a) may be an alkenyl group, examples of which are, but not limited to, vinyl, allyl, butenyl (including n-butenyl, isobutenyl, and tert-butenyl), and hexenyl (including straight and branched chain isomers thereof). Alternatively, for R2The group having a terminal aliphatic unsaturated bond of (a) may be an alkynyl group, and examples thereof are, but not limited to, ethynyl, propynyl and butynyl groups (including branched and linear isomers thereof). Alternatively, each R2May be an alkenyl group. Alternatively, each R2May be selected from the group consisting of vinyl, allyl, and hexenyl. Alternatively, each R2It may be vinyl or allyl. Alternatively, each R2May be a vinyl group.
For R3Suitable monovalent organic groups include monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups. Examples of monovalent hydrocarbon groups include, but are not limited to, alkyl groups, as described above for R1Those mentioned as alkyl groups; and aryl, as hereinbefore described for R1Those mentioned as aryl groups. Examples of monovalent halogenated hydrocarbon groups include, but are not limited to, chlorinated alkyl groups such as chloromethyl and chloropropyl; fluorinated alkyl groups such as fluoromethyl, 2-fluoropropyl, 3, 3, 3-trifluoropropyl, 4, 4, 4-trifluorobutyl, 4, 4, 4,3, 3-pentafluorobutyl, 5,5, 5, 4, 4, 3, 3-heptafluoropentyl, 6, 6, 6,5, 5, 4, 4, 3, 3-nonafluorohexyl and 8, 8, 8,7, 7-pentafluorooctyl; chlorinated cycloalkyl groups such as 2, 2-dichlorocyclopropyl, 2, 3-dichlorocyclopentyl; and fluorinated cycloalkyl groups such as 2, 2-difluorocyclopropyl, 2, 3-difluorocyclobutyl, 3, 4-difluorocyclohexyl and 3, 4-difluoro-5-methylcycloheptyl. Examples of other monovalent organic groups include, but are not limited to, hydrocarbon groups substituted with oxygen atoms, such as glycidoxyalkyl; and hydrocarbon groups substituted with nitrogen atoms, such as aminoalkyl groups; and cyano-functional groups such as cyanoethyl and cyanopropyl. Alternatively, each R3Are monovalent hydrocarbon radicals, examples of which are alkyl and aryl radicals, alternatively methyl and phenyl radicals.
In one embodiment, each R4Is R3Groups as described above. Alternatively, each R4Is R2Groups as described above. Alternatively, mixtures of polydiorganosiloxanes can be used as starting materials B), wherein R4Some examples of (A) are R3And R is4Is R2. The starting material B) may be a polydiorganosiloxane or may comprise two or more polyorganosiloxanes which differ in at least one of the following properties: structure, viscosity, average molecular weight, siloxane units, and sequence.
The starting materials B) may comprise polydiorganosiloxanes such as
i) An α, ω -dimethylvinylsiloxy terminated polydimethylsiloxane;
ii) α -dimethylvinylsiloxy terminated- ω -trimethylsiloxy terminated polydimethylsiloxane;
iii) α, ω -dimethylvinylsiloxy terminated poly (dimethylsiloxane/methylphenylsiloxane);
iv) α -dimethylvinylsiloxy terminated- ω -trimethylsiloxy terminated poly (dimethylsiloxane/methylphenylsiloxane);
v) an α, ω - (phenyl, methyl, vinylsiloxy) terminated polydimethylsiloxane;
vi) α, ω -dimethylhexenylsiloxy terminated polydimethylsiloxane;
vii) α -dimethylhexenylsiloxy terminated- ω -trimethylsiloxy terminated polydimethylsiloxane;
viii) a combination of two or more of i), ii), iii), iv), v), vi), and vii).
Methods for preparing polydiorganosiloxanes suitable for use as starting material B), such as hydrolysis and condensation of the corresponding organohalosilanes or equilibration of cyclic polydiorganosiloxanes, are well known in the art.
The amount of starting material B) used in step 1) of the process described herein will depend on various factors including whether a mixture of mono-and telechelic polydiorganosiloxanes is used, the desired structure of the polyolefin-polydiorganosiloxane block copolymer to be formed and the choice of starting materials a) and B), but the amount of starting material B) can be from 5% to 95% by combined weight of all starting materials combined in step 1). Alternatively, the amount of starting material B) may be from 10% to 60%, and alternatively from 10% to 40%, on the same basis.
C) Catalyst and process for preparing same
In the process for preparing the copolymers, the starting materials C) are hydrosilylation catalysts. Hydrosilylation reaction catalysts include platinum group metal catalysts, which are known in the art and are commercially available. Such hydrosilylation catalysts may be a metal selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the hydrosilylation Catalyst may be a compound of such a metal, for example, chlorotris (triphenylphosphine) rhodium (I) (Wilkinson's Catalyst), diphosphine rhodium chelates such as [1, 2-bis (diphenylphosphino) ethane ] dichlorodirhodium or [1, 2-bis (diethylphosphino) ethane ] dichlorodirhodium, chloroplatinic acid (Speier's Catalyst), chloroplatinic acid hexahydrate, platinum dichloride, and complexes of the compounds with low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core-shell structure. Complexes of platinum with low molecular weight organopolysiloxanes include 1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex with platinum (Karstedt's Catalyst). These complexes may be microencapsulated in a resin matrix. Alternatively, the hydrosilylation catalyst may comprise a1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex with platinum. Exemplary hydrosilylation catalysts are described in U.S. Pat. nos. 3,159,601; 3,220,972; 3,296,291, respectively; 3,419,593; 3,516,946, respectively; 3,814, 730; 3,989,668, respectively; 4,784,879, respectively; 5,036,117, respectively; and 5,175,325 and EP 0347895B. Microencapsulated hydrosilylation catalysts and methods for their preparation are known in the art, as exemplified in U.S. Pat. nos. 4,766,176 and 5,017,654.
The amount of catalyst used in step 1) of the process described herein will depend on various factors, including the selection of starting materials a) and B) and their respective levels of silicon-bonded hydrogen atoms and terminal aliphatic unsaturation, the presence or absence of an inhibitor, and the temperature during step 1), but the amount of catalyst is sufficient to catalyze the hydrosilylation reaction of the starting materials comprising a) and B), alternatively the amount of catalyst is sufficient to provide from 1ppm to 1000ppm of a platinum group metal based on the combined weight of all starting materials combined in step 1), alternatively from 5ppm to 100ppm on the same basis.
D) Solvent(s)
The starting material D) can optionally be added during the process for preparing the above-described copolymers. The solvent may be an organic solvent, and examples thereof are a) an alcohol such as methanol, ethanol, isopropanol, butanol or n-propanol; b) ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; c) aromatic hydrocarbons such as benzene, toluene or xylene; d) aliphatic hydrocarbons such as heptane, hexane or octane; e) glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether or ethylene glycol n-butyl ether; f) halogenated hydrocarbons such as dichloromethane, 1, 1, 1-trichloroethane or dichloromethane; g) chloroform; h) dimethyl sulfoxide; i) dimethylformamide; j) acetonitrile; k) tetrahydrofuran; 1) a white oil solvent; m) mineral spirits; n) naphtha; o) isoparaffins, such as Isopar, commercially available from Exxonmobil Chemical CompanyTME; or a combination of two or more of a), b), c), d), e), f), g), h), i), j), k), 1), m), n), and o).
