阅读说明：本技术 具有改进的适用期而没有损失耐候性的双组分聚氨酯涂料 (Two-component polyurethane coatings having improved pot life without loss of weatherability ) 是由 F·戈林 A·黑金 于 2020-04-02 设计创作，主要内容包括：本发明涉及双组分体系,其含有至少一种特定的含N、S、O和Si的化合物。本发明进一步涉及制备含硅聚氨酯的方法,其包括使根据本发明的双组分体系的第一组分与第二组分反应,还涉及由其获得的含硅聚氨酯。此外,本发明涉及根据本发明的双组分体系用于生产漆料、密封剂或胶粘剂的用途。(The invention relates to two-component systems which contain at least one specific N, S, O-and Si-containing compound. The invention further relates to a process for preparing a silicon-containing polyurethane comprising reacting a first component with a second component of the two-component system according to the invention, and to silicon-containing polyurethanes obtained therefrom. The invention further relates to the use of the two-component system according to the invention for producing paints, sealants or adhesives.)

1. Two-component system comprising or consisting of a first component and a second component

A first component comprising or consisting of

A1) At least one compound having at least one zerewitinoff-active group;

B1) optionally at least one catalyst;

C1) optionally at least one solvent; and

D1) optionally at least one additive selected from the group consisting of,

a second component comprising or consisting of

A2) At least one polyisocyanate; and

B2) at least one compound according to formula (I) below:

wherein

R¹To R³Each independently of the others, being identical or different, saturated or unsaturated, straight-chain or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals having up to 18 carbon atoms and optionally containing up to 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, with the proviso that the radicals R¹、R²And R³Is connected to the silicon atom via an oxygen atom,

x are each, independently of one another, identical or different saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals having up to 6 carbon atoms;

y are each, independently of one another, identical or different saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals having up to 18 carbon atoms and optionally containing up to 3 heteroatoms selected from oxygen, sulfur, nitrogen; and is

Z is derived from a polymer having a number average molecular weight M of from 270 to 22000 g/mol_nToBuilding blocks of a less difunctional polyol;

or

Is a polyol and/or an ether or ester alcohol containing 2 to 14 carbon atoms;

C2) optionally at least one solvent;

D2) optionally at least one compound different from the compound according to formula (I) and obtained by reacting at least one isocyanate group with a secondary amine containing silane groups.

2. Two-component system according to claim 1, characterized in that the at least one compound a1 is selected from the group consisting of polyols, polyamines, polyether polyols, polyester polyols, polyurethane polyols, polysiloxane polyols, polycarbonate polyols, polyether polyamines, polybutadiene polyols, polyacrylate polyols and polymethacrylate polyols and copolymers thereof.

3. Two-component system according to claim 1 or 2, characterized in that the at least one catalyst B1 is selected from the group consisting of tin catalysts, bismuth catalysts, zinc catalysts, zirconium catalysts and amine bases.

4. Two-component system according to any of the preceding claims, characterized in that the at least one solvent C1 is chosen from aromatic and aliphatic solvents and mixtures thereof.

5. Two-component system according to any of the preceding claims, characterized in that the at least one additive D1 is selected from the group consisting of uv stabilizers, antioxidants and leveling agents or mixtures thereof.

6. Two-component system according to any of the preceding claims, characterized in that the at least one polyisocyanate A2 is selected from diisocyanates or triisocyanates, such as butane 1, 4-diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 4-isocyanatomethyloctane 1, 8-diisocyanate, 4 '-methylenebis (cyclohexyl isocyanate), decamethylene 1, 10-diisocyanate, 3,5, 5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane, 1, 3-and l, 4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, naphthalene 1, 5-diisocyanate, diphenylmethane diisocyanates, such as 2,2' -, N-diisocyanate, 2,4 '-and 4,4' -MDI or mixtures thereof, diisocyanatomethylbenzenes, such as toluene 2, 4-and 2, 6-diisocyanate and technical-grade mixtures of the two isomers, and 1, 3-and/or 1, 4-bis (isocyanatomethyl) benzene, 3 '-dimethyl-4, 4' -biphenyldiisocyanate, 1, 4-p-phenylene diisocyanate, and cyclohexyl diisocyanate, and higher molecular weight oligomers obtainable from the above either independently or in mixtures and having biuret, uretdione, isocyanurate, iminooxadiazinedione, allophanate, urethane and carbodiimide/uretonimine structural units.

