阅读说明：本技术 具有聚醚和聚硅氧烷链段的聚合物 (Polymers having polyether and polysiloxane segments ) 是由 G·W·让基 M·埃伯哈特 M·黑克伦 S·滕布施 O·穆斯基奥里克 J·哈特曼 P·德 于 2018-07-23 设计创作，主要内容包括：本发明涉及一种聚合物,其具有a)聚合物骨架和b)共价连接到聚合物骨架的一个或多个聚合物侧链,其中所述聚合物侧链包含聚醚链段和聚硅氧烷链段,所述聚硅氧烷链段具有1050至6000的数均分子量,且所述聚醚链段位于聚合物骨架和聚硅氧烷链段之间。(The invention relates to a polymer having a) a polymer backbone and b) one or more polymeric side chains covalently linked to the polymer backbone, wherein the polymeric side chains comprise a polyether segment and a polysiloxane segment, the polysiloxane segment having a number average molecular weight of 1050 to 6000, and the polyether segment is located between the polymer backbone and the polysiloxane segment.)

1. A polymer having

a) A polymer backbone and

b) one or more pendant polymeric chains covalently attached to the polymeric backbone, wherein the pendant polymeric chains comprise a polyether segment and a polysiloxane segment,

the polysiloxane segment has a number average molecular weight of 1050 to 6000, and the polyether segment is located between the polymer backbone and the polysiloxane segment.

2. The polymer according to claim 1, wherein the polysiloxane segment has a number average molecular weight of 1100 to 6000, preferably 1200 to 5000.

3. A polymer according to claim 1 or 2, wherein the polymer backbone is a (co) polymer of polymerisable ethylenically unsaturated monomers.

4. A polymer according to any preceding claim, wherein the polyether segment has a number average molecular weight of 450 to 5000.

5. A polymer according to any preceding claim, wherein the polyether segment comprises polymerized units of an alkylene oxide selected from ethylene oxide, propylene oxide and combinations thereof.

6. The polymer according to any of the preceding claims, wherein the polymer further comprises a functional group.

7. The polymer of claim 6, wherein said functional group is selected from the group consisting of hydroxyl, carboxylic acid, amino, etherified amino, amide, epoxy, alkoxysilyl and combinations thereof.

8. A process for preparing a polymer according to claim 3, comprising the step of copolymerizing

a) A macromonomer MM having one polymerizable ethylenically unsaturated group, a polyether segment and a polysiloxane segment, said polysiloxane segment having a number average molecular weight of 1050 to 6000, and said polyether segment being located between the polymerizable ethylenically unsaturated group and the polysiloxane segment, and

b) at least one other additional monomer having at least one polymerizable ethylenically unsaturated group.

9. The method according to claim 8, wherein the macromer MM is prepared by:

i) provide for

a) A monomer having a polymerizable ethylenically unsaturated group and an additional functional group different from the polymerizable ethylenically unsaturated group, and

b) a molecule having a group reactive with the at least one additional functional group, a polyether segment and a polysiloxane segment, the polysiloxane segment having a number average molecular weight of 1050 to 6000, and the polyether segment being located between the group reactive with the at least one additional functional group and the polysiloxane segment,

ii) forming a covalent bond between the monomer a) and the molecule b) by reacting the at least one additional functional group with a group reactive with the at least one additional functional group.

10. The method according to claim 8, wherein said macromer MM is prepared by

i) Provide for

a) A monomer having a polymerizable ethylenically unsaturated group, a polyether segment, and an additional ethylenically unsaturated functional group different from the polymerizable ethylenically unsaturated group, and wherein said polyether segment is located between the polymerizable ethylenically unsaturated group and said additional ethylenically unsaturated functional group,

b) molecules having polysiloxane segments with a number average molecular weight of 1050 to 6000 and one Si-H group, and

ii) forming a covalent bond between the monomer a) and the molecule b) by hydrosilylation of the Si-H groups on the additional ethylenically unsaturated functional groups.

11. A process for preparing a polymer according to any one of the preceding claims 1 to 7, comprising the steps of

i) Provide for

a) A polymer backbone having at least one functional group and

b) a molecule having a group reactive with the at least one functional group, a polyether segment and a polysiloxane segment, the polysiloxane segment having a number average molecular weight of 1050 to 6000 and the polyether segment being located between the group reactive with the at least one functional group and the polysiloxane segment, and

ii) forming a covalent bond between the polymer backbone a) and the molecule b) by reacting the at least one functional group with a group reactive with the at least one functional group.

12. A composition comprising

a) A polymer according to any of the preceding claims 1 to 7 in an amount of from 0.1 to 15% by weight, based on the total non-volatile content of the composition, and

b) a binder different from the polymer a).

13. A composition according to claim 12, wherein the composition is liquid at a temperature of 20 ℃ and comprises a volatile diluent.

