US 11,535,751 B2 · Asymmetrically substituted polyorganosiloxane derivatives

Abstract

An asymmetrically substituted polyorganosiloxane comprising at least one or more siloxane blocks and different reactive groups at each end of the siloxane chain, e.g. an alkoxysilyl, alkenyl, epoxy, hydroxyaromatic or an ionic substituent. Each polyorganosiloxane block has substantially a monomodal chain length distribution and is suitable for the use as a surface modifying agent for organic or inorganic particles, as a surface active material, and/or as a compatibilizer in compositions having more two or more non-miscible phases.

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Claims31

Dependent claims

A polyorganosiloxane comprising two different terminal groups Z1 and Z2 of the formula (I)

Z1-{-L[SiR2O]p—SiR2}m-L-Z2 (I)
p is 4 or 9, and 80% or more of the polyorganosiloxane of the formula (I) has the same chain length,
m=1 to 5
wherein R═R1
R or R1 is a saturated hydrocarbon substituent selected from the group consisting of a monovalent C1 to C22-alkyl, optionally substituted by F, a C6-C22-aryl, a C8-C22-polycyclic aryl, a C7-C23-alkylaryl, and a C7-C22-arylalkyl group,
L is a single bond, or a divalent L1 or L2 selected from the group consisting of a divalent C1-C12-alkylene group, which can be interrupted by one or more —O—, or —NR3—C(O)—, and/or —NR3—OC(O)NR3—,—N—R3HC(O)N—R3—, and substituted by one or more OH groups, wherein R3 is hydrogen, Me3Si— or C1-C8-alkyl,
bonded via a carbon bond to an adjacent silicon atom of the polyorganosiloxane,
Z1 is (R1X)xR13-xSi—, where X is O, x is 1-3, and R1 is a saturated hydrocarbon substituent selected from the group consisting of a monovalent C1 to C22-alkyl, optionally substituted by F, a C6-C22-aryl, a C8-C22-polycyclic aryl, a C7-C23-alkylaryl, and a C7-C22-arylalkyl group;
and
Z2 is selected from the group consisting of R1, R2, hydrogen, monovalent unsubstituted or substituted C1-C30 hydrocarbons, and an ionic group comprising one or more O, N, S and P atoms,
wherein
R2 is selected from a monovalent unsaturated, unsubstituted or substituted alkenyl or alkynyl group selected from the group consisting of a C2-C22-alkenyl, C6-C22-cycloalkenyl, C7-C22-bicycloalkenylalkylene, C2-C22-alkynyl, and an oxiranyl or carbonate derivative thereof, selected from
C3-C22-oxiranyl groups and C4-C23-carbonate compounds,
and a group selected from Cl, Br, I, —SH, —S—R1, —OH, —O—R1, —CN, —NCO, blocked NCO, and a group selected from
(R1X)xR13-xSi—, R6xR13-xSi—, wherein x is 1-3, wherein
X is selected from —O—, —NR1—, and —C(O)—O— wherein
R6 is selected from C6-C10-aryl, C7-C12-arylalkyl, C6-C12-cycloalkyl, C7-C16-bicycloalkyl, C3-C12-epoxy alkyl, C6-C12-epoxy cycloalkyl, C7-C16-epoxy bicycloalkyl, C6-C12-thiocycloalkyl, C5-C12-hetero, —N-aryl, —O-aryl, —S-aryl, and
selected from an ionic group derived from an ester of a carboxylic acid, sulfur or phosphorous based acid selected from —C(O)—O—R3, (R3O)2—P(O)—O—, (R3O)2—P(O)—, (R3—O)2—P—, betaines, —NHR3—CH2—COOH, —NHR3—CH2—O—S(O)2(OH), —S—S(O)2(OR3), —NR32, —PR32, and an acid addition salt of an amine, or phosphine, and
alkyl or aryl enamine of the formula
wherein R3 is selected from the group consisting of hydrogen, C1-C8 alkyl, C2-C8 alkenyl, and R13Si—,
all Z groups are bonded via a single bond or carbon bond of L to the silicon atom of the polyorganosiloxane (I), whereby
-L-Z2 and -L-Z1 are different.

19 more elements

Dependencies are inferred from the claim text.

Description15,277 words

Summary605 words

#The present invention relates to siloxane materials, and particularly to siloxane materials that are suitable as dispersion aids, surfactants, or compatibilizers in various systems. The present invention relates to asymmetrically substituted di- and pentasiloxane derivatives and oligomers thereof suitable for coating of organic and inorganic surfaces, organic and inorganic particles, and/or which can enhance compatibilization of materials or separated liquid phases, e.g., solutions or polymer systems that are mixed together and tend to separate into phases. The work leading to this invention has received funding from the European Union Seventh Framework Program (FP7-NMP-2010-LARGE-4) under “grant agreement” no 263382. The antifouling project received funding from the Federal Ministry for Economic Affairs and Energy of Germany under“grant agreement” 03SX370H.

