CN115943189A - Fluorine-containing polymer - Google Patents
Fluorine-containing polymer Download PDFInfo
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- CN115943189A CN115943189A CN202180051395.6A CN202180051395A CN115943189A CN 115943189 A CN115943189 A CN 115943189A CN 202180051395 A CN202180051395 A CN 202180051395A CN 115943189 A CN115943189 A CN 115943189A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
Abstract
The present invention relates to novel fluorine-containing block copolymers, to compositions comprising block copolymers, to the use of block copolymers in coating compositions, especially as surface-active additives in coating compositions, to compositions comprising such block copolymers and to products coated with such compositions.
Description
The present invention relates to novel fluorine-containing block copolymers, to compositions comprising block copolymers, to the use of block copolymers in coating compositions, especially as surface-active additives in coating compositions, to compositions comprising such block copolymers and to products coated with such compositions.
Fluorosurfactants are an important component in industrial process chemicals. However, these materials are problematic for the user and the environment due to their durability and toxicity. Fluorosurfactants can be used in a very wide variety of applications and help, for example, improve wetting of surfaces. They are therefore used, for example, as interface promoters or levelling agents, emulsifiers or viscosity reducers in paints, coatings or adhesives.
Classical fluorosurfactants consist of long perfluorinated alkyl chains (C6-C8) and are considered potentially bioaccumulating and toxic. However, often fluorosurfactants contain perfluoroalkyl substituents that decompose in the environment through biological and other oxidative processes to give perfluoroalkane carboxylic acids and perfluoroalkane sulfonic acids.
Thus, there is still a need for alternative fluorosurfactants, which should be suitable for use as an additive in coating compositions, and which should show some advantages, such as improved soil or oil repellency and/or improved wetting or leveling properties, and which should be beneficial in terms of their ecotoxicological properties.
It has been found that one or more of these objects can be achieved by providing a block copolymer as disclosed and claimed hereinafter.
The present invention relates to block copolymers (hereinafter also simply referred to as "polymers") comprising at least one first block a and at least one second block B, wherein block a comprises monomer units derived from at least one monomer of formula (I) and block B comprises monomer units derived from at least one monomer of formula (II)
(Rf-CHF-CF 2 -Y-CHR 1 ) m -L-X 1 (I)
R 2 -X 2 (II)
Wherein
Rf is a perfluorinated alkyl group, preferably a perfluorinated C1-C30 alkyl group, very preferably a perfluorinated C1-C15 alkyl group, optionally containing one or more heteroatoms,
y is O or S, and Y is O or S,
R 1 is H or alkyl, preferably C1-C6 alkyl,
l is a single bond or a divalent organic group,
R 2 is an alkyl group, preferably a C1-C20 alkyl group, which is linear, branched, monocyclic or polycyclic, and optionally contains one or more heteroatoms,
X 1 and X 2 Independently of one another, ethylenically unsaturated groups，
m is an integer of 1 to 5.
Preferably, rf is selected from the following groups:
CF 3 -(CF 2 ) 0-3 -，CF 3 -(CF 2 ) 0-3 -O-，
CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -，
CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -O-，
CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -O-CF 2 -，
CF 3 -(CF 2 ) 0-3 -O-(CF 2 -O) 1-8 -and
CF 3 -(CF 2 ) 0-3 -O-(CF 2 -O) 1-8 -CF 2 -。
in a particularly preferred variant of the invention, rf is selected from the following groups:
CF 3 -(CF 2 ) 1-2 -，CF 3 -(CF 2 ) 1-2 -O-，
CF 3 -O-(CF 2 ) 1-3 -，
CF 3 -O-(CF 2 ) 1-2 -O-，
CF 3 -(CF 2 ) 1-2- O-CF 2 -，
CF 3 -O-(CF 2 ) 1-2 -O-CF 2 -，
CF 3 -O-(CF 2 -O) 1-8 -and
CF 3 -O-(CF 2 -O) 1-8 -CF 2 -。
preferably, R 1 Selected from H and C1-C3 alkyl.
Preferably, L is selected from single bonds; and organic groups, in particular alkylene groups, which are saturated, branched or unbranched, optionally containing heteroatoms, in particular O and/or S atoms, and/or functional groups. Very preferably, L is methylene, ethylene or propylene, most preferably methylene.
Preferably, R 2 Is a C2-C12 alkyl group, which is optionally branched and optionally contains one or more heteroatoms. Very preferably, R 2 Is a C2, C3, C4, C5 or C6 alkyl group.