The amount of solvent will depend on various factors, including the type of solvent selected and the amount and type of other starting materials selected for use in step 1) of the process for preparing the polyolefin-polydiorganosiloxane block copolymer described herein. However, when present, the amount of solvent may range from 1% to 99%, alternatively from 2% to 50%, by combined weight of all starting materials combined in step 1). Solvents may be added during the combining of the starting materials comprising a), B) and C), for example to aid in mixing and transport. Alternatively, one or more starting materials may be dissolved in a solvent prior to combining with other starting materials in step 1) of the process described herein.
E) Inhibitors
Starting material E) inhibitor may be added in step 1) of the above process to alter the reaction rate of the starting material compared to a reaction containing the same starting material but omitting the inhibitor. Examples of inhibitors for hydrosilylation reactions are (E1) alkynols, such as methylbutynol, ethynylcyclohexanol, dimethylhexynol and 3, 5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol and 1-ethynyl-1-cyclohexanol, and combinations of two or more thereof; (E2) cycloalkenylsiloxanes, such as methylvinylcyclosiloxane, exemplified by 1, 3,5, 7-tetramethyl-1, 3,5, 7-tetravinylcyclotetrasiloxane, 1, 3,5, 7-tetramethyl-1, 3,5, 7-tetrahexenylcyclotetrasiloxane, and combinations of two or more thereof; (E3) alkene-alkyne compounds, such as 3-methyl-3-penten-1-yne, 3, 5-dimethyl-3-hexen-1-yne, and combinations of two or more thereof; (E4) triazoles, such as benzotriazole; (E5) a phosphine; (E6) a thiol; (E7) hydrazine; (E7) amines, such as tetramethylethylenediamine; (E8) fumarates, such as dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, and combinations of two or more thereof; (E9) maleates, such as diallyl maleate; (E10) a nitrile; (E11) an ether; (E12) carbon monoxide; (E13) alcohols, such as benzyl alcohol; (E14) silylated acetylenic compounds; and a combination of two or more of (E1) to (E14).
Silylated acetylenic compounds can be used to reduce or minimize the coloration (yellowing) of the reaction product produced in step 1 compared to reaction products that do not contain silylated acetylenic compounds or reaction products that contain organic acetylenic alcohols such as those described above. Examples of silylated acetylenic compounds are (3-methyl-1-butyn-3-oxy) trimethylsilane, ((1, 1-dimethyl-2-propynyl) oxy) trimethylsilane, bis (3-methyl-1-butyn-3-oxy) dimethylsilane, bis (3-methyl-1-butyn-3-oxy) silanemethylvinylsilane, bis ((1, 1-dimethyl-2-propynyl) oxy) dimethylsilane, methyl (tris (1, 1-dimethyl-2-propynyl)) silane, methyl (tris (3-methyl-1-butyn-3-oxy)) silane, (3-methyl-1-butyn-3-oxy) dimethylphenylsilane, (3-methyl-1-butyn-3-oxy) dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy) triethylsilane, bis (3-methyl-1-butyn-3-oxy) methyltrifluoropropylsilane, (3, 5-dimethyl-1-hexyn-3-oxy) trimethylsilane, (3-phenyl-1-butyn-3-oxy) diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy) dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy) dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy) dimethylhexenylsilane, and mixtures thereof, (cyclohexyl-1-acetylene-1-oxy) dimethylhexenylsilane, (cyclohexyl-1-acetylene-1-oxy) dimethylvinylsilane, (cyclohexyl-1-acetylene-1-oxy) diphenylmethylsilane, (cyclohexyl-1-acetylene-1-oxy) trimethylsilane, and combinations thereof. Alternatively, examples of inhibitors are methyl (tris (1, 1-dimethyl-2-propynyloxy)) silane, ((1, 1-dimethyl-2-propynyloxy) trimethylsilane, or a combination thereof. Silylated acetylenic compounds useful as inhibitors may be prepared by methods known in the art, such as silylation of the above-mentioned alkynols by reacting them with chlorosilanes in the presence of acid acceptors.
The amount of inhibitor added to the starting materials will depend on various factors including the desired pot life of the starting materials, the temperature selected for step 1, the particular inhibitor used, and the selection and amount of other starting materials used. However, when present, the amount of inhibitor may be in the range of > 0% to 1%, alternatively > 0% to 5%, alternatively 0.001% to 1%, alternatively 0.01% to 0.5%, and alternatively 0.0025% to 0.025%, by combined weight of all starting materials.
Starting materials F) alkoxysilyl-functional organosilicon Compounds
The starting material F) is an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom. Examples of suitable alkoxysilyl-functional organosilicon compounds are alkoxy-functional organohydrogensiloxane oligomers of the unit formula (F1):
(HR3 2SiO1/2)dd(R3 3SiO1/2)ee(HR3SiO2/2)ff(R3 2SiO2/2)gg(R3SiO3/2)hh(HSiO3/2)ii(SiO4/2)jjwherein R is1And R3As described above; each subscript aa is independently 0, 1, or 2; alternatively 0 or 1; each subscript bb is independently 0, 1, or 2; subscript cc > 0; each RDIndependently a divalent hydrocarbon group of 2 to 18 carbon atoms; subscript dd is more than or equal to 0, subscript ee is more than or equal to 5 and more than or equal to 0, subscript ff is more than or equal to 0, subscript gg is more than or equal to 0, subscript hh is more than 0, subscript ii is more than or equal to 0, subscript jj is more than or equal to 0, and the amount (cc + dd + ee + ff + gg + hh + ii + jj) is less than or equal to 50. For RDExamples of suitable divalent hydrocarbon groups are alkylene groups such as ethylene, propylene, butylene or hexylene; arylene, such as phenylene, or alkylarylene such as:
alternatively, each RDIs of the formula-C2H4-a group of (a). Examples of such alkoxy-functional organohydrogensiloxane oligomers can be prepared by the methods in U.S. Pat. No. 3,175,993 to Weyenberg and co-pending U.S. provisional patent application Ser. Nos. 62/524636, 62/524637, and 62/524639, all filed on 6.26.2017, and all incorporated herein by reference.
Alternatively, the starting material F) may have the formula (F2):
Alternatively, the starting material F) may have the formula (F3):
Alternatively, the starting material F) may comprise the formula (F4), (F5), or both, wherein formula (F4) isAnd is
Formula (F5) is
Alternatively, the starting material F) may have the unit formula (F6):
(R3 2SiO2/2)E(R3HSiO2/2)F wherein R is1、R3、RDAnd subscript aa is as described above, subscript E is 0 or greater, subscript F is 1 or greater, and subscript G is 1 or greater and 4 ≦ (E + F)+G)≤50。
In the unit formula (I) for the polyolefin-polydiorganosiloxane block copolymers described herein, the group R10Forming a hydrosilylation reaction product of silicon-bonded hydrogen atoms as starting material F and terminal aliphatically unsaturated organic groups of starting material B). When starting material F) is included, starting material B) comprises a telechelic polydiorganosiloxane. The amounts of starting materials B) and F) may be selected such that there are up to 1.05 molar equivalents of starting material F) to 1 molar equivalent of the terminal aliphatic unsaturated group (F: b mole ratio). Alternatively, for example, when a triblock copolymer having a BAB structure is to be formed, the F: B molar ratio can be 1.05: 1 to 1: 1. In one embodiment, the starting materials a), B), C) and F) may be combined simultaneously in step 1). Alternatively, the starting materials a), B) and C) may be combined in the following amounts: such that one aliphatically unsaturated group per molecule from starting material B) at the end of the polyolefin-polydiorganosiloxane block copolymer does not react with the SiH from starting material a), and then adding starting material F) such that the SiH on starting material F) reacts with the remaining aliphatically unsaturated groups from starting material B). In this way, copolymers with a BAB structure or copolymers with a b (ab) n structure comprising an alkoxy-silylhydrocarbylene functional end group can be prepared.