7. Two-component system according to any of the preceding claims, characterized in that D2 is selected from

i) At least one compound of the formula (II)

Wherein

R¹、R²And R³Each independently of the others, being identical or different, saturated or unsaturated, straight-chain or branched, aliphatic or cycloaliphatic or optionally substituted aromatic or araliphatic radicals having up to 18 carbon atoms and optionally containing up to 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, with the proviso that the radicals R¹、R²And R³Is connected to the silicon atom via an oxygen atom,

x is a linear or branched organic radical having up to 6 carbon atoms and

y is a linear or branched, aliphatic or cycloaliphatic radical having from 4 to 18 carbon atoms,

w independently of one another are formyl or acetyl or a COO group having a group G which in this case may be monofunctional, difunctional, trifunctional or tetrafunctional and is a linear or branched, aliphatic or cycloaliphatic radical having from 4 to 18 carbon atoms or a linking unit derived therefrom, or an optionally substituted aromatic or araliphatic radical, and/or

ii) at least one compound of the formula (III)

Wherein

X are each independently selected from alkoxy or alkyl groups, or two groups X together with the silicon atom to which they are bonded form a Si-substituted hydrocarbon ring, each of said alkoxy, alkyl and hydrocarbon ring having up to 10 carbon atoms, with the proviso that the Si atom has at least one alkoxy group,

q is a difunctional linear or branched aliphatic group having up to 10 carbon atoms; and is

Each Z is an alkoxy group having 1 to 10 carbon atoms.

8. Two-component system according to any of the preceding claims, characterized in that B2 preferably has an isocyanate content of less than 2%.

9. Two-component system as claimed in any of the preceding claims, characterized in that the parts by weight of component a1 and B1 of the first component are present in a weight ratio of 0.5 to 8 relative to the parts by weight of component C1 and the parts by weight of D1.

10. Two-component system as claimed in any of the preceding claims, characterized in that the parts by weight of component a2 and B2 of the second component are present in a weight ratio of 0.5 to 10 relative to the parts by weight of component C2 and the parts by weight of D2.

11. Two-component system as claimed in any of the preceding claims, characterized in that the parts by weight of component a1 and optionally B1, C1 and D1 of the first component are present in a weight ratio of 0.6 to 11 relative to the parts by weight of component a2, B2 and optionally C2 and D2 of the second component.

12. A process for preparing a silicon-containing polyurethane comprising reacting a first component with a second component of a two-component system as claimed in any one of claims 1 to 11.

13. A silicon-containing polyurethane obtainable by the process as claimed in claim 12.

14. Use of a two-component system as claimed in any of claims 1 to 11 for producing paints, sealants or adhesives.

Examples

The following examples serve to illustrate the invention, but are not to be construed as imposing limitations upon the scope of protection in any way.

All percentage data are based on weight unless otherwise indicated.

All experiments were performed at 23 ℃ and 50% relative humidity.

The NCO content was determined by titration in accordance with DIN EN ISO 11909: 2007-05.

The solids content was determined in accordance with DIN EN ISO 3251: 2008-06.

All viscosity measurements were carried out with a Physica MCR 51 rheometer from the company Anton Paar Germany GmbH (DE) according to DIN EN ISO 3219/A: 1994-10.

The residual monomer content was measured by gas chromatography using an internal standard according to DIN EN ISO 10283: 2007-11.