Preferably, X 1 And X 2 Independently of one another, is an acrylate or methacrylate group.
Preferably, m 1 Is 1, 2 or 3, particularly preferably 1 or 2.
Preference is given to polymers comprising monomer units derived from at least one monomer of the formula (I) and at least one monomer of the formula (II), where one or more of the variables have the preferred meaning. Especially preferred are polymers comprising monomer units derived from at least one monomer of formula (I) and at least one monomer of formula (II), wherein all variables have the preferred meaning simultaneously.
Particular preference is given to monomers of the formulae (I) and (II), where
Rf is selected from CF 3 -(CF 2 ) 1-2 -、CF 3 -(CF 2 ) 1-2 -O-、CF 3 -O-(CF 2 ) 1-3 -、CF 3 -O-(CF 2 ) 1-3 -O-、CF 3 -(CF 2 ) 1-2 -O-CF2-、CF 3 -O-(CF 2 ) 1-2 -O-CF 2 -、CF 3 -O-(CF 2 -O) 1-8 And CF 3 -O-(CF 2 -O) 1-8 -CF 2 -，
R 1 Is H or CH 3 ，
R 2 Is C2-C12 alkyl, which is linear or branched and optionally contains one or more heteroatoms,
l is C1-C4 alkylene which is linear or branched and optionally contains one or more heteroatoms, preferably one or more O atoms, and optionally contains a functional group,
X 1 and X 2 Independently of one another, acrylate or methacrylate groups,
m is 1 or 2.
Particularly preferred are polymers comprising monomeric units derived from at least one monomer selected from the following formulae (Ia) to (Id), especially (Ia) to (Ic), and/or (IIa).
Wherein Rf and R 2 Has one of the meanings given above and below, and R ' are independently of each other H or methyl, and preferably R ' and R ' have the same meaning.
Particularly preferred are polymers comprising monomer units derived from at least one monomer selected from the group consisting of formulae (Ia) to (Ib), wherein Rf is selected from the group consisting of:
CF 3 -(CF 2 ) 1-2 -，CF 3 -(CF 2 ) 1-2 -O-，
CF 3 -O-(CF 2 ) 1-3 -，
CF 3 -O-(CF 2 ) 1-2 -O-，
CF 3 -(CF 2 ) 1-2- O-CF 2 -，
CF 3 -O-(CF 2 ) 1-2 -O-CF 2 -，
CF 3 -O-(CF 2 -O) 1-8 -or
CF 3 -O-(CF 2 -O) 1-8 -CF 2 -
And R' is H or methyl.
In a particularly preferred variant of the invention, the polymer comprises monomer units derived from at least one monomer selected from formulae (Ia) to (Ib), wherein Rf is
CF 3 -(CF 2 ) 1-2 -，
CF 3 -(CF 2 ) 1-2 -O-，
CF 3 -O-(CF 2 ) 1-3 -
Or CF 3 -O-(CF 2 ) 1-2 -O-
And R' is H or methyl.
Preferably, the polymer comprises monomer units derived from at least one monomer selected from the group consisting of formula (Ia) to (Ib), wherein Rf is CF 3 -CF 2 -CF 2 -O-、CF 3 -CF 2 -O-or CF 3 -O-and R' is H or methyl.
Particularly preferred are polymers comprising monomer units derived from at least one monomer selected from the group consisting of formula (IIa) wherein R is 2 Is a linear or branched C2-C12 alkyl group, very preferably a C2, C3, C4, C5 or C6 alkyl group, and R' is H or methyl.
Further preferred are polymers comprising monomer units derived from at least one monomer of formula (IIa) selected from the following subformulae, wherein R "" is H or methyl, and n is an integer from 1 to 6:
the monomers of formula (I) and (II) can be prepared by simple standard process steps. For example, the monomers of formula (I) can be prepared by reaction of the corresponding alcohol with an acid or anhydride by methods known to those skilled in the art.
The monomers of the formula (II) can be prepared, for example, by reaction of the corresponding alkyl alcohols with the corresponding (meth) acrylic acid or (meth) acrylic acid derivatives.
The necessary starting materials are commercially available, can be prepared from commercially available products by known methods or can be prepared analogously by known syntheses,
monomers of formula (I) and processes for their preparation are also described, for example, in WO 2016/096129.