Copolymer
The polyolefin-polydiorganosiloxane block copolymer prepared as described above comprises the unit formula (I):
wherein R is1、R3、R10Subscript a and subscript b are as described above.
Each RLIs a divalent hydrocarbon group. R is as shown above in the unit formula (I)LGroup linked copolymersPolyolefin and polyorganosiloxane blocks. Each RLIs a starting material A) silicon-bonded hydrogen atoms of a silyl-terminated polyolefin and a starting material B) terminal aliphatically unsaturated organic group (R) of a polydiorganosiloxane2) The reaction product of (1). For RLExamples of suitable divalent hydrocarbon radicals are as hereinbefore defined for RDThe group as described. Alternatively, each RLIs of the formula-C2H4-or-C3H6-a group of (a).
Each R5Are independently selected hydrogen-terminated polyolefin blocks.
Each R5May have the unit formula: h [ (R)et)t(RO)u]gWherein R iset、ROAnd subscripts t, u, and g are as described above. Alternatively, each R5May have the unit formula (II): h [ (CH)2CH2)t(CHR7CH2)u]gWherein R is7And subscripts t, u, and g are as described above. Alternatively, the hydrogen terminated polyolefin block can be a hydrogen terminated ethylene polymeric block. Alternatively, the divalent polyolefin block may be a hydrogen terminated ethylene-octene copolymer block.
Each R6Are independently selected divalent polyolefin blocks. Each R6May have the formula [ (R)et)t(RO)u]gWherein R iset、ROAnd subscripts t, u, and g are as described above. Alternatively, each R6May have the unit formula (III): [ (CH)2CH2)t(CHR7CH2)u]gWherein R is7And subscripts t, u, and g are as described above. Alternatively, the divalent polyolefin block may be a divalent ethylene polymeric block. Alternatively, the divalent polyolefin block may be a divalent ethylene-octene copolymer block.
Each R10Independently selected from R3And groups containing alkoxysilyl-functional hydrocarbylene groups. In one embodiment, each R10Is R3(i.e., when the starting material F is not used to prepare a polyolefin-polydiorganosiloxaneAlkyl block copolymers). Alternatively, R10May have a formula selected from:
one or both of; and
(R3 2SiO2/2)E(R3RLSiO2/2)F
In the above unit formula (I), the subscript w is 0 to 2. Subscript x is 0 or a positive number. Subscript y is 0 or a positive number. Subscript z is 0 to 2. The amount (w + y) is not less than 1. The amount (x + z) is not less than 1. When subscript w is 0, subscript z > 0. When subscript z is 0, subscript w > 0.
In one embodiment, in unit formula (I), subscript x ═ 0, subscript y ═ 0, subscript w ═ 1, and subscript z ═ 1. In this example, the polyolefin-polydiorganosiloxane block copolymer has an AB structure. In this embodiment, the copolymer has formula (IV):
wherein R isL、R1、R3、R5、R10Subscript a and subscript b are as described above.
In an alternative embodiment, in unit formula (I), subscript w ≧ 2, subscript z ≧ 0, subscript x ≧ 1, and subscript y ≧ 0. In this example, the polyolefin-polydiorganosiloxane block copolymer has the formula (V):
wherein R isL、R1、R3、R5、R6Subscript a and subscript b are as described above; and subscript c is 0 or a positive number. Alternatively, subscript c may be 1 to 1,000; alternatively 2 to 1,000; alternatively 1 to 100, and alternatively 2 to 100. Alternatively, in formula (V), subscript c > 0, i.e., when in unit formula (I), subscript w > 2, subscript x > 1, subscript y > 1, and subscript z > 0. Alternatively, when subscript c ═ 0, the polyolefin-polydiorganosiloxane block copolymer has an (ABA) structure.
In an alternative embodiment, in unit formula (I), subscript w ═ 2, subscript x ═ 1, subscript y ═ 0, and subscript z ═ 0, and the copolymer has an (ABA) structure. The copolymer has the formula (VI):
wherein R isL、R1、R3、R5Subscript a and subscript b are as described above. The copolymer can be prepared in the above-described manner, wherein the starting material a) has one silyl end group per molecule and the starting material B) has two terminal organic groups (telechelics) having terminal aliphatic unsaturation per molecule.
In an alternative embodiment, in unit formula (I), subscript z ═ 2, subscript w ═ 0, subscript x ≧ 0, and subscript y ≧ 1, and the polyolefin-polydiorganosiloxane block copolymer has formula (VII):
wherein R isL、R1、R3、R6、R10Subscript a and subscript b are as described above; and subscript d is 0 or a positive number. Alternatively, subscript d may be 1 to 1,000; alternatively 2 to 1,000; alternatively 1 to 100, and alternatively 2 to 100. Alternatively, in formula (VII), subscript d > 0, i.e. when in unit formula (I), subscript w > 0, subscript x > 1, subscript y > 1, and subscript z > 2. Alternatively, subscript d ═ 0, andand the copolymer has a (BAB) structure.
In an alternative embodiment, in unit formula (I), subscript w ═ 0, subscript x ═ 1, subscript y ═ 0 and subscript z ═ 2, and the polyolefin-polydiorganosiloxane block copolymer has formula (VIII):
wherein R isL、R1、R3、R6、R10Subscript a and subscript b are as described above. The copolymers can be prepared as described above, wherein the starting material B) has one terminal organic group having a terminal aliphatic unsaturated bond per molecule, and the starting material A) is telechelic.
Alternatively, any of formulae (I) and (IV) to (VIII) may have one or more of the following: each R1Is methyl, each R3Is methyl, and each RLis-C2H4-. In this embodiment, each R5May be a hydrogen terminated polyethylene or a hydrogen terminated poly (ethylene/octene), and each R is6And may be polyethylene or poly (ethylene/octene).
Examples of the invention
These examples are intended to illustrate some embodiments of the invention and should not be construed as limiting the scope of the invention as set forth in the claims.
A polyethylene-polydimethylsiloxane diblock copolymer having an AB structure was prepared in this example 1 as follows:
having one formula-Si (CH) per molecule3)2The terminal groups of H and 1.6kDa polyethylene (200mg) and 900mg of a monovinyl-terminated polydimethylsiloxane having a Mw of 5,500 to 6,500 (commercially available from Gelest) were dissolved in 3mL of toluene at 100 ℃. Then, 1mL of a stock solution of Wilkinson's catalyst (5.8mg, 0.05 equiv.) was added and the resulting yellow solution was addedStirred for 21 hours and then precipitated into methanol. The resulting diblock copolymer was redissolved in toluene and reprecipitated into methanol, then filtered and dried under vacuum at 100 ℃ for 1 hour to give 850mg of a waxy copolymer.1The H NMR spectrum is consistent with 50% conversion to diblock copolymer, with no significant residual SiH functionality, as indicated by the disappearance of SiH resonance at 4.04 ppm.
A polyethylene-polydimethylsiloxane triblock copolymer having an ABA structure was prepared in this example 2 by combining 4.43 parts by weight of an α, omega-vinyl terminated polydimethylsiloxane having a DP of 124 and 1.6 mol% vinyl groups, 1 part by weight of a copolymer having one formula-Si (CH) per molecule in a container as follows3)2Polyethylene with an end group of H and Mn of 1,050 and 21.72 parts by weight of toluene. The vessel was heated at 105 ℃ with an external heater and a Karstedt's catalyst (Karstedt's catalyst) was added to the vessel in an amount sufficient to provide 320ppm of platinum to the reaction mixture. Heating was continued at 105C for 4 hours. IR analysis of the SiH indicated that the reaction was complete due to no detectable SiH. The resulting reaction product was stripped to dryness using a rotary evaporator at an oil bath temperature of 120 ℃ and a pressure of 1-2 mmHg. After 30 minutes, most of the toluene solvent was removed. At 120 ℃ the copolymer obtained was a cloudy viscous liquid. At room temperature, the copolymer was translucent to opaque wax.