The OH number was determined by titration in accordance with DIN 53240-2: 2007-11 and the acid number was determined in accordance with DIN EN ISO 2114: 2002-06. The OH content given is calculated from the OH number determined by analysis. The values given are in each case based on the total weight of the respective composition, including the solvents optionally used together.

The pot life was determined not using a doubling of the flow time conventionally determined according to DIN EN ISO 2431:2011-11 ("Bestimung der Auslaufzeit mit Auslaufberchem"), but using the skinning time of moisture-curing STP. By periodically touching the surface of the film with the tip of a wooden spatula, the point in time at which the peel attached to the tip of the spatula could be lifted from the surface was determined.

The drying times (T1, T3 and T4) were determined in accordance with DIN EN ISO 9117-5:2010-07 (drying test section 5: modified Bannow-Wolff method).

Solvent and water resistance were determined according to DIN EN ISO 4628-1: 2016-07. Solvent resistance tests were conducted using the solvents xylene (hereinafter also abbreviated as "Xy"), methoxypropyl acetate (hereinafter also abbreviated as "MPA"), ethyl acetate (hereinafter also abbreviated as "EA"), and acetone (hereinafter also abbreviated as "Ac"). The contact time was in each case 5 minutes. For the measurement of the water resistance, the contact time was in each case 24 hours. The check is performed according to the criteria listed. Visual evaluation and evaluation of the test surfaces by scoring, the following classifications are used herein: 0 = no change found; 1 = swelling ring, hard surface, only visible change; 2 = swelling ring, slightly softened; 3 = visibly softened (possibly slightly foamed); 4 = significant softening (possibly severe blistering), strikethrough to the substrate; 5 = complete destruction of the coating without external influence.

The trinig pendulum damping was determined on glass plates according to DIN EN ISO 1522: 2007-04. The STP film was applied to a glass plate using a doctor blade. The dry film thickness of all films was 35-40 μm.

All STP films were applied to the glass plates using a doctor blade. The film thickness of all films was 35-40 μm.

List of trade names and abbreviations

Borchi Kat 22 (zinc carboxylate based catalyst, 100%) was obtained from Borchers, Inc.

Setalux DA HS 1170 BA (OH content 3.6%, solids content 70%, viscosity 1200 mPas) and Setalux DA 870 BA (OH content 3.6%, solids content 70%, viscosity 1200 mPas) polyacrylates are from Allnex.

Stabaxol 1 tetraisopropyldiphenylcarbodiimide was obtained from RheinChemie. Methoxypropyl acetate (MPA), Butyl Acetate (BA), Ethyl Acetate (EA), acetone (Ac) and xylene (Xy) were obtained from Azelis.

Hexamethylene Diisocyanate (HDI), Desmodur XP 2565 (IPDI allophanate, 80% solids, 12% NCO content, viscosity 2800 mPa. multidot.s) were obtained from Covestro.

Dibutyl tin Dilaurate (DBTL) is available from rhein chemie under the trade name Addocat 20140P. Mercaptopropyltrimethoxysilane, orthophosphoric acid, tetraethyl orthoformate (TEOF), aminopropyltriethoxysilane, diethyl maleate were obtained from Sigma-Aldrich.

Leveling agents, such as BYK-141 and BYK-311, were obtained from BYK Additives & Instruments.

Light stabilizers such as Tinuvin 292 and Tinuvin 1130 are available from BASF corporation.

Black primer (Basisilack) from Spiess Hecker was used (Permahyd, Base Coat 280).

All reagents and chemicals were used without further purification.

Synthesis of Cross-Linked raw Material

Preparation of example 1

A glass reactor was initially charged with 934 grams of HDI and 1.3 grams of Borchi Kat 22 was added. 364 g of 3-mercaptopropyltrimethoxysilane were then added dropwise. The reaction solution was stirred for so long until an NCO content of 24% by weight was reached. After addition of orthophosphoric acid (20% in i-PrOH), unconverted monomeric HDI was isolated by means of two-stage thin-film distillation at a temperature of 130 ℃ and a pressure of 0.1 mbar.