The novel polymers may comprise only monomer units derived from at least one monomer of formula (I) and at least one monomer of formula (II).
In a variant of the invention, the new polymer may comprise a first block a comprising monomer units derived from at least one monomer of formula (I), a second block B comprising monomer units derived from at least one monomer of formula (II), and optionally a third block C comprising monomer units derived from at least one functional comonomer. Such polymers may be represented by formula (III)
Wherein Ra is a fluorinated group (Rf-CHF-CF) as defined for the monomer of formula (I) 2 -Y-CHR 1 ) m -L-, rb is an alkyl radical R as defined for the monomers of formula (II) 2 Rc is a functional group as defined below, R 'and R' represent H or methyl, and x, y and z represent the total number of the corresponding monomers, wherein x is>1，y>1，z≥0。
The functional comonomer of block C is preferably selected from the group comprising OH, epoxy, -Si (OMe) 3 、-Si(OEt) 3 、CO 2 H or tertiary amino group. Particularly preferred functional comonomers are selected from the following monomers, wherein R' "is H or methyl:
in a preferred variant of the invention, the polymer consists of monomer units derived from at least one monomer of formula (I) and at least one monomer of formula (II).
Preferably, the block copolymers according to the invention have a number average molecular weight M of from 1000 to 100,000, more preferably from 2000 to 50,000, very preferably from 3,000 to 30,000g/mol n 。
The polymer may comprise between 1-99% of the three types of monomer units (units Rf-U formed from fluorinated monomers of formula I, units a-U formed from alkyl monomers of formula II and units F-U formed from monomers having functional groups) in each ratio, giving a total of 100% in the final polymer,% = wt%).
Preferred combinations are shown in table 1 below.
TABLE 1
| Rf-U | 20-80％ | 40-70％ |
| A-U | 20-80％ | 30-60％ |
| F-U | 2-20％ | 2-30％ |
| Total of | 100％ | 100％ |
Balancing the composition of the copolymer is critical to the final properties of the polymer in the final composition or coating.
The synthesis of the block copolymers can be achieved by standard methods known to the person skilled in the art and described in the literature, preferably by free-radical polymerization in solution, in bulk or in emulsion.
Preferably, the block copolymer is prepared by a process comprising the steps of
(a) Polymerizing one of the monomers of formulae (I) and (II), or their respective subformulae, as defined above, in a composition comprising one or more of an initiator, a solvent and a comonomer,
(b) Reacting the resulting polymer with the other of formulae (I) and (II), as defined above, or monomers of their respective subformulae, in a composition comprising one or more of an initiator, a solvent and a comonomer,
(c) Optionally reacting the resulting polymer with a functional comonomer as defined above in a composition comprising one or more of an initiator, a solvent and a comonomer,
(d) Optionally isolating the polymer.
It is also possible to prepare blocks a, B and C of the block copolymer in another of the sequences shown above by changing the sequence of steps a, B and C accordingly. For example, it is possible to first polymerize a functional comonomer to form block C and then copolymerize the resulting polymer with monomers of formulae (I) and (II) in two further steps to form blocks a and B. Alternatively, one of the monomers of formula (I) and (II) may be polymerized first to form one of blocks a and B, then the resulting polymer is copolymerized with a functional comonomer to form block C, and finally the resulting polymer is copolymerized with the other of the monomers of formula (I) and (II) to form the other of blocks a and B. In all such cases, at least the first of steps a, b and c is preferably carried out in the presence of an initiator.
The synthesis of the blocks A, B and/or C is preferably carried out using controlled polymerization, very preferably controlled radical (free radial/radial) polymerization. Suitable and preferred examples of controlled polymerization reactions include, but are not limited to
Group Transfer Polymerization (GTP)
-reversible addition-fragmentation chain transfer polymerization (RAFT),
atom Transfer Radical Polymerization (ATRP),
polymerization in the presence of nitroxide initiators, such as Nitroxide Mediated Polymerization (NMP).
These polymerization processes are known to the skilled worker and are described in the literature. For example GTP is described in US4,656,226, RAFT is described in WO98/01478, ATRP is described in WO96/30421 and NMP is described in WO 94/11412.
ATRP and NMP are highly preferred, with NMP being most preferred.