In this example 3a polyethylene-polydimethylsiloxane-polyethylene triblock copolymer was prepared as follows. The copolymer had the following corresponding block number average molecular weights: 1030g/mol PE-9,200g/mol PDMS-1030g/mol PE. The reagents used to prepare the copolymer were:
vinyl terminated PDMS, where DP ═ 124, FW ═ 74.47g/mol Si; 1.60 mol% M (Vi); and 4654g/mol of vinyl.
·Mono-SiMe2H-terminated polyethylene (Mn-1030)
toluene-Fisher Scientific ACS grade
Pt Karster's catalyst
Synthesis procedure: in a 100mL round-bottom flaskLoading: vinyl terminated PDMS (6.78g, 0.00146mol Vi), Single SiMe2H-terminated polyethylene (1.50g, 0.00146mol SiH) and toluene (33.12 g). The solution was heated to reflux for 15 minutes to remove any water that may be present. The amount of Karster catalyst added to the solution (solution containing 300ppm Pt) was 20ppm Pt as solids. An aluminum block heater was used. After 24 hours of heating at reflux, IR analysis indicated the reaction was complete as inferred from the disappearance of SiH absorption. The product was stripped to dryness using a rotary evaporator (rotavapor) at an oil bath temperature of 120 ℃ and 1 mmHg. The resulting product is a low viscosity liquid with slight haze at 120 ℃ and is a hard, translucent wax at room temperature.
Based on the procedure in example 3, an additional triblock copolymer with an ABA structure was prepared (Mn in g/mol) with the following characteristics:
examples of the invention
MN PE
MN PDMS
PE% in the triblock
3
869
4362
28.5％
4
1205
9308
20.6％
5
1429
9308
23.5％
6
1037
9308
18.2％
7
1429
4362
39.6％
8
1205
13402
15.2％
9
1050
9308
18.4％
10
1050
4362
32.5％
11
1429
13402
17.6％
12
2062
13402
23.5％
13
3500
13402
34.4％
14
3500
24642
22.1％
15
1500
9308
24％
16
869
9308
16.1％
A mixture of polyethylene-polydimethylsiloxane-polyethylene triblock/polyethylene-polydimethylsiloxane diblock copolymer was also prepared, and their characteristics are detailed in table 1B. These mixtures are prepared by reacting mono SiMe2The H-terminated PE was prepared by reacting a telechelic vinyl-terminated polydimethylsiloxane (Vi-PDMS-Vi) in a stoichiometric molar ratio of vinyl to SiH of 2 to 1. One such copolymer is described in detail herein, specifically example 22 in table 1 bB. The procedure is as follows. 10g of a telechelic vinyl terminated PDMS having an Mn of 13,402g/mol and a vinyl equivalent of 6,701g/mol vinyl was charged to a 100mL round bottom flask together with 1.07g of a single SiH terminated polyethylene having an Mn of 1,429g/mol and 44.3g of toluene. The mixture was heated to 105 ℃ using an aluminum block heater. Once the solution was homogeneous, 10ppm Pt (Karster's catalyst, 0.17g of a solution containing 636ppm Pt) on a solids basis was added. The mixture was held at 105 ℃ for a total of 2.5 hours. Infrared of SiHAnalysis confirmed that the reaction was complete after this time. The solvent was then stripped using a rotary evaporator at a 120 deg.C oil bath temperature and 1-2mmHg vacuum. After 30 minutes, the solvent has been removed and the product is a low viscosity, nebulized liquid at this temperature. Once cooled to room temperature, the product was a translucent soft wax.
By varying the amounts of starting materials, additional mixtures of diblock/triblock copolymers were prepared based on the procedure in example 11, and these are listed in table 1B.
Table 1B: from single Si (CH)3)2The diblock/triblock copolymers prepared from H (SiH) -functional high density Polyethylene (PE) and α, omega-vinyl terminated polydimethylsiloxane (Vi-PDMS-Vi) are characterized by the number average molecular weight Mn from GPC in addition to the total weight percent of PE in the copolymer
BCP example
MN PE
MN PDMS
％PE
17
869
4362
17
18
1205
9308
11
19
1429
9308
13
20
1429
4362
25
21
1205
4362
22
22
1429
13402
10
23
1037
4362
19
24
1429
13402
10
25
1205
9308
11
26
1037
9308
10
27
1429
4362
25
28
869
13402
6
29
880
4362
17
30
4750
13402
26
31
1500
9308
13.9
Reference example 1 GPC measurement method
Samples of the copolymer prepared as described above (and samples of silyl terminated polyolefin prepared as described in the reference examples below) were analyzed on a PolymerChar GPC-IR maintained at 160 ℃. Each sample was eluted through a1 XPlgel 20 μm 50X 7.5mm guard column and a LS 300X 7.5mm LS chromatography column mixed with 1, 2, 4-Trichlorobenzene (TCB) at a flow rate of 1 mL/min stabilized with 300ppm Butylated Hydroxytoluene (BHT) at 20 μm 4 XPlgel 20 μm. A16 mg sample of the copolymer was weighed out and diluted with 8mL of TCB by the instrument. For molecular weight, the apparent units were adjusted to homopolyethylene (PE) using the known Mark Houwink coefficients of PS and PE in TCB using a conventional calibration of Polystyrene (PS) standards (Agilent PS-1 and PS-2) at this temperature. Decane was used as the internal flow marker and the retention time was adjusted to this peak. For comonomer incorporation, a calibration curve of incorporation was prepared using copolymers of known composition.
The silyl terminated polyolefins used in examples 1 to 29 as described above were prepared as described in the reference examples below.
Reference example 2 Using HMe2Procedure for silylation of zinc dipolyethylene with SiCl
Zinc dipolyte and Isopar (Mw 1580Da, 10mM) were placed in vials. The vial was heated at 120 ℃ until the contents became clear and homogeneous. Dimethylhydrochlorosilane and NMI were added to the vial. The vial was heated at 90 ℃ for 3 hours. Then iodine (I) is added2) To quench the unreacted zinc dimer. By passing1The resulting product was evaluated by H NMR. HMe2The molar equivalents of SiCl and conversion to product results are shown in reference Table 2.
Reference table 2
Silyl groups: iodine ratio by1H NMR integral measurement
Reference example 2 shows that improved silylation is achievable with additional equivalents of chlorosilane when relatively volatile chlorosilanes are used.
REFERENCE EXAMPLE 3-USE of HPh2Procedure for silylation of zinc dipolyethylene with SiCl
Reference example 2 was repeated except that diphenylhydrochlorosilane was used instead of dimethylhydrochlorosilane. The results are shown in the following reference table 3.
Refer to Table 3
Entry NMI equivalent silyl polymer: iodine polymer
Silyl groups: iodine ratio by1H NMR integral measurement
Reference example 3 shows that complete silylation of zinc dipolytes is possible using NMI as an additive.
Reference example 4-with H2Procedure for silylation of zinc dipolyethylene with PhSiCl
Zinc dipolyte and Isopar (Mw 1580Da, 10mM) were placed in vials. The vial was heated at 120 ℃ until the contents became clear and homogeneous. Phenyldichlorochlorosilane and additive NMI or a blend of NMI and TMEDA were added to the vial. The vial was heated for a period of time. Then iodine (I) is added2) To quench the unreacted zinc dimer. By passing1The resulting product was evaluated by H NMR. The results of the chlorosilane molar equivalents, additive molar equivalents, heating time and temperature, and conversion to product are set forth in reference table 4 below.