#Dispersion aids based on poly- or oligosiloxane are well known in the prior art. For example polydiorganosiloxandiols are useful for the dispersion of silicas and inorganic oxides. Filler materials such as, e.g., silicas, metal oxides of aluminum, titanium, zinc, zirconium or tin, and other metal oxides, are employed in various compositions. Such fillers are applied for several reasons in coating or rubber compositions. For example, fillers can be added to improve the physical properties, e.g., to provide mechanical strength or even to enhance the optical properties of those compositions. In order to improve the quality of the dispersion of fillers, to better adjust optical properties between a matrix polymer or the chemical bonding between a filler, and a matrix polymer it is desired to provide siloxanes having two different terminal groups. Without being bound to any particular theory, one group may have a preferred ability to interact with the filler or any first substrate and a second group may be accessible for a reaction with matrix polymer of the composition or may provide groups which can shielding those filler particles or substrates. Many attempts have been made to achieve such asymmetric polyorganosiloxanes having two different end groups. Either the syntheses are (i) restricted to specific end groups or (ii) do not exclude equilibrating reactions, i.e., the reaction results in other by-products having two identical terminal groups or comprise cyclic siloxanes having none of the desired functionality.

#Therefor there is still a need for asymmetric polysiloxanes which have less of the disadvantages of previous siloxanes and can provide beneficial effects in the use as surface modifying agent and/or dispersion aid or compatibilizer.

Brief description of the drawings2 figures

#FIG. 1 is a graph showing the antifouling/fouling release performance of antifouling coating compositions comprising asymmetrically substituted polyorganosiloxane derivatives in accordance with aspects of the invention; and

#FIGS. 2-4 are images showing the fouling coverage of panels A to F coated with different materials after 85 days of sea immersion, 189 days of sea immersion, and 219 days of sea immersion respectively.

Detailed description14,610 words

#Provided are polyorganosiloxanes comprising two different terminal groups where the polyorganosiloxane exhibits a low polydispersity index. The polyorganosiloxanes may find use in a variety of applications and materials.

#Based on the use of specific uniform siloxane precursors the inventors could synthesize polyorganosiloxanes having exactly two different reactive groups at both ends at a level of high purity respectively a small polydispersity index, which is characterized by the ratio of the weight-average molecular weight to the number-average molecular weight Mw/Mn. Here it is in the range from 1 to 1.2. The inventors found a way to insert terminal groups stepwise, whereby after each reaction step a purification step could be applied, which allows to control the completeness of the addition of a first terminal end group and then the addition of a second different terminal group. It is part of the inventive concept to apply the stepwise addition of reactive terminal groups on monomodal polyorganosiloxane precursors which are generated in a non-equilibrium siloxane synthesis.

#In one aspect, provided is a polyorganosiloxane of the formula (I) comprising two different terminal groups Z1 and Z2: Z1-{-L[SiR2O]p—SiR2}m-L-Z2 (I) where

Facts

Application

15/745,499Filed 20 Jul 2016 · us provisional application

Priority

20 Jul 2015

Published

US 2018/0371248 A127 Dec 2018

Granted

27 Dec 2022

Term ends

20 Jul 2036

Estimated · how

20 years from earliest known nonprovisional domestic filing plus recorded patent term adjustment. Maintenance-fee lapses, terminal disclaimers and statutory extensions have not been checked. The continuity chain may be incomplete; this is not an enforceability determination.

Classification8 codes

C08L 83/08
Polysiloxanes: containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
C08G 77/045
Polysiloxanes: containing less than 25 silicon atoms
C09D 5/1675
Synthetic film-forming substance: polyorganosiloxane-containing compositions
G02B 1/14
Optical coatings produced by application to, or surface treatment of, optical elements: protective coatings, e.g. hard coatings

Timeline

20 Jul 2015Priority claimedParent application 62/194,563
20 Jul 2016Application filedUS 15/745,499
20 Mar 2018Assigned to Momentive Performance Materials GmbHassignment of assignor's interest
27 Dec 2018PublishedUS 2018/0371248 A1
5 Jun 2019Assigned to Citibank, N.A., AS Administrative Agentabl patent agreement
27 Dec 2022GrantedUS 11,535,751 B2
12 Oct 2026TodayWithin its term
20 Jul 2036Term endsEstimated

Asymmetrically substituted polyorganosiloxane derivatives

Life of this patent

Asymmetrically substituted polyorganosiloxane derivatives

Life of this patent

Life of this patent

Abstract

Drawings

Drawings

Claims31

Description15,277 words

Drawings

Classification8 codes

Life of this patent

Description15,277 words