Suitable nitroxide initiators are known from the prior art and are disclosed, for example, in WO2009/103613 A1. Preferred nitroxide initiators are selected from the following formulas
Very preferred are initiators of the formula
Further suitable and preferred polymerization processes are illustrated by way of example in the experimental section. The polymer may be isolated or used in dispersion or solution. Preferably, the polymerization is carried out in the same solvent as the coating dispersion used later. If the solvent is not suitable, a solvent exchange can be carried out after the polymerization. Preferably, the polymerization is carried out as a free radical polymerization under an inert atmosphere with a heat-activated initiator such as AIBN.
The polymers according to the invention can be used, for example, as coating materials or as additives for conventional coatings.
Polymers according to the present invention comprising two or more blocks of monomeric units derived from monomers of formulae (I) and (II) or their subformulae, in particular their preferred variants, offer several advantages compared to polymers of the prior art, such as good water and soil repellency and beneficial environmental properties. Thus, they do not degrade chemically or biologically to form long chain PFCA or PFAS.
A particular advantage of the polymers according to the invention is that they are easily degradable, since they have a specific nominal breaking point in the molecule. Thus, during the degradation process, corresponding low molecular weight fragments are formed which can pass into the atmosphere and can therefore be decomposed in the stratosphere under UV light.
The hydrofluoroethers of the following structure can be converted into volatile and UV-decomposable compounds, for example, by hydrolysis and oxidation. The decomposition products can then be washed out of the atmosphere with rainwater, transferred to the ground and mineralized there.
A preferred field of use is, for example, the use of the polymers according to the invention as additives in: in formulations in special coatings (e.g. photoresists, top anti-reflection coatings, bottom anti-reflection coatings) for surface coatings such as paints, varnishes, protective coatings, in electronic or semiconductor applications, or in optical applications (e.g. photographic coatings, coatings for optical elements), in agrochemicals, in polishes and waxes, for example for furniture, floor coverings and automobiles, in particular in floor polishes, in fire extinguishing compositions, lubricants, or in lithographic processes, in particular in immersion lithographic processes, for example in developer solutions, rinse solutions, immersion oils and/or in photoresists themselves, in particular in additive formulations for the production of printed circuits or for corresponding formulations.
For use, the polymers according to the invention are generally incorporated into correspondingly designed formulations. The polymers according to the invention are generally used in concentrations of from 0.01 to 30.0% by weight, preferably from 0.01 to 10.0% by weight, based on the entire composition. The invention likewise relates to corresponding compositions comprising the polymers according to the invention. Such compositions preferably comprise a solvent suitable for the respective application, and optionally further active substances and/or optionally additives. Preferred compositions are paint and coating formulations, fire-extinguishing agents, lubricants, cleaning agents and detergents and deicing agents or developer solutions, rinse solutions, immersion oils and photoresists for lithographic processes, in particular for immersion lithographic processes and in particular for the production of printed circuits, agrochemicals, floor polishes, cosmetic products for textile finishing or glass treatment or hydrophobicizers. Preferred compositions herein are paint and coating formulations and printing inks.
In addition, the invention relates to water-based surface coating formulations comprising the polymers according to the invention alone or in admixture with additives. The use of surface coating formulations based on the following synthetic film formers is preferably considered: polycondensation resins such as alkyd resins, saturated/unsaturated polyesters, polyamide/imides, silicone resins; a phenolic resin; urea-formaldehyde and melamine resins, polyaddition resins, such as polyurethanes and epoxy resins, polymeric resins, such as polyolefins, polyvinyl compounds and polyacrylates.
In addition, the polymers according to the invention are also suitable for surface coatings based on natural products and modified natural products. Surface coatings based on oils, polysaccharides (such as starch and cellulose), and also on natural resins (such as cyclic oligomeric terpenes, polyterpenes and/or shellac) are preferably considered.
The polymers according to the invention can be used in aqueous surface coating systems both as physical hardeners (thermoplastics) and as cross-linkers (elastomers and thermosets). The polymers according to the invention preferably improve the water repellency and/or soil repellency of the coated surface.
The present invention relates to all the uses mentioned herein of the polymers to be employed according to the invention. The corresponding use of the polymers for the stated purposes is known to the person skilled in the art and therefore there is no problem with the use of the polymers to be employed according to the invention.
The invention relates in particular to the use of the polymers according to the invention described above and their preferred embodiments as and in functional coatings, for example for improving the water repellency and/or soil repellency of coating formulations, such as epoxy, acrylic and PUR coatings.
