polysiloxane polymer

Abstract

The present invention relates to the use of a polymer for improving the cleanability or reducing the soiling of a surface coating, wherein the polymer is a non-crosslinked polymer having a polymer backbone comprising i) a polysiloxane segment containing repeating units of formula (I), wherein R 1 independently at each occurrence represents a hydrocarbyl group, and n is an integer in the range of 6-150; and ii) a non-polysiloxane segment having at least one functional group comprising at least one of a hydroxyl group, an acryloyl group, a methacryloyl group, an acetyl group, a carbamate group, and a methyl ether group; wherein the number of linkages between the non-polysiloxane segments and the polysiloxane segments in the polymer is less than 9.5% based on the average number of silicon atoms per polysiloxane segment, and wherein at least one non-polysiloxane segment is located between two polysiloxane segments.

Description

[0001] This invention relates to the use of polysiloxane polymers to improve the cleanability of surface coatings or reduce dirt pick-up of surface coatings, and to methods for improving the cleanability of surface coatings or reducing dirt pick-up of surface coatings.

[0002] US 6534188 B describes a film-forming composition for preparing a transparent topcoat with improved scratch resistance. The film-forming composition comprises a polysiloxane containing polysiloxane segments and an organic polyvalent linking group selected from alkylene, oxoalkylene, and alkylaryl groups.

[0003] US 2002 / 0103288A relates to coating compositions and polymer molding compounds having anti-stick and anti-fouling properties. The composition comprises 0.1-10% by weight of a branched polymer containing a polymer backbone molecule and polydiorganosiloxane side chains covalently linked to the backbone molecule via Si-C bonds. The long-term anti-stick and anti-fouling properties provided by this branched polymer are not always satisfactory.

[0004] US 8486188 B relates to polyhydroxy functionalized polysiloxanes used as anti-sticking and anti-fouling additives. Polyhydroxy functionalized polysiloxanes can be prepared by an addition reaction of at least one branched glycidyl-based polyhydroxy functionalized allyl polyether with a Si-H functionalized alkyl polysiloxane in the presence of an acid buffer. A disadvantage of using glycidyl-based materials on an industrial scale is the high cost of glycidyl and the need to consider industrial health and safety issues.

[0005] EP 1496080A relates to alternating copolymers of organopolysiloxanes and glycerol derivatives, and cosmetic compositions comprising such alternating copolymers as oils or emulsifiers. These alternating copolymers can be added to paints to prevent adhesion of the paint layer or to improve smoothness, gloss, and abrasion resistance.

[0006] US 2021 / 0029111A relates to amphiphilic polysiloxane prepolymers suitable for use in the preparation of hydrogel contact lenses.

[0007] EP 2662400 A relates to block polysiloxanes and cosmetics containing such block polysiloxanes. Block polysiloxanes are prepared from polysiloxanes having two terminal Si-H groups and compounds having two olefinic unsaturated groups and polyether groups and being capped with hydroxyl groups.

[0008] Additives that can provide anti-stick and anti-fouling properties to coatings and other polymer surfaces are still needed. In particular, additives that can provide these properties over long periods of time, through abrasion and cleaning cycles are needed.

[0009] This invention relates to the use of polymers for improving the cleanability of surface coatings or reducing contamination of surface coatings, wherein the polymer is a non-crosslinked polymer having a polymer backbone comprising the following segments:

[0010] i) Polysiloxane segments containing repeating units of formula (I):

[0011]

[0012] Where R 1 Each occurrence independently represents a hydrocarbon group, and n is an integer in the range of 6-150, and

[0013] ii) a non-polysiloxane segment having at least one functional group, said functional group comprising at least one group selected from hydroxyl, acryloyl, methacryl, acetyl, urethane, and methyl ether groups.

[0014] The number of links between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%, calculated based on the average number of silicon atoms per polysiloxane segment, and at least one non-polysiloxane segment is located between two polysiloxane segments.

[0015] This polymer is ideally suited for use as an additive in coating compositions. It provides anti-sticking and anti-fouling properties to both the coating and the polymer surface. Other properties of the coating, such as leveling, gloss, and cratering, are not adversely affected.

[0016] The polymer is a non-crosslinked polymer. A non-crosslinked polymer has a measurable molecular weight that is less than an infinite value. The non-crosslinked polymer is a liquid or can form a liquid melt at elevated temperatures. In some embodiments, the polymer is a linear polymer or a substantially linear polymer. In other embodiments, the polymer may be branched or have a comb-like morphology.