14. A multi-layer coating system on a substrate, comprising at least one base coat and one top coat, wherein at least one layer is based on a composition according to claim 12 or 13.

15. The multi-layer coating system according to claim 14, wherein the substrate is an automobile or a part thereof.

16. A method of forming a multi-layer coating system on a substrate comprising the steps of

i) Applying a coating composition a) to a substrate to form a coating layer a) and

ii) applying a coating composition b) on the coating layer a) to form a coating layer b),

wherein at least one of the coating compositions a) or b) comprises a polymer according to any one of the preceding claims 1 to 7 in an amount of from 0.1 to 15% by weight, based on the total non-volatile content of the coating composition.

17. Use of a polymer according to any of the preceding claims 1 to 7 as an additive in a composition to control one or more properties of the composition selected from levelling, surface smoothness, cratering, electro-staining, overcoatability, shrinkage, open time, dirt adhesion, self-cleaning, air flow sensitivity, electro-staining, fogging and electrostatic properties.

Examples

Raw materials:

GPC analysis of the resulting macromonomers and copolymers

The number average and weight average molecular weights and molecular weight distributions were determined in accordance with DIN 55672-1:2007-08 at 40 ℃ using a high pressure liquid chromatography pump (WATERS 600 HPLC pump) and a refractive index detector (Waters 410). A combination of 3 Styragel columns from WATERS (with dimensions of 300mm x 7.8mm ID/column, particle size of 5 μm and pore size HR4, HR2 and HR1) was used as separation columns. The eluent used for the copolymer was tetrahydrofuran containing 1% by volume of dibutylamine, the elution rate being 1 ml/min. Conventional calibration was performed using polystyrene standards.

For Polydimethylsiloxane (PDMS) macromonomers, the eluent was toluene and the elution rate was 1 ml/min. Routine calibration was performed using polydimethylsiloxane standards. The molecular weights reported and referred to herein always have units of g/mol.

Iodine number

By H according to DIN 53241-1₂To determine the Si-H group content of the Si-H functional PDMS macromonomers SM1 to SM4 and the Si-H conversion during the hydrosilylation reaction for preparing the PDMS-polyether block copolymer.

OH number

The hydroxyl content of the OH-functional PDMS-polyether block copolymers and the OH conversion during the transesterification reaction for the preparation of the PDMS-polyether block macromonomers were determined according to DIN ISO 4629.

Non-volatile content

The amount of non-volatiles (solids content) was determined by means of DIN EN ISO 3251:2008-06 at 150 ℃ for 20 minutes.

General procedure for preparing SiH-functional polysiloxane segments

A four-necked flask equipped with an agitator, a thermometer, a dropping funnel and a nitrogen inlet tube was heated to 150 ℃ under a nitrogen stream using a heat gun to remove a trace amount of water. After cooling the apparatus to ambient temperature under a stream of nitrogen, the vessel was loaded with a solution of hexamethylcyclotrisiloxane (D3) in cyclohexane, which had been dried for 24 hours over molecular sieve A3. At a reaction temperature of 20 deg.C, a solution of butyllithium (1.7M in hexane) was introduced over 5 minutes. The reaction mixture was not allowed to exceed 30 ℃ by cooling with a water bath. After 30 minutes, THF was added slowly to start the polymerization. The temperature was monitored and kept below 30 ℃. After 5 hours, the reaction was quenched by addition of dimethylchlorosilane and stirred for another 30 minutes. Thereafter, the mixture was neutralized by adding an aqueous sodium bicarbonate solution (8.0 wt%) and vigorously stirred for 1 hour. The organic layer was separated, distilled (20 mbar, 100 ℃) in vacuo to remove all solvent and filtered through a piece of Celite. The product (asymmetric, SiH functional polydimethylsiloxane) is a clear colorless liquid of low viscosity.

Table 1: overview of the prepared SiH-functional polysiloxane segments PSS

General procedure for the preparation of macromonomers MM having polyether segments, polysiloxane segments and polymerizable ethylenically unsaturated groups

A four-necked flask equipped with stirrer, thermometer, dropping funnel and nitrogen inlet was charged with α -allyl- ω -methacryloxy functional polyether (which was used in a 25% molar excess relative to the SiH functional polysiloxane), SiH functional polysiloxane segments PSS and ethyl acetate, the components were mixed and heated to 40 ℃.

The SiH conversion is monitored by means of the iodine value. It usually takes 1.5 to 2.5 hours to reach complete exhaustion of all SiH functions. The reaction mixture was then cooled to ambient temperature and filtered through a cellulose filter paper. 2, 6-di-tert-butyl-4-methylphenol and 4-methoxyphenol (0.026 g each) were added to stabilize the product.

The macromer was obtained as a clear, yellow and slightly viscous liquid.