In addition to the polymers comprising monomer units derived from monomers of the formulae (I) and (II), the coating formulations according to the invention may also comprise solvents, additives, auxiliaries and fillers, and also non-fluorinated polymers.
Solutions or dispersions comprising one or more polymers according to the invention can be used as additives for conventional coatings, but it is also advantageous to spin-coat the solution or dispersion itself as a thin layer on a substrate. Suitable substrates are, for example, glass, ceramics, metals, textiles, clothing or leather.
Polymers and coatings comprising such polymers can be beneficial in terms of their ecotoxicological properties, and show good water and soil repellency simultaneously. Furthermore, the polymers and coatings according to the invention may show good processability and/or storage stability.
The complete disclosures of all applications and publications specifically mentioned are also incorporated by reference into the disclosure of this application. Further features, advantages and variants of the invention emerge from the claims and the exemplary embodiments. The following examples explain the invention in more detail without limiting the scope of protection.
Examples
The following abbreviations are used:
M n number average molecular weight
M w Weight average molecular weight
D polydispersity
RT Room temperature
wt.% of
General procedure for polymerization
One or more monomers, initiator and solvent are first introduced into a dry three-neck round-bottom flask. An inert atmosphere was created by alternating vacuum and argon inlet. The composition was heated to 115 ℃ and stirred for 48h. To synthesize the block copolymer, the comonomer was added after 24h and the mixture was heated and stirred for a further 24h. The solvent and residual monomers were removed under reduced pressure using a rotary evaporator.
Example 1:synthesis of non-fluorinated blocks
Polymer 1 (Poly-nBA) was prepared as follows:
a premix of the following materials was prepared:
32mg (0.086 mmol) of N-tert-butyl-O- [1- [4- (chloromethyl) phenylethyl ] -N- (2-methyl-1-phenylpropyl) hydroxylamine (NBOP),
1.00g (7,80mmol) of n-butyl acrylate (nBA)
0.56g of chlorobenzene
M n ＝6794，M w ＝11,788，D＝1.74
Example 2:synthesis of fluorinated blocks
Polymer 2 (Poly-AMPFE) was prepared as follows:
a premix of the following materials was prepared:
32mg (0.086 mmol) of N-tert-butyl-O- [1- [4- (chloromethyl) phenylethyl ] -N- (2-methyl-1-phenylpropyl) hydroxylamine (NBOP),
2.717g(7.80mmol)AMPFE
0.56g of chlorobenzene
M n ＝5452，M w ＝8745，D＝1.60
Example 3 (comparative):synthesis of fluorinated blocks
Polymer 3 (Poly-AFT 6: 2) was prepared as follows:
a premix of the following materials was prepared:
32mg (0.086 mmol) of N-tert-butyl-O- [1- [4- (chloromethyl) phenylethyl ] -N- (2-methyl-1-phenylpropyl) hydroxylamine (NBOP),
3.262g(7.80mmol)AFT6:2
0.56g of chlorobenzene
M n ＝4560，M w ＝7291，D＝1.60
Example 4:synthesis of Block copolymer
Polymer 4 (Blc-nBA-AMPFE) was prepared as follows:
a premix of the following materials was prepared:
32mg (0.086 mmol) of N-tert-butyl-O- [1- [4- (chloromethyl) phenylethyl ] -N- (2-methyl-1-phenylpropyl) hydroxylamine (NBOP),
1.000g(7.80mmol)nBA
0.56g of chlorobenzene
After 24h, 0.408g (1.048 mmol) of AMPFE was added
M n ＝9614，M w ＝13,273，D＝1.38
Example 5 (comparative):synthesis of random copolymer
Polymer 5 (Rnd-nBA-AMPFE) was prepared as follows:
a premix of the following materials was prepared:
32mg (0.086 mmol) of N-tert-butyl-O- [1- [4- (chloromethyl) phenylethyl ] -N- (2-methyl-1-phenylpropyl) hydroxylamine (NBOP),
1.000g(7.80mmol)nBA
0.408g(1.048mmol)AMPFE
0.56g of chlorobenzene
M n ＝5054，M w ＝12,694，D＝2.51
Example 6 (comparative):synthesis of Block copolymer
Polymer 6 (Blc-nBA-AFT 6: 2) was prepared as follows:
a premix of the following materials was prepared:
32mg (0.086 mmol) of N-tert-butyl-O- [1- [4- (chloromethyl) phenylethyl ] -N- (2-methyl-1-phenylpropyl) hydroxylamine (NBOP),
1.000g(7.80mmol)nBA
0.56g of chlorobenzene
After 24h, 0.438g (1.048 mmol) of AFT6:2 are added
M n ＝7844，M w ＝9970，D＝1.27
Example 7 (comparative):synthesis of random copolymer
Polymer 7 (Rnd-nBA-AFT 6: 2) was prepared as follows:
a premix of the following materials was prepared:
32mg (0.086 mmol) of N-tert-butyl-O- [1- [4- (chloromethyl) phenylethyl ] -N- (2-methyl-1-phenylpropyl) hydroxylamine (NBOP),
1.000g(7.80mmol)nBA
0.438g (1.048 mmol) of AFT6:2,0.56g of chlorobenzene
M n ＝5054，M w ＝12,694，D＝2.51
Example 8: application testing
The synthesized polymers were tested for suitability as surface active additives in coating applications. For this purpose, the polymer was dispersed in 2K-PUR and deposited on a drawdown chart (drawdown chart). After curing, each polymer was tested for its repellency to water and Diiodomethane (DIM) by contact angle measurement. The instrument used was a droplet shape analyzer (DSA 100 from Kruess, germany).