[0017] The polymer contains polysiloxane segments with repeating units of formula (I):

[0018]

[0019] Where R 1 Each occurrence independently represents a hydrocarbon group, and n is an integer in the range of 6-150. In some embodiments, the polysiloxane segment is composed of repeating units of formula (I). In formula (I), R... 1 Each time it appears, it independently represents a hydrocarbon group. In a preferred embodiment, R 1This represents a hydrocarbon group having 1-12 carbon atoms. Preferred examples of hydrocarbon groups include methyl, octyl, and phenyl. In a typical embodiment, R in formula (I) 1 Each time it appears, it independently represents a C1-C4 alkyl or phenyl group. In some embodiments, 70-100% R 1 The group is methyl.

[0020] Preferably, n in formula (I) is an integer in the range of 10-120, more preferably in the range of 10-60.

[0021] The polymer also comprises a non-polysiloxane segment having at least one functional group, said functional group comprising at least one group selected from hydroxyl, acryloyl, methacryl, acetyl, urethane, and methyl ether groups. Preferred functional groups are hydroxyl, acryloyl, and methacryl. Hydroxyl is particularly preferred. These functional groups allow the polymer of the present invention to be suitable for use as an additive in a curable composition, or to be chemically bonded to a polymer network.

[0022] In some embodiments, the non-polysiloxane segment is composed of a hydrocarbon backbone. In other embodiments, the non-polysiloxane segment is composed of a backbone having ether groups, ester groups, or combinations thereof. In some embodiments, hydroxyl groups, as functional groups, are directly attached to the non-polysiloxane backbone. In other embodiments, functional groups are attached to the non-polysiloxane segment via groups containing at least one ester group or ether group.

[0023] In a preferred embodiment, non-polysiloxane segments are linked to polysiloxane segments via Si-C bonds. Generally, polysiloxane and non-polysiloxane segments are arranged in an alternating order in the polymer of the present invention. In one preferred embodiment, the terminal segments of the polymer of the present invention are non-polysiloxane segments.

[0024] In all embodiments, at least one non-polysiloxane segment is located between two polysiloxane segments.

[0025] Based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%.

[0026] In a preferred embodiment, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.0%, preferably less than 8.5%, more preferably less than 8.0%, and most preferably less than 7.5%.

[0027] Generally, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is greater than 0.8%, preferably greater than 1.0%, and most preferably greater than 1.2%.

[0028] In a typical implementation, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is in the range of greater than 0.8% and less than 8.0%, calculated based on the average number of silicon atoms per polysiloxane segment.

[0029] The number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer of the present invention is determined by the number of Si-H groups in the polysiloxane raw material used to prepare the polymer of the present invention. Generally, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer of the present invention is equal to the percentage (%) of silicon atoms in the polysiloxane raw material having Si-H groups.

[0030] In addition to non-polysiloxane segments with functional groups, the polymer may also contain non-polysiloxane segments without functional groups. Generally, the average number of functional groups per non-polysiloxane segment is in the range of 0.8-2.5.

[0031] The polymer preferably has a number-average molecular weight Mn in the range of 1800 g / mol to 15000 g / mol. The weight-average molecular weight Mw is generally in the range of 2000 to 100000 g / mol, preferably 3000 to 60000 g / mol, more preferably 4000 to 50000 g / mol, and even more preferably 5000 to 40000 g / mol.

[0032] Number-average molecular weight and weight-average molecular weight were determined by gel permeation chromatography at 22°C using a Waters 2695 separation module and a Waters 2414 refractive index detector. Toluene or THF was a suitable eluent, and calibration was performed using a polydimethylsiloxane standard.

[0033] In a preferred embodiment, the polymer can be obtained by a method comprising the following steps:

[0034] a) Provides a polysiloxane comprising repeating units of formula (I) above and having at least two Si-H groups, wherein less than 9.5% of the silicon atoms of the polysiloxane have Si-H groups.

[0035] b) Provide a non-polysiloxane compound having at least two olefinically unsaturated groups per molecule.

[0036] c) Provide a non-polysiloxane compound having one olefinic unsaturated group per molecule.

[0037] At least one compound in b) or c) has at least one functional group per molecule, said functional group comprising at least one group selected from hydroxyl, acryloyl, methacryl, acetyl, carbamate, and methyl ether groups.