Table 2: overview of the macromonomers MM prepared

Preparation of inventive copolymers A1 to A6 and of comparative copolymers B1 to B3

In a beaker, a monomer mixture according to table 3 was prepared, comprising an initial amount of the radical initiator Trigonox 21 and diluted with 30% of the total amount of isobutanol mentioned in table 3. This monomer mixture was transferred to a dropping funnel. A four-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet was charged with the remaining amount of isobutanol and heated to 110 ℃. A dropping funnel with monomer mixture was mounted on the reaction vessel and nitrogen was passed through the reaction apparatus for 10 minutes. After the reaction temperature had been reached, the monomer mixture was slowly metered in over 90 minutes. Thereafter, the reaction temperature was maintained at 110 ℃ for 60 minutes, after which 0.1 g Trigonox 21 was added. The reaction temperature was kept at 110 ℃ for a further 60 minutes, after which the solvent used was removed by distillation under vacuum (20 mbar, 120 ℃) on a rotary evaporator.

Table 3: raw material amounts (g) and analytical data for synthesis of the double comb block copolymers A1 to A7 and the comparative copolymers B1, B2 and B3 used in the present invention

Application test in solvent-borne varnishes

Preparation of solvent-borne clearcoat SC1

For greater clarity, the preparation of solvent-based varnishes is divided into several steps. The method comprises the following steps:

a) preparation of liquid formulations

b) Preparation of liquid formulation for applying, curing and evaluating solvent-borne clear coat SC1

TABLE 4 raw materials for solvent-based varnishes

Raw material	Amount, g
		Setalux 1760 VB 64	33.4
Setalux C 91760 SS 53	26.2
		Setamine US 138 BB 70	21.2
BYK 306	0.05
		BYK 331	0.1
Tinuvin 292	0.5
		Tinuvin 1130	0.75
N-butanol	2.2
		Shellsol A	3.5
Xylene	12.1
		Surface additives according to Table 5	0.1, 0.3 and 0.7% wt of the total formulation

All components according to table 4 were loaded separately and subsequently stirred in a PE beaker for 20 minutes at 1000rpm using a dispermat cv with a 50mm dissolution disc. After the formulations were stored at room temperature overnight, the surface additives according to the invention and the comparative examples according to table 5 were added. Three concentrations of surface additives (0.1% wt, 0.3% wt and 0.7% wt of the total formulation) were evaluated.

Application, curing and evaluation in solvent-borne clearcoats SC1

The modified varnish formulation was adjusted to 27sec DIN 4 cup application viscosity by Shellsol a/xylene (1:1) and applied to the panel by manual application method (coil coated primed metal panel + aqueous basecoat.) thereafter, the panel was dried at ambient temperature for 10 minutes and then cured in an oven at 140 ℃ for 20 minutes the dry film thickness was about 30-40 μm.

TABLE 5 Water contact Angle and leveling Properties in solvent-borne clearcoats SC1

From table 5 it can be concluded that the polymers of the present invention are effective in reducing the coefficient of friction when included in small amounts in coating compositions, in particular compared to the comparative polymers B1, B2 and B3. The coefficient of friction is reduced more effectively than the comparative polymer. A low coefficient of friction means that the coating exhibits improved surface smoothness. This is achieved without negatively affecting the shrinkage cavity.

Furthermore, with the polymers of the invention, the surface energy is at a sufficiently high level and the water contact angle is sufficiently low. Both of these properties indicate good overcoatability. However, when the Mn of the polysiloxane segment in the polymer is outside the range of the present invention, these properties become poor.

Application test in aqueous medium alkyd emulsions

Preparation of liquid formulations

50 g of the aqueous medium oleic acid emulsion (without additives) were placed in a PE beaker and stirred slowly at room temperature using a Dispermat CV fitted with a dissolution dish 30 mm.

The additives were added in the amounts listed in table 6 and stirring was continued at 2000rpm for 2 minutes. After the formulations were stored at room temperature overnight, a first coating of the respective formulation was applied on a byko-chart (also available from BYK-Gardner GmbH) using a 150 μm rod coater (available from BYK-Gardner GmbH, lauster str.8, 82538gerertsried). The remaining liquid coating formulation was sealed and stored overnight at room temperature. The respective byko-charts with the first layer were dried horizontally overnight at room temperature.

The next day a second layer of the same liquid coating formulation (the same as for the first layer) was applied to the first layer using a 150 μm rod coater. After complete horizontal drying of the bilayer systems, the appearance of the respective systems was visually assessed.

Application test results (anti-shrinkage)

The results are shown in the table below.

Table 6:

additive agent	Dosage, weight%
			Is free of		High shrinkage
B1	0.5	Shrinkage of
			A1	0.5	Without shrinkage
A2	0.5	Without shrinkage
			A3	0.5	Without shrinkage
A4	0.5	Without shrinkage
			A5	0.5	Without shrinkage
A6	0.5	Without shrinkage
			B2	0.5	Shrinkage of
B3	0.5	Shrinkage of

The polymers of the present invention improve the performance of the coating system by preventing cratering.