Refer to Table 4
Silyl groups: iodine ratio by1H NMR integral measurement
Reference example 5 shows that, with the conditions described in entry 6, complete silylation is observed in the case of phenyldihydrochlorosilane. At least 1 equivalent of NMI is capable of completing hydrosilylation. A blend of NMI and another amine base was used as an additive in entry 5 for comparison purposes.
Reference example 5
Zinc dipolyate and Isopar (Mw 1080Da, 10mM) were placed in vials. The vial was heated at 120 ℃ until the contents became clear and homogeneous. Phenyldichlorochlorosilane and additives were added to the vial. The vial was heated at 100 ℃ for 1 hour. Then iodine (I) is added2) To quench the unreacted zinc dimer. By passing1The resulting product was evaluated by H NMR. The results of additives and conversion to product are shown in the following reference table 5.
Refer to Table 5
Silyl groups: iodine ratio by1H NMR integral measurement
Reference example 5 shows that complete silylation is observed under the conditions tested using 4-dimethylaminopyridine and pyridine-N-oxide as additives. This example also shows that N-methylpyridone and DMPU can also be used as additives to promote silylation, since more silyl polymer is formed as shown in entries 2 and 3, compared to the comparative control without additive (entry 8).
Reference example 6
Using phenyldichlorosilane (HPhSiCl)2) In place of HMe2SiCl and 1.2 equivalents of NMI instead of 2 equivalents were used as additives, the amounts being repeated with reference to example 2. The results are shown in the following reference table 6.
Silyl groups: iodine ratio by1H NMR integral measurement
Reference example 6 shows that substitution occurs at only one of the two Si — Cl bonds, even though the amount of phenyldichlorosilane is reduced.
Reference example 7
Zinc dipolyate and Isopar (Mw 1205Da, 10mM) were placed in vials. The vial was heated at 120 ℃ until the contents became clear and homogeneous. Dimethylhydriodosilane and NMI were added to the vial. The vial was heated at 110 ℃ for 3 hours. Then iodine (I) is added2) To quench the unreacted zinc dimer. By passing1The resulting product was evaluated by H NMR. HMe2The molar equivalents of Sil and conversion to product results are shown in reference table 7 below.
Reference table 7
Silyl groups: iodine ratio by1H NMR integral measurement
Reference example 7 shows that NMI also promotes silylation in the case of halosilanes other than chlorosilanes (e.g., iodosilane). In the absence of NMI, the iodosilane was not sufficiently electrophilic to react completely with the dimeric ethylene-zinc under the conditions tested in this example.
Reference example 8
Silylation of the zinc ethylene/octene copolymer with phenyldihydrochlorosilane was performed as follows. In a glove box, a20 mL vial was charged with zinc copolyol (Mn. 1940Da, 30.66% octene, Isopar)TM3.10% polymer in E, 14.95g, 0.117mmol, 0.500 equiv). The mixture was stirred and heated to 110 ℃ until the mixture became clear and homogeneous. NMI (22.5. mu.L, 0.282mmol, 1.20 equiv.) was added followed by chlorobenzylsilane (37.6. mu.L, 0.282mmol, 1.20 equiv.). The mixture was stirred for 1 hour. A portion of the solution was removed and quenched with excess iodine for conversion analysis. Pouring the polymer solution into an excessIn methanol, the polymer was precipitated. The polymer was isolated by filtration and dried in a vacuum oven.
Reference example 8 shows that silylation is possible using NMI in the case of zinc ethylene/octene copolymer bases.
Reference example 9
This reference example 9 shows a water washing process for the purification of 850g/mol Mn single SiH-terminated polyethylene prepared as described above. In a 100mL round bottom flask equipped with a magnetic stir bar, 0.90g of the monosh polyethylene prepared as described above was diluted to 10% in toluene. The solution was heated by placing the flask in an aluminum block at a temperature of 85 ℃. The mono SiH terminated polyethylene is dissolved. Deionized water (6g) was added and mixed for 5 minutes. The stirring was then stopped and the aqueous phase was removed (at the bottom) using a plastic pipette. A good separation is achieved. Both phases are clear and the pH of the wash water is alkaline.
The following procedure was carried out 7 times at 85 ℃. Deionized water (4g) was added and mixed for 5 minutes. The aqueous phase was removed. The resulting solution of toluene and mono-SiH terminated polyolefin was poured onto TeflonTMThe sheets were dried overnight. The pH of the final water wash was on the weakly acidic side, indicating successful imidazole removal.
Reference example 10 general procedure for preparation of silyl terminated organometallic
The polymerization was carried out in a 2L PARR batch reactor. The reactor was heated by an electric heating mantle and cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating/cooling system were computer controlled and monitored by the CAMILE TG process. The bottom of the reactor was fitted with a dump valve that emptied the reactor contents into a stainless steel dump kettle. The decanted pot was discharged into a 30 gallon blowdown tank, and both the pot and tank were purged with nitrogen. All solvents used for the polymerization or catalyst composition were run through a solvent purification column to remove any impurities that could affect the polymerization. Reacting 1-octene with IsoparTME and toluene were passed through two columns, the firstThe column contained a2 alumina and the second column contained Q5. Ethylene was passed through 2 columns, the first column containing A204 alumina andthe second column contains the Q5 reactant. Passing the transferred nitrogen through a reactor containing A204 alumina,A single column of molecular sieve and Q5 reactant.
Will be a desired amount of IsoparTME and/or toluene solvent and/or 1-octene is added to the loaded column via a shooting pot, depending on the desired reactor loading. The load column was packed to the load set point by using a laboratory scale equipped with a load column. After the liquid feed addition, the reactor is heated up to the polymerization temperature set point. If ethylene is used, it is added to the reactor while at the reaction temperature to maintain the reaction pressure set point. Ethylene addition was monitored by a micro-motion flow meter.
Scavenger MMAO-3A (which is commercially available from Akzo Nobel) was processed in an inert glove box, drawn into a syringe and pressure transferred to a catalyst launch tank. Then toluene was washed 3 times, 5mL each, before injection into the reactor. The chain shuttling agent was handled in an inert glove box, drawn into a syringe and pressure transferred to the catalyst launch tank. Then toluene was washed 3 times, 5mL each, before injection into the reactor. The procatalyst and activator are mixed with an appropriate amount of purified toluene to obtain the desired molarity solution. The catalyst and activator were processed in an inert glove box, drawn into a syringe and transferred under pressure to a catalyst launch tank. Then, the mixture was washed with 5mL of toluene 3 times. Immediately after the catalyst addition, a running timer was started. If ethylene is used, ethylene is added via CAMILE to maintain the reaction pressure set point in the reactor. These polymerizations were run for 10 minutes or to reach the target ethylene uptake. The stirrer was then stopped and the bottom dump valve was opened to empty the reactor contents into a clean dump pan that had been stored in an oven at 130 ℃ for more than 60 minutes prior to use to dissipate any excess water absorbed by the metal surfaces. Once the contents of the reactor were emptied into the dump kettle, the normal nitrogen inerting flow was switched to argon via a ball valve. Argon gas was flowed for a calculated period of time to allow five exchanges of gas volumes in the kettle. When the inerting of the argon is complete, the decanting pot is lowered from its holding device and a second lid with inlet and outlet valves is sealed to the top of the pot. The pan was then inerted with argon for an additional five gas exchanges via the supply line and inlet/outlet valve. When complete, the valve is closed. The pan was then transferred into a glove box without the contents coming into contact with the outside atmosphere.