[0038] d) Covalently linking the nonpolysiloxane compound having at least two olefinic unsaturated groups per molecule and the nonpolysiloxane compound having one olefinic unsaturated group per molecule to the polysiloxane having at least two Si-H groups.

[0039] In some embodiments, the polysiloxane provided in step a) of the method is a polysiloxane having two terminal Si-H groups.

[0040] In another embodiment, the polysiloxane backbone provided in step a) is a polysiloxane having at least two lateral Si-H groups.

[0041] Suitable polysiloxanes having at least two Si-H groups can be represented by the following general formula (II):

[0042] MaM′bDcD′dTeQf(II)

[0043] in

[0044] ·M represents [R1SiO 1 / 2 ],

[0045] ·M′ represents [R1SiHO 1 / 2 ],

[0046] ·D represents [R1SiO] 2 / 2 ],

[0047] ·D′ represents [R1SiHO 2 / 2 ],

[0048] ·T represents [R1SiO 3 / 2 ],

[0049] Q represents [SiO] 4 / 2 ],

[0050] •a is an integer from 0 to 10, preferably an integer from 0 to 2, and more preferably 0.

[0051] b is an integer from 0 to 10, preferably an integer from 0 to 2, and more preferably 2.

[0052] c is an integer from 0 to 300, preferably an integer from 2 to 250, and more particularly an integer from 5 to 200.

[0053] ·d is an integer from 0 to 10, preferably an integer from 0 to 2, and more particularly 0.

[0054] ·e is an integer from 0 to 10, preferably an integer from 0 to 5, and more particularly 0.

[0055] f is an integer from 0 to 10, preferably an integer from 0 to 5, and more particularly 0.

[0056] • R1 is an independent hydrocarbon group as defined in equation (I) above each time it appears, provided that b+d≧2.

[0057] It is generally known in the art to describe polysiloxanes using M, D, T, and Q units. Compounds of formula (I) can be prepared by well-known equilibration methods.

[0058] Non-polysiloxane compounds having at least two olefinically unsaturated groups per molecule do not contain polysiloxane segments. Generally, the compound has two or three olefinically unsaturated groups, preferably two. Allyl ethers and allyl esters are very suitable olefinically unsaturated groups. Suitable examples of such non-polysiloxane compounds are diallyl ethers of triols, such as trimethylolpropane or glycerol, and alkoxylated derivatives of such triols.

[0059] Non-polysiloxane compounds having one olefin unsaturated group per molecule do not contain polysiloxane segments. Allyl ethers and allyl esters are very suitable olefin unsaturated groups. Suitable examples of such non-polysiloxane compounds are monoallyl ethers of diols.

[0060] In step d), the polysiloxane having at least two Si-H groups, the non-polysiloxane compound having at least two olefinically unsaturated groups per molecule, and the non-polysiloxane compound having one olefinically unsaturated group per molecule are covalently linked by a hydrosilylation reaction between the Si-H groups and the olefinically unsaturated groups. This hydrosilylation reaction is as described in WO 2019 / 020542.

[0061] Generally, all or substantially all of the Si-H groups react in the hydrosilylation reaction. Therefore, the polymers of the present invention generally contain no or substantially no Si-H groups.

[0062] In some embodiments, non-polysiloxane compounds having hydroxyl groups are used. This initially yields a polymer with hydroxyl functional groups. If desired, the hydroxyl groups can be converted to other functional groups in subsequent reaction steps. In exemplary embodiments, the hydroxyl groups can be converted to acryloyl or methacryloyl groups, respectively, through esterification with acrylic acid or methacrylic acid. Instead of acrylic acid or methacrylic acid, lower alkyl esters of these acids can also be used in transesterification reactions.

[0063] Therefore, in some embodiments of the method for preparing the polymer, the non-polysiloxane compound provided in step b), or the non-polysiloxane compound provided in step c), or both of the non-polysiloxane compounds, contains at least one hydroxyl group, and the method further includes step e), wherein one or more hydroxyl groups are reacted via esterification / exchange, acetylation, reaction with isocyanate, or alkoxylation to provide acryloyl, methacryl, acetyl, carbamate, or alkyl ether groups, respectively.

[0064] As described above, this polymer is well-suited for use as an additive to provide anti-stick and anti-fouling properties to coatings and other polymer surfaces. This use can also be described as a method for improving the cleanability of surface coatings or reducing contamination of surface coatings, which includes incorporating the polymer into a coating composition.

