Essay title - Polyurethane Isocyanate Catalyst

PUR general information

The abbreviation for polyurethane is noted as PU. It is formed by a reaction of an isocyanate with a monomer. The isocyanate must have at least two functional groups and the monomer at least two alcohol groups. The reaction occurs under influence of a catalyst. The catalyst can be a tertiary amine like dimethylcyclohexylamine or organic metallic materials like dibutyltin dilaturate. PUs are very versatile in application and have a wide range in stiffness, hardness and densities. Urethane Isocyanate Hydroxyl alcohol (diol) Different types of isocyanates can be used. The most popular isocyanates for paints are MDI, aliphatics such as H12MDI, HDI, IPDI and TDI. Consumption of aromatic MDI exceeds 45 % of all isocyanates used in paints, closely followed by Aliphatics (35-40%) and TDI (15%). Aliphatic isocyanates react more slowly and result into softer coatings than those made of aromatic isocyanates. They are used when UV or light stability is a must and in many water-based recipes. HDI and adducts are most commonly used, whilst H12MDI is ending up in water-borne systems. Aromatics being cheaper, these isocyanates are used where light stability is not an issue. The polyol is mainly responsible for the properties of the PU and many diols can be used. EG, BDO, DEG, glycerine and TMP. Acrylic and polyester polyols tend to be preferred for harder coats with above average weatherability. The low molecular weight polyols as the main reactants produces polymer chains with fewer urethane groups and more flexible alkyl chains. Long-chain polyols with low functionality give soft, elastomeric PU while short-chain polyols of high functionality give more rigid, cross-linked product. The reaction mechanism of the formation of polyurethane, catalysed with a tertiary amine is given by: Several additives can be used in the formulation of a polyurethane coating. These include a catalyser, surfactants, blow agents, cross-linkers, flame retardants, light stabilizers and fillers. Testing methods for coatings:

Mar and Scuff resistance Taber abrasion Chemical resistance Yellowness index Knig hardness

Costs

Different types of PUs: - Solvent borne:- 1k- Moisture cure - Heat cure - 2k- Heat cure - Air drying - Waterborne:- 1k- Oxidation cure - Heat cure - UV cure - 2k-Air drying - Heat cure Reactive systems (2K) The primary reaction is of isocyanate with polyols.

2K solvent-based system:

Utilised quite frequently in the automotive and aviation finish, where PU has replaced traditional nitrocellulose and acrylic lacquers. PUs can accept high solids loading and have better properties. 2K systems are used also in topcoats for aeroplanes. Aliphatic isocyanates are mixed with polyester polyols or blends of polyester with acrylic grades.

2K water-based system:

Commonly used in transportation, machinery, furniture and protective metal coating applications, whilst their high flexibility also makes them applicable on polymeric and wooden substrates. These 2K paints contain dispersible isocyanates and polyols such as polyacrylates or polyesters that are emulsifiable or soluble in water. The principal isocyanate is an HDI trimer but IPDI trimers are also being used as is allophanate modified HDI. Aromatic grades are avoided because they react too vividly with water. The hydrophobic isocyanate grades can be used as such or can be emulsified by partial reaction with a hydrophilic polyol. Most water-based paint formulations still need up to 10% solvent to make the polymer form a homogeneous film. The coat is cured at temperatures ranging from 20 C to 80 C. To ensure adequate polymer network formation an excess of isocyanate is added so as to compensate for the isocyanate consumed during the urea reaction. Formulations are presently available containing no solvent at all and they are predominantly used in the building sector. Most of these systems are based on MDI and polyether or oil-modified polyester polyols, chain extenders and catalysts. Oven-curing or stoving systems

Stoving curing paints are obtained by blending a blocked isocyanate with a polyol to form a pseudo onecomponent mix that is stable at ambient temperature. When heated to its activation temperature (100-200 C) the isocyanate unblocks and reacts with the polyol thereby forming the coat. Isocyanates may be aromatic or aliphatic all contain one active hydrogen and contain a blocking agent most of the time a caprolactam. Another method of blocking is to form uretidinedione or dimmer links. Their use is restricted to applications withstanding heating/cooling cycles. In practices their main uses is for coating metals.