Reference example 11-preparation of samples according to the general procedure of reference example 10
A homopolyethylene sample was prepared following the general procedure in reference example 10 using the following conditions: 120 ℃, 23g of initial ethylene loaded, 600g of toluene, 10. mu. mol of MMAO-3A, 1.2 equivalents of activator-to-procatalyst. The amount of procatalyst used is adjusted to achieve the desired efficiency. Reactor pressure and temperature were kept constant by feeding ethylene during the polymerization and cooling the reactor as needed. Polymerization was carried out using bis (hydrogenated tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borate as an activator, bis (N-isobutyl-6-mesitylylpyridin-2-amine) hafnium dimethyl as a procatalyst and bis (8- (dimethylsilyl) octyl) zinc as a chain shuttling agent.1H-NMR Mn: each chain 1586, GPC Mn: each chain 1310.
A sample of poly (ethylene/octene) copolymer was prepared according to the general method in reference example 10 using the following conditions: 120 ℃ 23g of initial ethylene loaded, 397g of IsoparTME, 115g of 1-octene, 10. mu. mol of MMAO-3A, 1.2 equivalents of activator to procatalyst. The amount of procatalyst used is adjusted to achieve the desired efficiency. Reactor pressure and temperature were kept constant by feeding ethylene during the polymerization and cooling the reactor as needed. Bis (hydrogenated tallow alkyl) methylammonium tetrakis (pentafluorophenyl) borate as activator, [ N- [2, 6-bis (1-methylethyl) phenyl [ ]]- α - [2- (1-methylethyl) -phenyl]-6- (1-naphthalene)radical-C2) -2-pyridinemethylamino]Hafnium dimethyl was prepared as the procatalyst and bis (8- (dimethylsilyl) hexyl) zinc was polymerized as the chain shuttling agent. GPC Mn: per chain 25,020, comonomer incorporation: 48% of 1-octene.
Reference example 12 preparation of telechelic silyl terminated polyolefin
In a nitrogen-filled glove box, the polymer-based zinc is placed in IsoparTM4.6% suspension in E (per strand)1H-NMR Mn 1586, GPC Mn 1310 per chain) was roughly split into two 1-L round bottom flasks. Flask one contained 355g (16.3g of polymer-based zinc) and flask two contained 379.7g (17.5g of polymer-based zinc). Both flasks were heated to 110 ℃ in a glove box until the solution became homogeneous.
Once the solution became homogeneous, the following starting materials were added. Then to flask one was added 0.91g NMI (11.1mmol, 0.88mL, 1.1 equivalents per chain) and 2.2g 87% pure dimethylhydriodosilane (17.5mmol, 1.1 equivalents per chain). To flask two was added 0.97g of NMI (11.87mmol, 0.95mL, 1.1 equivalents per chain) and 2.37g (11.87mmol, 1.1 equivalents per chain) of 87% pure dimethylhydriodosilane. The flask was heated at 110 ℃ for 45 minutes, and then an aliquot was taken for NMR analysis to confirm the disappearance of the C-Zn species. After confirmation and a total heating time of 1.5 hours, the solution in the jar was cooled to room temperature. The solutions were then poured into separate stirred beakers of methanol (1L). The precipitate was collected on a disposable plastic sintered filter and dried in a vacuum oven at 40 ℃ overnight.
The precipitate was then transferred to two 1L round bottom flasks and dissolved in 200mL toluene at 110 ℃. Then, 80mL of deionized water was added to the flask and stirred vigorously under a reflux condenser and nitrogen atmosphere. After at least 10 minutes of stirring, the stirring was stopped and the two phases were allowed to separate. Using a pipette, the aqueous layer was removed as much as possible and discarded. This process was repeated three more times for a total of four washes. After the fourth wash, the flask was cooled to room temperature and precipitated from a stirred methanol solution (1L each). The precipitate was washed with methanol and then dried in a vacuum oven at 40 ℃ overnight.
Isolation of 30.55g of telechelic HMe2Si-terminated polyethylene (90% yield). By functionalized materials comprising chain ends after taking into account the percentage of dead chains1Mn by H-NMR was 1427. The Mn of the polyethylene segment of the functionalized chain only was 1307. The signal with triplet multiplicities at 0.97ppm was due to methyl terminated chain ends, which corresponds to 13.5% dead chain ends. GPC Mn is 1280, Mw is 1670, and D is 1.28.
Example 30 preparation of a polyethylene-polydimethylsiloxane Block copolymer comprising An (AB) n Structure Using the telechelic silyl terminated polyolefin of reference example 13
In this example, 0.300g (0.154 mmol per SiH function, 1 equivalent) of single SiMe are introduced2H-functionalized polyethylene and telechelic SiMe2A mixture of H-terminated polyethylene (per GPC, Mn 1390, per NMR 1948) was placed in a20 mL scintillation vial in a nitrogen-filled glove box. 0.72g of telechelic vinyl terminated polydimethylsiloxane (DMS-V21, commercially available from Gelest; by NMR, Mn 5038) was weighed directly into a vial in a glove box. The vial was heated to 100 ℃ and gently stirred to avoid splattering. The polyethylene melted but did not become completely homogeneous. Then 0.039mL of a 0.1% Pt dilution of the Karster's catalyst in toluene was added and the reaction was stirred at 100 ℃. After 2 hours, small aliquots were removed for1H-NMR analysis, which indicated complete disappearance of the SiH signal. The reaction was cooled to room temperature, removed from the glove box, cooled to room temperature, and precipitated from isopropanol to remove excess PDMS. 0.835g of material was isolated. Of the final product1H-NMR confirmed complete consumption of SiH. There was a small amount of vinyl indicating some remaining PDMS. GPC estimated by weighted averaging of the polyethylene/polydimethylsiloxane signals indicates a degree of polymerization of about 5 (polyethylene/polydimethylsiloxane)Siloxane) units.
Example 31 preparation of polyethylene-polydimethylsiloxane Block copolymer having BAB Structure Using telechelic silyl terminated polyolefin of reference example 13
In this example, 0.300g (0.154 mmol as SiH function, 1 equivalent) of 81.5% -SiMe2The H-functionalized telechelic polyethylene (according to GPC, Mn 1390, according to NMR, 1948) was placed in a20 mL scintillation vial in a nitrogen-filled glove box. 2.49g (0.329mmol, 2.1 equiv.) of monovinyl-terminated PDMS (MCR-V21, commercially available from Gelest, Mn 7570 as determined by NMR) was weighed directly into a vial in a glove box. 1.5mL of toluene was added and the vial was heated to 100 ℃ and stirred gently to avoid splashing. The polyethylene melted but did not become completely homogeneous. First, 0.039mL of a 0.1% Pt dilution of the Karster catalyst in toluene was added and the reaction mixture was stirred at 100 ℃ for 1 hour. The reaction mixture became clearer upon addition of the catalyst. However, 39% SiH still remained, so 0.017mL of the Karster catalyst solution was added. The reaction mixture was stirred at 85 ℃ overnight. The resulting mixture was removed from the glove box, cooled to room temperature, and precipitated from isopropanol to remove excess PDMS. Due to the soft nature of the material, a large amount of material is lost during transfer and settling. 0.991g is isolated, and1H-NMR indicated that the reaction reached 95% conversion by disappearance of the SiH peak. Assuming 81.5% of the functionalized polyethylene reacted with the polydimethylsiloxane statistically, the material was calculated to be 56.9% triblock, 41.1% diblock, and 2.0% unreacted polyethylene.