[0065] The present invention also relates to a curable composition comprising:

[0066] a) An adhesive having functional groups, said functional groups comprising at least one group selected from hydroxyl, acryloyl, methacryl, acetyl, carbamate, and methyl ether groups.

[0067] b) A crosslinking agent or crosslinking initiator for the functional groups of the adhesive, and

[0068] c) The polymer used according to the present invention.

[0069] In a preferred embodiment of the curable composition, the adhesive a) comprises at least one of polyacrylate polyol, polyester polyol, polyether polyol or polyurethane polyol.

[0070] The composition preferably contains 0.10-10.00% by weight of the polymer used according to the invention, preferably 0.20-8.00% by weight, more preferably 0.30-7.00% by weight, or 0.30-6.00% by weight, or 0.30-5.00% by weight, particularly 0.50-5.00% by weight, in each case based on the total weight of the composition.

[0071] The polymer used according to the present invention can be included in the composition as a 100% substance, as a solution, as a dispersion, or as an emulsion.

[0072] The properties of the compositions, particularly coating compositions, molding compounds, and cosmetic formulations, are not impaired by the content of the polymers of the present invention. The presence or use of these polymers has no negative impact, for example, on the corrosion resistance, gloss retention, weather resistance, and / or mechanical strength of coatings made from these compositions.

[0073] In addition, curable coating compositions may contain pigments or fillers. These pigments or fillers can be selected by those skilled in the art as needed in specific circumstances.

[0074] Curable coating compositions may also contain degassing agents, defoamers, emulsifiers, wetting and dispersing agents, adhesion promoters, film-forming aids, rheology control additives (thickeners), flame retardants, driers, desiccants, anti-skinning agents, corrosion inhibitors, waxes, matting agents, and other additives known to those skilled in the art. These additives may be selected by those skilled in the art based on their expertise and used in accordance with conventionally known effective amounts as needed in specific circumstances.

[0075] The present invention also relates to a method for improving the cleanability of a surface coating or reducing contamination of a surface coating, the method comprising including a non-crosslinked polymer in a surface coating composition, said polymer having a polymer backbone comprising the following segments:

[0076] i) Polysiloxane segments containing repeating units of formula (I):

[0077]

[0078] Where R 1 Each occurrence independently represents a hydrocarbon group, and n is an integer in the range of 6-150, and

[0079] ii) a non-polysiloxane segment having at least one functional group, said functional group comprising at least one group selected from hydroxyl, acryloyl, methacryl, acetyl, urethane, and methyl ether groups.

[0080] Based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%, and at least one non-polysiloxane segment is located between two polysiloxane segments. According to this method, the polymer is included in the composition in an amount sufficient to improve the cleanability of the surface coating or reduce contamination of the surface coating. Example

[0081] Preparation of polymers

[0082] Comparative Example A

[0083] The reaction of methyl-hydrosiloxanes with the average formula MH2D14 with trimethylolpropane diallyl ether and ethylene glycol monoallyl ether (molar ratio 3.0:2.0:2.3).

[0084] 12.5% ​​of the silicon atoms in polysiloxane MH2D14 have Si-H groups. This corresponds to a reaction product in which, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 12.5%.

[0085] 201.415 g of methylhydrosiloxane was charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.550 g of a 0.2% solution of Karstedt catalyst in xylene was added. Subsequently, 23.300 g of trimethylolpropane diallyl ether was added over 20 minutes via a dropping funnel, followed by stirring at 100 °C for 30 minutes. Then, 25.285 g of ethylene glycol monoallyl ether was added over 20 minutes via a dropping funnel, followed by stirring at 100 °C for 3 hours. The volatiles were then removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction product was characterized by gel permeation chromatography: Mn = 2266 g / mol, Mw = 5682 g / mol.

[0086] Comparative Example B

[0087] The reaction of methyl-hydrosiloxanes with the average formula MH2D6 with trimethylolpropane diallyl ether and ethylene glycol monoallyl ether (molar ratio 3.0:2.0:2.3).

[0088] 25.0% of the silicon atoms in polysiloxane MH2D6 have Si-H groups. This corresponds to a reaction product in which, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 25.0%.