Solvent-based oven-curing coats:

Typically used for high-speed paint processes. Coatings in this category require high flexibility and are typically applied in a one-machine operation, with TDI commonly used for the base coat whilst the topcoat contains an IPDI trimer.

Water-based oven-curing coats:

Water-borne systems are mainly used for coating of appliance and vehicles as primer of base layer, to provide against corrosion and where needed against stone chips. These recipes have dispersions of blocked aromatic isocyanates, usually modified with hydrophilic components for emulsification and also polyester polyols or modified epoxies.

Powder coatings

One-component or 1K polyurethane paints 1K moisture-cure PUs are widely used for maintenance and repair, capitalising on their easy application and superior mechanical behaviour. They are good candidates for painting steel constructions such as bridges, cranes and primers for sealers for concrete and in synthetic mortar. These coatings are prepolymers, liquid at room temperature and are obtained by reacting MDI, HDI or TDI with polyester or polyester polyols that are linear branched with an isocyanate content below twenty percent. These one-component formulations offer the advantage of no metering nor mixing being required and of being storage stable with a shelf life of up to six months. These 1K systems perform particularly well in anti-corrosion applications. Technology of Non-Reactive Coatings Non-reactive PU systems have in common that they all contain fully formed polymers with urethane or urea linkages, but no free isocyanates.

Solvent-based lacquers:

High molecular weight linear PUs are formed or dissolved in solvents. These PUs are obtained through reacting aromatic or aliphatic isocyanates (mainly MDI and IPDI) with polyesters or polyether polyols and chain

extenders. The film is formed by evaporation the solvent. These films are reportedly extremely flexible and elastic on top of being remarkably resistant to mild solvents.

Polyurethane dispersions:

PUDs are fully reacted polyurethane systems under the form of small discrete particles of maximum one tenth of a micrometer. These particles are dispersed in water to provide a material that is both chemically and colloidally stable.

Urethane oils and alkyds:

Natural oils such as linseed or soybean can be heated with polyols such as glycerol and pentaerythritol. In that case, the reaction converts them to diglycerides and monoglycerides. These hydroxyl-containing oils can then be reacted with isocyanates (TDI or IPDI) and thereby form long chain hydroxyl-terminated polymers that can be dissolved in solvents. They are applied by brush or spray and after solvent evaporation one obtains a film that cross-links by air oxidation of the unsaturated oils with the help of catalysts. Urethane alkyds consist of an alkyd resin in which a portion of the dibasic acid (usually phtalic acid) is replaced by a diisocyanate. Ester links are synthesised during the reaction by polycondensation, and the isocyanate is added for reaction with the remaining hydroxyl groups to form urethane linkages. Urethane alkyds are similar to traditional alklyds and may be drying or non-drying. Above described urethane alkyds should be labelled urethane-modified alkyds as urethane oils are often described as urethane alkyds or urethane oil and even uralkyds. They all exhibit better mechanical and weathering properties than unmodified alkyds, but are not nearly as good as the other reactive PU paints. Main uses are in varnishes for flooring and boats, undercoats and for industrial maintenance finishes.

Radiation curing:

Consists mainly of urethane acrylate coatings that are one-component, low viscosity and hundred percent solid products. They normally are easy to apply and can be rapidly cured by ultraviolet or electron beam energy sources at room temperature. Different drying systems:

Physical No cross-linking Oxidative (1k) Cross-linking 2k cross-linking Polyester modified PU Thermal Typically resistance against stone impact

UV (1k) Cross-linking Moisture cure (1k) Cross-linking

ASTM D16 states that there are 6 different types of PU coatings.

PUD general information

Waterborne polyurethane dispersions (PUDs) are more environment friendly because of a low volatile organic content (VOC). They have several advantages upon solvent borne polyurethanes:

Environment friendly Easy in use Respectable mechanical performance Improved adhesion properties Weather resistant (hydrolysis) Good chemical resistance