Example 32
To a 250mL glass jar was added 15.5g (2.71mmol, 1 equivalent) of SiH-terminated poly (ethylene-co-octene) (as1H-NMR，Mn5731 g/mol; according to GPC, Mn4690g/mol，Mw12.710g/mol, PDI 2.71, 12.8 mol% octene), and placed in a nitrogen-filled glove box. Then, it is aligned on top of the polyolefin5.46g (1.08mmol, 0.4 eq) of divinylPDMS (Gelest DMS-V21, M by NMR)n5038). 125mL of toluene was added to the jar and heated to 110 ℃ to dissolve. Then, 18.5mg of PtMe2COD (2 mol%) was added as a solid to the jar and the clear colorless solution was stirred overnight.
After 15 hours, an aliquot was removed for1H-NMR. Based on the stoichiometry of the polyolefin and silicone, and integrating the main aliphatic peak to the known value of the starting material, a conversion of about 98% was calculated. No vinyl or SiH groups were detected by NMR.
The reaction was cooled to a warm touch and poured into a steel pan to dry over the weekend. 20.4g of product was collected. The high temperature liquid chromatography analysis showed that the sample contained < 1.5 wt% silicone, with1The H-NMR data were in agreement. 65.1% of the polyolefin is in the triblock.
Example 33
To a 250mL jar was added 9.1g (0.608mmol, 1 equivalent) of SiH-terminated poly (ethylene-co-octene) (as1H-NMR，Mn14978 g/mol; according to GPC, Mn：14246g/mol，Mw: 32784, 15.2 mol% octene), and placed in a nitrogen-filled glove box. Then, 4.16g (0.24mmol, 0.4 eq) of divinyl PDMS (DMS-V31, Gelest, by NMR, M) were weighed directly on top of the polyolefinn17135 g/mol). 160mL of toluene was added to the jar and heated to 90 ℃ to dissolve. Then, 0.81mL (2 mol%) of 5mg/mL of PtMe2A solution of COD catalyst in toluene was added to the reaction and the jar was stirred at 90 ℃ overnight.
After 18 hours, an aliquot was removed and dried for NMR.1H-NMR indicated that there was no more observable SiH. Based on the stoichiometry of the polyolefin and silicone, and integrating the main aliphatic peak to the known value of the starting material, a conversion of about 64% was calculated. 0.29 protons corresponding to the vinyl group can be observed.
The reaction was then cooled to a warm touch and removed from the glove box. The jars were then poured into metal trays and dried in a fume hood. The pan was then placed in a vacuum oven and dried overnight at 55 ℃. 12.76g of total material were isolated. High temperature liquid chromatography indicated that the sample was about 7.4 wt% free PDMS, or about 37.2% triblock and 47.6% diblock copolymer. 63.6% of the polyolefin is in the triblock.
Industrial applicability
An important distinguishing feature of the process described herein is that the Si-H functional groups are located on the polyolefin, which allows a hydrosilylation reaction with the silicon-bonded groups with terminal aliphatic unsaturation at the polyorganosiloxane terminal, which does not allow a detrimental isomerization reaction and enables higher conversions compared to previous systems where polyolefins with terminal aliphatic unsaturation (not silyl groups) were reacted with polyorganosiloxanes with SiH functionality. The production of block copolymers by the methods described herein is represented by the Si-CC-Si (red) bonds shown in the following exemplary scheme.
Synthesis of AB Block copolymers
Synthesis of ABA Block copolymers
Synthesis of BAB Block copolymer
ii.(AB)nSynthesis of Block copolymer
The above exemplary scheme illustrates the synthesis of polyethylene-block-polydimethylsiloxane coupled with vinyl-terminated polydimethylsiloxane via hydrosilylation.
Definition and use of terms
All amounts, ratios, and percentages are by weight unless otherwise indicated in the context of the specification. The amount of all starting materials in the composition totals 100% by weight. The summary and abstract of the invention are incorporated herein by reference. The articles 'a (a)', 'an (an)' and 'the (the)' each mean one or more unless the context of the specification indicates otherwise. The disclosure of a range includes the range itself as well as any contents and endpoints contained therein. For example, disclosure of a range of 1 to 20 includes not only the range of 1 to 20 (including the endpoints), but also 1, 2,3, 4, 6, 10, and 20, respectively, as well as any other numbers contained within the range. Further, disclosure of a range such as 1 to 20 includes, for example, a subset of 1 to 3,2 to 6, 10 to 20, and 2 to 10, as well as any other subset included in the range. Similarly, the disclosure of a markush group includes the entire group as well as any individual members and sub-groups contained therein. For example, the disclosure of a markush group hydrogen atom, alkyl, alkenyl, or aryl group respectively includes a member alkyl group; subgroups hydrogen, alkyl and aryl; subgroups hydrogen and alkyl; as well as any other individual members and subgroups contained therein.
"periodic Table of elements" refers to the periodic Table of elements as published in CRC Handbook of Chemistry and Physics, 68 th edition, 1987 by CRC Press, Inc. Any reference to one or more groups means that the group or groups numbered using the IUPAC system are reflected in this periodic table of elements.
The term "comprises" and its derivatives (e.g., comprise, comprises), comprise, etc.) are intended to include and are not intended to exclude the presence of any additional component, starting material, step or procedure, whether or not the same is explicitly recited herein.
The term "hydrocarbyl" means a group containing only hydrogen and carbon atoms, and includes branched or straight chain, saturated or unsaturated, cyclic or acyclic groups. Monovalent hydrocarbon groups include alkyl (including cycloalkyl), alkenyl, dienyl, cycloalkenyl, cycloalkadienyl, aryl, and alkynyl groups.
The term "telechelic" refers to a reactive polymer, and means that the reactive polymer has a reactive functional group at the chain end, where the polymer chain ends may have the same or different reactive functional groups. As used herein, one, two, or none of a) the silyl terminated polyolefin and B) the polydiorganosiloxane can be telechelic.
The following abbreviations are used throughout the specification.
Table X-abbreviations.
Examples of the invention
In a first embodiment, a method for preparing a polyolefin-polydiorganosiloxane block copolymer comprises:
1) combining starting materials comprising
A) A silyl-terminated polyolefin having 2 terminal silyl groups in 1 per molecule, wherein the terminal silyl groups have the formula
B) a polydiorganosiloxane having 1 to 2 terminal silicon-bonded terminal aliphatically unsaturated organic groups capable of undergoing a hydrosilylation reaction; and
C) a hydrosilylation reaction catalyst.
In a second embodiment, in the method of the first embodiment, a) the silyl terminated polyolefin has the unit formula:wherein subscript f is 0 to 1, and subscripts t and u have relative values such that t is greater than 0 and less than or equal to 1, u is greater than 0 and less than or equal to 1, subscript g is greater than or equal to 1, and each R is7Independently of 2 to 20 carbon atomsA monovalent hydrocarbon group.
In a third embodiment, in the method of the second embodiment, subscript g ranges from 1 to 500.
In a fourth embodiment, in the method of the third embodiment, subscript g ranges from 10 to 400.
In a fifth embodiment, in the method of the fourth embodiment, subscript g ranges from 18 to 360.
In a sixth embodiment, in the method of any one of the first to fifth embodiments, the silyl terminated polyolefin is a silyl terminated polyethylene or a silyl terminated poly (ethylene/octene) copolymer.
In a seventh embodiment, in the method of any one of the preceding embodiments, starting material B) comprises a polydiorganosiloxane of formula (B1):
In an eighth embodiment, in the method of the seventh embodiment, each R2Is an alkenyl group, alternatively a vinyl group.
In a ninth embodiment, each R is3Selected from alkyl and aryl, alternatively methyl and phenyl.
In a tenth embodiment, in the method of the seventh or eighth embodiment, the subscript b ranges from 2 to 2,000.