[0089] 171.011 g of methylhydrosiloxane was charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.550 g of a 0.2% solution of Karstedt catalyst in xylene was added. Subsequently, 37.881 g of trimethylolpropane diallyl ether was added over 20 minutes via a dropping funnel, followed by stirring at 100 °C for 3 hours. Then, 41.108 g of ethylene glycol monoallyl ether was added over 20 minutes via a dropping funnel, followed by stirring at 100 °C for 3 hours. The volatiles were then removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction product was characterized by gel permeation chromatography: Mn = 1827 g / mol, Mw = 3563 g / mol.

[0090] Example 1

[0091] The reaction of methyl-hydrosiloxane with the average formula MH2D79.3 with trimethylolpropane diallyl ether and ethylene glycol monoallyl ether (molar ratio 3.0:2.0:2.3).

[0092] The polysiloxane MH2D79.3 has 2.46% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 2.46%.

[0093] 238.427 g of methylhydrosiloxane was charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.550 g of a 0.2% solution of Karstedt catalyst in xylene was added. Subsequently, 5.550 g of trimethylolpropane diallyl ether was added over 20 minutes via a dropping funnel, followed by stirring at 100 °C for 3 hours. Then, 6.023 g of ethylene glycol monoallyl ether was added over 20 minutes via a dropping funnel, followed by stirring at 100 °C for 3 hours. The volatiles were then removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction product was characterized by gel permeation chromatography: Mn = 2813 g / mol, Mw = 22909 g / mol.

[0094] Example 2

[0095] The reaction of methyl-hydrosiloxane with the average formula MH2D106.3 with trimethylolpropane diallyl ether and ethylene glycol monoallyl ether (molar ratio 3.0:2.0:2.3).

[0096] The polysiloxane MH2D106.3 has 1.84% silicon atoms with Si-H groups. This corresponds to a reaction product in which, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 1.84%.

[0097] 241.140 g of methylhydrosiloxane was charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.550 g of a 0.2% solution of Karstedt catalyst in xylene was added. Subsequently, 4.249 g of trimethylolpropane diallyl ether was added over 20 minutes via a dropping funnel, followed by stirring at 100 °C for 3 hours. Then, 4.661 g of ethylene glycol monoallyl ether was added over 20 minutes via a dropping funnel, followed by stirring at 100 °C for 3 hours. The volatiles were then removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction product was characterized by gel permeation chromatography: Mn = 3710 g / mol, Mw = 32053 g / mol.

[0098] Preparation of intermediate I1

[0099] The reaction of trimethylolpropane diallyl ether with ethoxylated trimethylolpropaneoxetane (average 3.3 vinyl oxide groups)

[0100] 137.32 g of trimethylolpropane diallyl ether and 0.25 g of trifluoromethanesulfonic acid were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The mixture was heated to 80 °C. At this temperature, 362.68 g of ethoxylated trimethylolpropane oxobutane (average 3.3 vinyl oxide groups) was added over 5 hours. The reaction was then continued for 3 hours. Alkaline inorganic clay was then added, and the reaction mixture was stirred for 2 hours, followed by filtration. The reaction product was characterized by gel permeation chromatography: Mn = 842 g / mol, Mw = 2014 g / mol.

[0101] Example 3

[0102] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I1 (molar ratio 2.4:3.4)

[0103] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0104] 104.49 g of methylhydrosiloxane, 45.00 g of intermediate I1, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction product was characterized by gel permeation chromatography: Mn = 3581 g / mol, Mw = 21060 g / mol.

[0105] Example 4

[0106] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I1 (molar ratio 2.9:3.9)

[0107] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0108] 106.51 g of methylhydrosiloxane, 43.49 g of intermediate I1, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction products were characterized by gel permeation chromatography: Mn = 3774 g / mol, Mw = 23394 g / mol.

[0109] Example 5

[0110] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I1 (molar ratio 3.2:4.2)

[0111] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0112] 107.76 g of methylhydrosiloxane, 42.24 g of intermediate I1, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction products were characterized by gel permeation chromatography: Mn = 4021 g / mol, Mw = 24922 g / mol.

[0113] Preparation of intermediate I2

[0114] The reaction of trimethylolpropane diallyl ether with ε-caprolactone and trimethylolpropaneoxetane in a molar ratio of 1:3:1

[0115] 143.47 g of trimethylolpropane diallyl ether and 0.23 g of trifluoromethanesulfonic acid were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The mixture was heated to 80 °C. At this temperature, a mixture of 229.06 g of ε-caprolactone and 77.47 g of trimethylolpropaneoxetane was added over 5 hours. The reaction was then continued for 90 minutes. Alkaline inorganic clay was then added, and the reaction mixture was stirred for 2 hours, followed by filtration. The reaction product was characterized by gel permeation chromatography: Mn = 1034 g / mol, Mw = 1811 g / mol.