There are three types of PUD namely based on 100% PU, a mixture of PUD and acrylic in a 1 component system and a PUD, polyisocyanate mixture as a 2k (two component) system. A coating based on 100% PU are characterised as high performance coatings but are expensive. Combinations with other, mostly cheaper compounds make cheaper coatings but perform less. PUDs in combination with a polyisocyanate however perform better than PUD/Acrylic coatings. PUDs are very easy to formulate and flexibility within a range of 50-700% can be achieved. PUDs can be formulated to cure under influence of UV radiation, cure by oxidation, moisture cure or air drying. UV cured PUD have outstanding adhesion to plastics and oxidation curing to metals. Oxidative curing PUDs are formulated with fatty acids of polyester modified PU (OMU). Moisture-cured PUs contains NCO-terminated PU prepolymer, which on cure with atmospheric moisture produce highly cross-linked networks. The advantages of MCPU coatings are their superior hardness, strength, stiffness and flexibility. 2k PUDs Dry mechanisms of PUDs Air drying Oxidative curing

UV curing Mechanical testing of coatings: For coatings there are three criteria making it suitable. These are abrasion, black heel resistance and flexibility. Coatings based on 100% PUD have outstanding abrasion resistance over coatings on 100% acrylic base. Thus PUD/Acrylic coatings have lower abrasion resistance with an increasing amount of acryl. Taber Abrasion resistance Gloss retention Chemical resistance A PUD has good chemical resistance to solvents and hydrolysis although tensile strength reduces trough hydrolysis. Within the PUD family the UV curing has the best chemical resistance, the 2k system performing intermediate and the 1k system performing the poorest. Production proces PUDs Solvent borne PUs A type of solvent borne PUs are oil modified polyurethanes (OMUs) and are synthesised by an addition reaction of isocyanate with a hydroxyl bearing, fatty acid modified ester (TDI). The drying oil reacts with polyhydric alcohol (glycerol or pentaerythritol) to form a polyol modified vegetable oil or a polyol modified fatty acid. Isocyanate quickly reacts with diol what results in an OMU. More isocyanate results in a higher density but also means that more solvent is needed, as high as 550 g/l. For the oil linseed can be used and for the solvent a mineral spirit can be chosen. The curing occurs by oxidation to form cross-links. Alternatives to OMUs:

2k waterborne polyisocyanate 275 g/l, less gloss, cures slower, less yellow, harder Waterborne PUD/Acrylic dispersions no cross-linking, less gloss, cures slower, less yellow, softer 350 g/l OMUs same gloss, cures slowly, more yellow, softer Water based OMU less gloss, cures quicker, softer

Waterborne PU versus solvent borne PU The main advantage of a PUD is that it needs less cross-linking to achieve the same performance as a solvent borne PU. Studies are highly objective, meaning the effecting party favours their coating above the other coating. This causes very diverse comparisons and quite misleading information. The film formation mechanism of a PUD differs strongly with a solvent based PU. Particle size of a PUD ranges between 0.01-5.0 microns in a watery phase.

A PUD can be formulated without isocyanate and a 30-65% solid content can be achieved. The main disadvantage of a PUD is the costs. Costs can be lowered by mixing the PUD with an Acrylic emulsion. This lowers the costs but also lowers the overall performance of the coating. VOC regulations forces formulators to lower the volatile organic content of their coatings to less than 350 g/l.

Property

Sb 2k

Sb OMU

2k UV

PUD/ Acrylic

Wb OMU

Wb 2k

100% PUD

VOC (g/l)

450520

240

<200

0350

Gloss @ 60

90

96

94

87

88

87

91

Gloss @ 20

102

85

104

72

67

69

77

Gardner dry times, min

Touch

15

15

10

Set

30

10

21

25

Hard

53

20

17

40

45

Through

82

90

57

110

Initial Yellowness Index

16.37

7.43

7.54

7.29

7.63

30 days dark

Yellowness Index

20.69

7.29

12.71

6.72

2.78

0.09

3.35

0.47

K nig, sec

Overnight

49

46

71

59

49

72

7 day

149

90

163

90

79

100

100

Taber abrasion, mg lost

500 cycles

21

56

15

131

34

20

15

1000 cycles

40

125

32

198

66

42

28

Mar & scuff resistance, % gloss retained

82

91

91

63

96

96

70

Stain resistance, total rating (8 stains)

85

63

95

58

61

79

60

UV-cured systems have a high gloss meaning high cross-linking but lack in flexibility. To overcome both disadvantages of the PUD en UV-cured solvent-borne systems, an UV curable polyurethane dispersions (UVPUDs) have been developed. Due to the lower cross-linking density UV-PUDs cannot provide excellent solvent resistance and mechanical properties. These problems can be resolved by incorporating a cross-linking agent.