NCO = 11.2%

Solid content = 100% by weight

Viscosity = 515 mPa · s.

Preparation of example 2

764.91 g of 2-Setalux DA HS 1170 BA and 38.83 g of Stabaxol 1 are added at 80 ℃ under dry nitrogen to 478.03 g of the resulting compound from preparation example 1, 15.02 g of TEOF and 10 drops of DBTL and reacted for so long until a residual NCO content of < 0.3% is reached. 203.21 g of BuAc were added to the crude product. An almost colorless clear silane was obtained.

NCO residual content 0.26%

723 mPas of viscosity (23 ℃ C.)

The solid content is 70 percent.

Preparation of example 3

The HDI polyisocyanate used here was prepared according to example 11 of EP-A330966. The reaction was interrupted at an NCO content of the crude product of 40% by adding dibutyl phosphate. Subsequently, unconverted HDI was removed by means of thin-film distillation at a temperature of 130 ℃ and a pressure of 0.2 mbar. A product having the following properties was obtained:

NCO content 21.8%

Viscosity (23 ℃) of 3000 mPas

Solid content = 100% by weight

0.1 percent of monomeric HDI.

Resin formulation

Example 4 (comparative example)

47.4 grams of Setalux DA 870 BA were mixed with 0.25 grams of BYK-141, 1.48 grams of BYK-311, 0.99 grams of Tinuvin 292, 1.97 grams of Tinuvin 1130, 3 grams of Addocat 201, and 20.33 grams of a butyl acetate/MPA/xylene mixture (1: 1: 1). After addition of 15.91 grams of the mixture of preparative example 3 and 8.72 grams of butyl acetate/xylene (1: 1), the mixture was coated onto a black primer (Spiess Hecker, Permahyd, Base Coat 280) and heated at 60 ℃ for 30 minutes for curing.

Example 5

40.61 grams of Setalux DA 870 BA were mixed with 0.21 grams of BYK-141, 1.27 grams of BYK-311, 0.84 grams of Tinuvin 292, 1.69 grams of Tinuvin 1130, 2.57 grams of Addocat 201, and 21.42 grams of a butyl acetate/MPA/xylene mixture (1: 1: 1). After addition of a mixture of 13.63 g of preparation example 3, 14.29 g of the compound from preparation example 2 and 7.47 g of butyl acetate/xylene (1: 1), the mixture was applied to black paint (Spiess Hecker, Permahyd, Base Coat 280) and heated at 60 ℃ for 30 minutes for curing.

Examples of the use

When STP is added to 2K PU paint formulations, it was surprisingly observed that an extension of the pot life can be achieved. The addition of 10 wt.% of STP's with different structures was sufficient to increase the pot life by 40% -70% (Table 1). The processing time of the 2K PU formulations can thereby be increased. Furthermore, improved scratch resistance is observed at the same gloss retention in weathering (see below).

TABLE 1 pot life extension of 2K PU systems compared with STP-containing 2K PU formulations. Catalyst DBTL (0.1 wt%) was used. The viscosity at RT doubled.

Numbering		Shelf life (h)
			1	2K PU (comparative example 4)	1.5
2	2K PU + 10% STP (example 5)	2.4

The addition of 10% by weight of STP (based on solids content) has a slight effect on the pendulum hardness of the paint films (Table 2). The solvent resistance of the various 2K PU paint films with STP added is comparable to that of the comparative system (number 1). The gloss values (60 ℃ C.) provide values comparable to the comparative system. It was observed that the scratch resistance of the coating system could be improved by adding STP.

Table 2:

xy = xylene, MPA = methoxypropyl acetate, EA = ethyl acetate, Ac = acetone.

The addition of STP for extending the pot life of the 2K PU formulations did not affect the weathering resistance, since the STP-containing varnishes did not show any change over a period of 1000 h in the CAM 180 test. Gloss measurements at different angles before and after the weathering period confirm this finding.

TABLE 3 weathering study after 1000 h (CAM 180)

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