[0116] Example 6

[0117] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I2 (molar ratio 2.4:3.4)

[0118] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0119] 109.09 g of methylhydrosiloxane, 40.91 g of intermediate I2, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction product was characterized by gel permeation chromatography: Mn = 4366 g / mol, Mw = 27109 g / mol.

[0120] Example 7

[0121] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I2 (molar ratio 2.9:3.9)

[0122] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0123] 110.91 g of methylhydrosiloxane, 39.09 g of intermediate I2, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction products were characterized by gel permeation chromatography: Mn was 4882 g / mol, and Mw was 29284 g / mol.

[0124] Example 8

[0125] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I2 (molar ratio 3.2:4.2)

[0126] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0127] 112.08 g of methylhydrosiloxane, 37.92 g of intermediate I2, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction products were characterized by gel permeation chromatography: Mn = 4839 g / mol, Mw = 31244 g / mol.

[0128] Preparation of intermediate I3

[0129] The reaction of trimethylolpropane diallyl ether with ethoxylated trimethylolpropaneoxetane (average 3.3 vinyl oxide groups) at a molar ratio of 1:1

[0130] 215.46 g of trimethylolpropane diallyl ether and 0.25 g of trifluoromethanesulfonic acid were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The mixture was heated to 80 °C. At this temperature, 284.54 g of ethoxylated trimethylolpropaneoxetane (average 3.3 vinyl oxide groups) was added over 5 hours. The reaction was then continued for 6 hours. Alkaline inorganic clay was then added, and the reaction mixture was stirred for 2 hours, followed by filtration. The reaction product was characterized by gel permeation chromatography: Mn = 782 g / mol, Mw = 1887 g / mol.

[0131] Example 9

[0132] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I3 (molar ratio 2.4:3.4)

[0133] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0134] 117.35 g of methylhydrosiloxane, 32.65 g of intermediate I3, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction products were characterized by gel permeation chromatography: Mn = 4691 g / mol, Mw = 27770 g / mol.

[0135] Example 10

[0136] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I3 (molar ratio 2.9:3.9)

[0137] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0138] 118.97 g of methylhydrosiloxane, 31.03 g of intermediate I3, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction products were characterized by gel permeation chromatography: Mn = 4856 g / mol, Mw = 29320 g / mol.

[0139] Example 11

[0140] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with intermediate I3 (molar ratio 3.4:4.2)

[0141] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0142] 119.96 g of methylhydrosiloxane, 30.04 g of intermediate I3, and 45.00 g of xylene were charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.52 g of a 0.2% solution of Karstedt catalyst in xylene was added. The temperature was observed to rise to 104 °C. The reaction mixture was stirred at 100 °C for 1 hour. Then, volatiles were removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction products were characterized by gel permeation chromatography: Mn = 4482 g / mol, Mw = 31658 g / mol.

[0143] Preparation of intermediate I4

[0144] The reaction of methyl-hydrosiloxane with the average formula MH2D37 with trimethylolpropane diallyl ether and allyl ethylene glycol (molar ratio 3:2:2.3).

[0145] The polysiloxane MH2D37 has 5.12% silicon atoms with Si-H groups. This corresponds to a reaction product where, based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is 5.12%.

[0146] 91.31 g of methylhydrosiloxane was charged into a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen purging. The flask was heated to 75 °C, and 0.22 g of a 0.2% solution of Karstedt catalyst in xylene was added. 4.34 g of trimethylolpropane diallyl ether was added via a dropping funnel over 5 minutes. An initial temperature rise to 106 °C was observed. The reaction mixture was stirred at 100 °C for 3 hours and then at 110 °C for another 1 hour. Subsequently, 4.93 g of allyl ethylene glycol was added via a dropping funnel over 5 minutes, followed by stirring at 100 °C for another 3 hours. Volatiles were then removed by vacuum distillation at 130 °C and 15 mbar for 1 hour. The reaction product was characterized by gel permeation chromatography: Mn = 2861 g / mol, Mw = 22112 g / mol.