In an eleventh embodiment, in the method of any one of the first to tenth embodiments, any one of conditions a) to D) is satisfied, wherein:
with the proviso that A) the silyl terminated polyolefin has one terminal silyl group per molecule,
with the proviso that B) the silyl terminated polyolefin has two terminal silyl groups per molecule,
condition C) is that the polyorganosiloxane has one terminal organic group per molecule having a terminal aliphatic unsaturation, and.
Condition D) is that the polyorganosiloxane has two terminal organic groups per molecule having terminal aliphatic unsaturation.
In a twelfth embodiment, in the method of the eleventh embodiment, any one of conditions E to I) is satisfied, wherein
Condition E) represents both condition a) and condition C),
condition F) represents both condition a) and condition D),
condition G) represents both condition B) and condition C),
condition H) represents all three of A), B) and D), and
condition I) represents all three of B), C) and D).
When the condition H) is satisfied, both the silyl-terminated polyolefin having one terminal silyl group per molecule and the silyl-terminated polyolefin having two terminal silyl groups per molecule are used. The copolymer obtained in this example may have An (AB) n structure. When the condition I) is satisfied, both a polyorganosiloxane having one terminal organic group having a terminal aliphatic unsaturated bond per molecule and a polyorganosiloxane having two terminal organic groups having a terminal aliphatic unsaturated bond per molecule are used. The copolymer obtained in this example may have An (AB) n structure. Alternatively, when any of conditions D), H) and I) is satisfied, then an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom may be included in the starting material, and an alkoxy-functional polyolefin-polydiorganosiloxane may be synthesized.
In a thirteenth embodiment, in any of the first to twelfth embodiments, the starting materials further comprise one or more additional starting materials selected from the group consisting of: D) a solvent, E) a hydrosilylation reaction inhibitor, F) an alkoxysilyl-functional organosilicon compound having at least one silicon-bonded hydrogen atom, and a combination of two or more of D), E), and F).
In a fourteenth embodiment, the polyolefin-polydiorganosiloxane block copolymer comprises the unit formula (I):
wherein each RLIs an independently selected divalent hydrocarbon radical, each R1Is an independently selected monovalent hydrocarbon radical, each R3Independently selected from hydrogen atoms and monovalent hydrocarbon groups free of terminal aliphatic unsaturation, each R5Is an independently selected hydrogen-terminated polyolefin block, each R6Is an independently selected divalent polyolefin block, each R10Independently selected from R3And an alkoxysilyl-functional hydrocarbylene-containing group, each subscript a is independently 1 or 2, and each subscript b is independently 0 or a positive number; subscript w is 0 to 2, subscript x is ≧ 0, subscript y is ≧ 0, subscript z is 0 to 2, an amount (w + y) is ≧ 1, an amount (x + z) is ≧ 1, provided that when subscript w is 0, subscript z > 0, and when subscript z is 0, subscript w > 0.
In a fifteenth embodiment, the polyolefin-polydiorganosiloxane block copolymer has the formula (IV):
In a sixteenth embodiment, in the copolymer of formula (IV) in the fifteenth embodiment, each RLis-C2H4-, each R1Is methylEach R3Is methyl, each R5 is selected from the group consisting of hydrogen terminated polyethylene and hydrogen terminated poly (ethylene/octene), each R6Selected from polyethylene and poly (ethylene/octene), each subscript a ═ 1, and each subscript b from 2 to 2,000.
In a seventeenth embodiment, the polyolefin-polydiorganosiloxane block copolymer has the formula (V):
wherein each RLIs an independently selected divalent hydrocarbon radical, each R1Is an independently selected monovalent hydrocarbon radical, each R3Independently selected from hydrogen atoms and monovalent hydrocarbon groups free of terminal aliphatic unsaturation, each R5Is an independently selected hydrogen-terminated polyolefin block, each R6Each subscript a is independently 1 or 2, each subscript b ≧ 0, and subscript c is 1 to 1,000, which is an independently selected divalent polyolefin block.
In an eighteenth embodiment, in the copolymer of formula (V) in the seventeenth embodiment, each RLis-C2H4-, each R1Is methyl, each R3Is methyl, each R5Selected from the group consisting of hydrogen terminated polyethylene and hydrogen terminated poly (ethylene/octene), each R6Selected from polyethylene and poly (ethylene/octene), each subscript a ═ 1, each subscript b from 2 to 2,000, and subscript c from 1 to 100.
In a nineteenth embodiment, a polyolefin-polydiorganosiloxane block copolymer has the formula (VI):
wherein each RLIs an independently selected divalent hydrocarbon radical, each R1Is an independently selected monovalent hydrocarbon radical, each R3Independently selected from hydrogen atoms and monovalent hydrocarbon groups free of terminal aliphatic unsaturation, each R5Is an independently selected hydrogen-terminated polyolefin block, each R6Is an independently selected divalent polyolefin block, each subscript aIndependently 1 or 2, and subscript b ≧ 0.
In a twentieth embodiment, in the copolymer of formula (VI) in the nineteenth embodiment, each RLis-CH2-CH2-, each R1Is methyl, each R3Is methyl, each R5Selected from hydrogen terminated polyethylene and hydrogen terminated poly (ethylene/octene), each subscript a ═ 1, and each subscript b from 2 to 2,000.
In a twenty-first embodiment, a polyolefin-polydiorganosiloxane block copolymer has the formula (VII):
wherein each RLIs an independently selected divalent hydrocarbon radical, each R1Is an independently selected monovalent hydrocarbon radical, each R3Independently selected from hydrogen atoms and monovalent hydrocarbon groups free of terminal aliphatic unsaturation, each R5Is an independently selected hydrogen-terminated polyolefin block, each R6Is an independently selected divalent polyolefin block, each R10Independently selected from R3And an alkoxysilyl functional hydrocarbylene-containing group, each subscript a is independently 1 or 2, each subscript b ≧ 0, and subscript d is 1 to 1,000.
In a twenty-second embodiment, in the copolymer of formula (VII) in the twenty-first embodiment, each R isLis-C2H4-, each R1Is methyl, each R3Is methyl, each R5Selected from the group consisting of hydrogen terminated polyethylene and hydrogen terminated poly (ethylene/octene), each R6Selected from polyethylene and polyethylene/octene, each subscript a ═ 1, each subscript b from 2 to 2,000, and subscript d from 1 to 100.
In a twenty-third embodiment, a polyolefin-polydiorganosiloxane block copolymer has the formula (VIII):
wherein each RLIs an independently selected divalent hydrocarbon radical, each R1Is an independently selected monovalent hydrocarbon radical, each R3Independently selected from hydrogen atoms and monovalent hydrocarbon groups free of terminal aliphatic unsaturation, each R5Is an independently selected hydrogen-terminated polyolefin block, each R6Is an independently selected divalent polyolefin block, each R10Independently selected from R3And an alkoxysilyl-functional hydrocarbylene-containing group, each subscript a is independently 1 or 2, and each subscript b ≧ 0.
In a twenty-fourth embodiment, in the copolymer of formula (VIII) in the twenty-third embodiment, each RLis-C2H4-, each R1Is methyl, each R3Is methyl, each R6Selected from polyethylene and poly (ethylene/octene), each subscript a ═ 1, and each subscript b from 2 to 2,000.
In a twenty-fifth embodiment, the silyl terminated polyolefin used to prepare the polyolefin-polydiorganosiloxane block copolymer in any of the preceding embodiments is prepared by a method comprising:
1) combining starting materials comprising
a) A metal of a polymer base,
b) a nitrogen-containing heterocycle, and
c) a halosilane, and
optionally d) a solvent; thereby forming a product comprising a silyl terminated polyolefin;
2) washing the product with water, thereby removing unwanted substances comprising the starting material b); and
3) recovering the silyl terminated polyolefin.
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