The basecoat compositions are shown in table 2.
Table 2:2K PUR coating formulations
Preparation of the base coat:
in a 250ml flask, add components 1-6 and mix with a magnetic stirrer for 12h.
The following mixtures were prepared with the base coat, hardener and polymers 1 to 7 from examples 1 to 7:
TABLE 3
The base coat and additives were mixed and homogenized for 45min with a magnetic stirrer (multirex). After addition of the hardener, the mixture was homogenized for a further 20min with a magnetic stirrer.
For coating applications, the following equipment was used:
-byko-Chart/Opacity Chart (byk-Gardner GmbH AG-5305) black/white draw down paper
Scraper (Erichsen, model 360, 30 μm)
Automatic film applicator (byk-Gardner GmbH)
-vacuum oven
Preparing a coating:
application of the lacquer at a wet film thickness of 30 μm
Allowing the drawdown paper (chart) to level for 15min
Curing conditions at 130 ℃ and 250 mbar for 30min.
As a result:
table 4 shows the contact angle of water or Diiodomethane (DIM) droplets on 2K-PUR coatings with and without polymer additives, and the surface energy calculated therefrom. The measurements were repeated ten times for 2 drops on different areas of the coated substrate.
TABLE 4
| Numbering | Polymer and method of making same | CA water [ ° [)] | CA DIM[°] | SFE[mN/m] |
| Blank space | - | 84.42 | 38.79 | 42.31 |
| 1 | (Poly-nBA) | 81.37 | 22.23 | 48.99 |
| 2 | (Poly-AMPFE) | 83.00 | 50.22 | 37.25 |
| 3 | (Poly-AFT6:2) | 85.00 | 50.45 | 32.17 |
| 4 | (Blc-nBA-AMPFE) | 98.00 | 50.00 | 35.00 |
| 5 | (Rnd-nBA-APMFE) | 93.57 | 46.00 | 41.08 |
| 6 | (Blc-nBA-AFT6:2) | 97.24 | 49.00 | 39.39 |
| 7 | (Rnd-nBA-AFT6:2) | 92.80 | 45.00 | 38.99 |
As can be seen from Table 4
Coatings comprising copolymers with fluorinated side chains (numbers 2-7) show improved water and soil repellency compared to coatings without fluoropolymer (numbers 1 and blank),
copolymers containing both fluorinated and non-fluorinated side chains (nos. 4-7) show higher contact angles of water than homopolymers with fluorinated side chains (nos. 2+ 3), indicating higher water repellency,
the block copolymer with fluorinated and non-fluorinated side chains (code 4+ 6) shows higher contact angles with water and DIM than the corresponding random copolymer (code 5+ 7), indicating higher water and soil repellency,
the block copolymer No. 4 according to the present invention shows higher contact angles of water and DIM than the block copolymer No. 5 of the prior art, indicating higher water and soil repellency.
Thus, the block copolymer No. 4 according to the present invention combines the advantages of higher water repellency and soil repellency with easier degradability.