[0147] Example 12

[0148] The reaction of intermediate I4 with methyl methacrylate

[0149] In a flask equipped with a stirrer, thermometer, reflux condenser, air inlet, and water separator, 83.22 g of intermediate I4, 16.78 g of methyl methacrylate, 0.1 g of 4-methoxyphenol, and 0.1 g of 2,6-di-tert-butyl-4-methylphenol were charged. The mixture was heated to 105 °C, and water was removed by azeotropic distillation. After all water was removed, the mixture was cooled to 50 °C, and 0.50 g of zirconium acetylacetonate was added. The mixture was heated to reflux and distilled for 12 hours to remove methanol. Subsequently, volatiles were removed by rotary evaporation (80 °C, 45 mbar). NMR analysis showed that approximately 90% of the hydroxyl groups had been converted to methacrylamide. The reaction product was further characterized by gel permeation chromatography: Mn was 4043 g / mol, and Mw 20136 was 0.22 g / mol.

[0150] Application Trial

[0151] Preparation of solvent-based transparent coating compositions

[0152] Prepare transparent coating compositions from the raw materials shown in Table 1 below:

[0153]

[0154] Mix the components of part A to form a homogeneous solution.

[0155] Just before the coating composition is applied to the substrate, portions A and B are mixed to form a homogeneous solution.

[0156] To prepare the transparent coating, the transparent coating composition was applied to a glass plate using a 100 μm spiral doctor blade. After rapid air drying at room temperature for 20 minutes, the coated layer was cured at 60°C for 16 hours.

[0157] After curing, the surface of the transparent coating was subjected to the following tests.

[0158] Detecting water contact angle

[0159] The water contact angle was measured using a Krüss instrument (the "Easydrop" model equipped with an integrated camera) on the coated substrate prepared as described above. The water contact angle was measured to characterize the surface's hydrophobicity. Measurements were performed at 23°C and 65% relative humidity. The results were evaluated using software provided with the Krüss instrument. A higher contact angle indicates better hydrophobicity and ease of cleaning.

[0160] Detection of surface energy and its polar and dispersive components

[0161] For these tests, five different test liquids with known surface tensions, polar components, and dispersion components were used. These test liquids were water, glycerol, ethylene glycol, 1-octanol, and n-dodecane. The contact angles of these test liquids on the coated substrate were measured using the contact angle method described above, ranging from 5 to 11 μL droplet volumes. Surface energy was measured using the Owens-Wendt-Rabel & Kaelble method. Lower polar components of surface energy generally indicate better ease of cleaning.

[0162] Edding test as a marker resistance test

[0163] Use Edding 400 permanent markers to etch lines onto the film surface and visually assess its writability. Assess whether the ink spreads or shrinks on the surface. After the ink dries, attempt to remove it by wiping with a dry cloth. Rating: 1-5:

[0164] 1 = The ink shrinks and can be removed with a paper towel without leaving any residue.

[0165] 5 = The ink spreads well on the substrate and is virtually impossible to remove.

[0166] Carbon black slurry test as a staining resistance test

[0167] Carbon black FW 200 slurry has the following composition: 57.6g water, 26.3g of [unspecified ingredient] from BYK-Chemie GmbH. (40%), 1.0 g of BYK-024 from BYK-Chemie GmbH, 0.1 g of ActicideMBS (a biocide from Thor Chemie), and 15.0 g of coloring carbon black FW 200 (available from Evonik Industries). The above components were milled using a Dispermat CV (Teflon blade, 60 minutes, 10000 rpm (18 m / sec), 40°C). The milling medium was mixed with glass beads. The weight ratio between them is 1:1.

[0168] Apply the slurry to the surface of the transparent coating with a brush and store the test panel at 100°C for 1 hour. Then, wash off the pigment with water and a soft cloth to remove the loose pigment.

[0169] Rating: 1-5

[0170] Identify the remaining residue:

[0171] 1 = No residue

[0172] 5 = Most of the residue.

[0173] Mineral oil efflux test as a hydrophobic / oleophobic test:

[0174] Place a drop of commercially available mineral oil on the membrane surface. Then, tilt the coated membrane surface until the oil droplet has flowed approximately 10 cm. After 5 minutes, visually evaluate the oil trail or droplet remodeling.

[0175] Rating: 1-5

[0176] 1 = The oil trajectory immediately reassembles into a single oil droplet.

[0177] 5 = The oil trajectory has not been reorganized, but may spread further.

[0178] Table 2 below summarizes the test results of the transparent coating.