Claims (25)
1. A block copolymer comprising at least one first block a and at least one second block B, wherein block a comprises monomer units derived from at least one monomer of formula (I) and block B comprises monomer units derived from at least one monomer of formula (II)
(Rf-CHF-CF 2 -Y-CHR 1 ) m -L-X 1 (I)
R 2 -X 2 (II)
Wherein
Rf is a perfluorinated alkyl group optionally containing one or more heteroatoms,
y is O or S, and Y is O or S,
R 1 is a hydrogen atom or an alkyl group,
l is a single bond or a divalent organic group,
R 2 is an alkyl group which is linear, branched, monocyclic or polycyclic and optionally contains one or more heteroatoms,
X 1 and X 2 Independently of one another are ethylenically unsaturated groups,
m is an integer of 1 to 5.
2. The block copolymer of claim 1, wherein Rf is a perfluorinated C1-C30 alkyl group optionally containing one or more heteroatoms, R 1 Is C1-C6 alkyl, and R 2 Is a C1-C20 alkyl group which is linear, branched, monocyclic or polycyclic and optionally contains one or more heteroatoms.
3. The block copolymer of claim 1 or 2, wherein Rf is selected from the group consisting of
CF 3 -(CF 2 ) 0-3 -，CF 3 -(CF 2 ) 0-3 -O-，
CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -，
CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -O-，
CF 3 -(CF 2 ) 0-3 -O-(CF 2 ) 1-3 -O-CF 2 -，
CF 3 -(CF 2 ) 0-3 -O-(CF 2 -O) 1-8 -and
CF 3 -(CF 2 ) 0-3 -O-(CF 2 -O) 1-8 -CF 2 -。
4. block copolymers according to one or more of claims 1 to 3, characterized in that Rf is selected from the following groups
CF 3 -(CF 2 ) 1-2 -，CF 3 -(CF 2 ) 1-2 -O-，
CF 3 -O-(CF 2 ) 1-3 -，
CF 3 -O-(CF 2 ) 1-2 -O-，
CF 3 -(CF 2 ) 1-2- O-CF 2 -，
CF 3 -O-(CF 2 ) 1-2 -O-CF 2 -，
CF 3 -O-(CF 2 -O) 1-8 -and
CF 3 -O-(CF 2 -O) 1-8 -CF 2 -。
5. the block copolymer according to one or more of claims 1 to 4, wherein R is 1 Selected from H or C1-C3 alkyl.
6. Block copolymer according to one or more of claims 1 to 5, characterized in that L is a single bond or a saturated C1-C20 alkylene group, which is linear or branched, optionally containing one or more heteroatoms, preferably one or more O atoms, and optionally containing one or more functional groups.
7. Block copolymer according to one or more of claims 1 to 6, characterized in that X 1 And X 2 Independently of one another, acrylate or methacrylate groups.
8. Block copolymer according to one or more of claims 1 to 7, characterized in that m is 1, 2 or 3.
9. Block copolymer according to one or more of claims 1 to 8, characterized in that R 2 Is a C2-C12 alkyl group which is linear or branched and optionally contains one or more heteroatoms.
10. The block copolymer according to one or more of claims 1 to 9, wherein R is 2 Is a C2, C3, C4, C5 or C6 alkyl group.
11. Block copolymer according to one or more of claims 1 to 10,
rf is selected from CF 3 -(CF 2 ) 1-2 -、CF 3 -(CF 2 ) 1-2 -O-、CF 3 -O-(CF 2 ) 1-3 -、CF 3 -O-(CF 2 ) 1-3 -O-、CF 3 -(CF 2 ) 1-2 -O-CF2-、CF 3 -O-(CF 2 ) 1-2 -O-CF 2 -、CF 3 -O-(CF 2 -O) 1-8 And CF 3 -O-(CF 2 -O) 1-8 -CF 2 -，
R 1 Is H or CH 3 ，
R 2 Is C2-C12 alkyl, which is linear or branched and optionally contains one or more heteroatoms,
l is a C1-C4 alkylene group, which is optionally branched and optionally contains one or more heteroatoms, preferably one or more O atoms, and optionally contains a functional group,
X 1 and X 2 Independently of one another, acrylate or methacrylate groups,
m is 1 or 2.
12. The block copolymer according to one or more of claims 1 to 11, characterized in that the monomers of formulae (I) and (II) are chosen, independently of one another, from the following formulae:
wherein
Rf has one of the meanings given in claims 1, 2, 3 or 10, R 2 Has the meaning given in claim 1, 8 or 9, and R' and R "are independently of one another H or CH 3 。
13. Block copolymer according to one or more of claims 1 to 12, characterized in that it additionally comprises a third block C comprising monomer units derived from at least one functional comonomer.
14. The block copolymer of claim 13, wherein the functional comonomer is selected from the group consisting of OH, epoxy, -Si (OMe) 3 、-Si(OEt) 3 、CO 2 H or a tertiary amino comonomer.
15. Method for producing functional coatings and/or surface modifications, in particular for coating compositions, by using at least one block copolymer according to one or more of claims 1 to 14.
16. Method for treating a substrate, comprising contacting a substrate with a composition comprising at least one block copolymer according to one or more of claims 1 to 14, optionally a film-forming binder, optionally a solvent and optionally additives, and drying the composition on the substrate.
17. A coated substrate formed according to the method of claim 16.
18. Use of the block copolymers according to one or more of claims 1 to 14 for the preparation of functional coatings and/or surface modifications.
19. Use of the block copolymer according to one or more of claims 1 to 14 in paints, coatings, printing inks, protective coatings, special coatings in electronic or optical applications, photoresists, top or bottom antireflective coatings, cosmetic products, agrochemicals, floor polishes, photographic coatings or coatings for optical elements.
20. Composition comprising at least one block copolymer according to one or more of claims 1 to 14, optionally a film-forming binder, optionally a solvent and optionally additives.
21. The composition according to claim 20, wherein the composition is a paint composition, a coating composition, a fire-extinguishing composition, a lubricant, a deicer composition, a photoresist composition, a lithographic composition, a cosmetic product, an agrochemical, a floor polish or a hydrophobic composition for fabric finishing or glass treatment.
22. A film prepared by curing the composition of claim 20.
23. Product having a coating comprising at least one block copolymer according to one or more of claims 1 to 14.
24. A process for preparing a block copolymer comprising
(a) Polymerizing one of the monomers of formulae (I) and (II) as defined in one or more of claims 1 to 12, or their respective subformulae, in a composition optionally comprising one or more of an initiator, a solvent and a comonomer,
(b) Reacting the resulting polymer with another of the formulae (I) and (II) as defined in one or more of claims 1 to 12, or with a monomer of their respective subformula, in a composition comprising one or more of an initiator, a solvent and a comonomer,
(c) Optionally reacting the resulting polymer with a functional comonomer, preferably a functional comonomer as defined in claim 13 or 14, in a composition comprising one or more of an initiator, a solvent and a comonomer, and
(d) Optionally isolating the polymer(s) of interest,
wherein steps a, b and c may also be performed in a different order than shown above, and wherein in at least a first step the composition comprises an initiator.
25. The method according to claim 24, wherein the polymerization reaction in at least the first of steps a, b and c is carried out by Nitroxide Mediated Polymerization (NMP) in the presence of a nitroxide initiator.
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| EP20192617.7 | 2020-08-25 | ||
| EP20192617 | 2020-08-25 | ||
| PCT/EP2021/073213 WO2022043234A1 (en) | 2020-08-25 | 2021-08-23 | Fluorine containing polymers |
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| EP (1) | EP4204467A1 (en) |
| JP (1) | JP2023538760A (en) |
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| US4656226A (en) | 1985-09-30 | 1987-04-07 | E. I. Du Pont De Nemours And Company | Acrylic pigment dispersants made by group transfer polymerization |
| US5322912A (en) | 1992-11-16 | 1994-06-21 | Xerox Corporation | Polymerization processes and toner compositions therefrom |
| US5763548A (en) | 1995-03-31 | 1998-06-09 | Carnegie-Mellon University | (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization |
| EP0910587B1 (en) | 1996-07-10 | 2001-12-12 | E.I. Du Pont De Nemours And Company | Polymerization with living characteristics |
| CN101952379B (en) | 2008-02-22 | 2014-02-26 | 巴斯夫欧洲公司 | Fluoro levelling agents |
| CN107108456A (en) | 2014-12-19 | 2017-08-29 | 默克专利股份有限公司 | Fluorine compounds |
| JP2016145304A (en) * | 2015-02-09 | 2016-08-12 | ユニマテック株式会社 | Fluorine-containing 2-block copolymer having polymerizable unsaturated group |
| CN107513127A (en) * | 2016-06-17 | 2017-12-26 | 默克专利股份有限公司 | Fluoropolymer |
| AU2020218790A1 (en) * | 2019-02-08 | 2021-08-26 | The University Of Queensland | Capture of fluorinated carbon compounds |
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