[0179]

[0180] As can be seen from the results in Table 2, the polymers of the present invention result in a higher water contact angle on the transparent coating surface compared to the comparative examples. The polymers of the present invention also result in a lower polar component contribution to the total surface energy. This indicates that the polysiloxanes of the present invention make the coating surface hydrophobic and provide it with an "easy-to-clean" property. This is demonstrated in the contamination tests on the coating, represented by the Eddie test, carbon black slurry test, and mineral oil outflow test.

[0181] These results indicate that by using the polymer of the present invention as an additive, a dirt-resistant (as carbon black) and oil-repellent surface with improved anti-marking properties (Eddie test) was obtained, and the performance of the surface was superior to that of the comparative product.

Claims

1. Use of a polymer for improving the cleanability of a surface coating or reducing contamination of a surface coating, wherein said polymer is a non-crosslinked polymer having a polymer backbone comprising the following segments: i) Polysiloxane segments containing repeating units of formula (I): wherein R 1 independently at each occurrence represents a hydrocarbyl group, and n is an integer in the range of 10 to 120, and ii) a non-polysiloxane segment having at least one functional group, wherein the non-polysiloxane segment is composed of a backbone having an ether group, an ester group, or a combination thereof, the functional group comprising at least one hydroxyl group and optionally at least one group selected from acryloyl, methacryl, acetyl, and methyl ether groups. Based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%, and at least one non-polysiloxane segment is located between two polysiloxane segments. The functional group is connected to the non-polysiloxane segment via a group containing at least one ester group or ether group.

2. The use according to claim 1, wherein the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is less than 8.0%, calculated based on the average number of silicon atoms per polysiloxane segment.

3. The use according to claim 1, wherein R 1 Each time it appears, it independently represents a C1-C4 alkyl or phenyl group.

4. The use according to claim 2, wherein R 1 Each time it appears, it independently represents a C1-C4 alkyl or phenyl group.

5. The use according to any one of claims 1-4, wherein the average number of functional groups per non-polysiloxane segment is in the range of 0.8-2.

5.

6. The use according to any one of claims 1-4, wherein the polymer has a weight-average molecular weight of 2000 g / mol to 100000 g / mol.

7. The use according to any one of claims 1-4, wherein the terminal segment is a non-polysiloxane segment.

8. The use according to any one of claims 1-4, wherein said polymer is obtained by a method comprising the following steps: a) Provide a polysiloxane having at least two Si-H groups, wherein less than 9.5% of the silicon atoms in the polysiloxane have Si-H groups. b) Provide a non-polysiloxane compound having at least two olefinically unsaturated groups per molecule, and c) Provide a non-polysiloxane compound having one olefinic unsaturated group per molecule. At least one of the compounds in b) or c) has at least one functional group per molecule. The functional group comprises at least one hydroxyl group and optionally at least one group selected from acryloyl, methacryl, acetyl, and methyl ether groups. d) Covalently linking the nonpolysiloxane compound having at least two olefinic unsaturated groups per molecule and the nonpolysiloxane compound having one olefinic unsaturated group per molecule to the polysiloxane having at least two Si-H groups.

9. The use according to any one of claims 1-4, wherein the polymer is contained in a curable composition comprising: i) an adhesive having functional groups, said functional groups comprising at least one group selected from hydroxyl, acryloyl, methacryl, acetyl, carbamate, and methyl ether groups, and ii) A crosslinking agent or crosslinking initiator for the functional groups of the adhesive.

10. The use according to claim 9, wherein the polymer content in the composition is 0.10-10.00% by weight, based on the total weight of the composition.

11. A method for improving the cleanability of a surface coating or reducing contamination of a surface coating, the method comprising including a non-crosslinked polymer in a surface coating composition, said polymer having a polymer backbone comprising the following segments: i) Polysiloxane segments containing repeating units of formula (I): Where R 1 Each occurrence independently represents a hydrocarbon group, and n is an integer in the range of 10-120. ii) a non-polysiloxane segment having at least one functional group, wherein the non-polysiloxane segment is composed of a backbone having an ether group, an ester group, or a combination thereof, the functional group comprising at least one hydroxyl group and optionally at least one group selected from acryloyl, methacryl, acetyl, and methyl ether groups. Based on the average number of silicon atoms per polysiloxane segment, the number of connecting bonds between non-polysiloxane segments and polysiloxane segments in the polymer is less than 9.5%, and at least one non-polysiloxane segment is located between two polysiloxane segments. The functional group is connected to the non-polysiloxane segment via a group containing at least one ester group or ether group.

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