SOLVAY

CAPROLACTONES
A20L-009

CAPA 2200 IN CAST ELASTOMERS USING 4,4 DIPHENYL METHANE DI ISOCYANATE (MDI)
The physical properties of cast elastomers produced from MDI, CAPA 2200 and various chain extenders are given in this leaflet. CAPA based polyurethanes are particularly noted for: i) Lower cost, due to the fact that CAPA based urethanes have a lower density than those derived from polyadipates. Outstanding resilience giving rubbers with low hysteresis properties. Very good low temperature performance. Good hydrolysis resistance. Still better hydrolysis resistance may be obtained by using CAPA 2200A, a specially formulated 2000 molecular weight polycaprolactone, as a direct replacement for CAPA 2200.

ii) iii) iv)

GENERAL DISCUSSION OF PROPERTIES

DENSITY Elastomers based upon CAPA 2200 have a significantly lower density than those produced from other polyester diols, which can be as much as 8% lower. Since elastomers are generally used on a volume basis, the lower densities of those produced from CAPA polyols offer a considerable cost advantage. RESILIENCE Table 1 compares the resilience of a CAPA based MDI system with Adiprene L100 and an adipate based MDI system. It can readily be seen that the CAPA based system gives outstanding resilience resulting in low hysteresis properties. Table 1 Comparative Resilience of 90 Shore A Polyurethane Systems
TEMP C % RESILIENCE MEASURED BY LUPKE PENDULUM CAPA ADIPATE/BD/MDI ADIPRENE 2200/BD/MDI L100 62.5 57.5 48 67.5 63 58.5 70 66 64.5 71 67 65 70 66 60.5 66.5 63
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20 40 60 80 100 120

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CAPROLACTONES HYDROLYSIS RESISTANCE Tables 2 and 3 compare the hydrolysis resistance of 90 Shore A systems based upon various polymers. It can readily be seen that the standard grade CAPA 2200 based urethanes have good hydrolysis resistance compared with urethanes based on, for example, adipate polyesters and that CAPA 2200A is the preferred grade where excellent hydrolysis resistance is needed. (Measured by immersion in aerated water). Table 2 Comparative Hydrolysis Resistance at 100C
POLYURETHANE SYSTEM

TIME REQUIRED TO HALVE TENSILE STRENGTH 4.5 days 6.5 days 2 days

CAPA

2200/BD/MDI 2200A/BD/MDI

TIME REQUIRED TO REDUCE TENSILE STRENGTH TO 2 100 Kg/cm 7 days 11 days 9.5 days

CAPA

Polytetrahydrofuran (MW 2000)/BD/MDI Polyethylene Butylene Adipate/BD/MDI Polyethylene Adipate/ BD/MDI

3 days

5 days

2.7 days

4 days

Table 3 Comparative Hydrolysis Resistance at 80oC

Polyurethane System 5 days 97 97 % Tensile Strength Retention After Time 10 days 93 93 15 days 86 86 20 days 78 76 25 days 69 62 30 days 60 42 35 days 50 11

PTHF/BD/MDI CAPA 2200A/BD/MDI CAPA

2200/BD/MDI

97

93

82

57

Polyethylene/ Butylene Adipate/ BD/MDI

87

54

10

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CAPROLACTONES VISCOSITY CAPA Polycaprolactone diols are also of very low viscosity as shown by comparing them to other polyester diols at 100oC, a temperature commonly used for mixing elastomer components. Table 4 Polyol Viscosities
POLYESTER DIOL (2000 Mol. Wt.) CAPA 2200 Poly (ethylene/butylene) adipate Polyethylene adipate

VISCOSITY (cps) at 100oC 130 300 300

The lower viscosity of CAPA polycaprolactone diols ensure better mixing characteristics, long pot lives and greatly improved pourability. FORMULATION OF ELASTOMERS FROM MDI Choice of Chain Extender In general butane diol is the preferred chain extender for the highest performance polyurethane elastomers. However, elastomers softer than 80 Shore A based on butane diol will cold harden. For softer elastomers, ethane diol or diethylene glycol should be used as chain extenders since elastomers made with these do not cold harden. Choice of Index It is recommended that an index of 1.07 is used for optimum elastomer performance. Method of Calculation A simple general formula is used for calculation of formulations:
x= C [ a.M ( 100- a) ] M-C DI

y = 100 - a -x Where X = % chain extender Y = % polyol C = M.W chain extender M = M.W polyol a = % diisocyanate D = M.W diisocyanate I = isocyanate index

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For CAPA 2200, butane diol and isocyanate index of 1.07, this reduces to:
X = 0.40a - 4.71

The normal batch to batch variations in the molecular weight of CAPA 2200 can be tolerated without changes in formulation.
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CAPROLACTONES Table 5 Formulations using Butane Diol (80 - 96 Shore A)
% CAPA 2200 % MDI % Butane Diol Hardness Shore A Shore D 3 Density g/cm Lupke Resilience % o 25 C o 70 C Modulus 2 25 kg/cm 100% 300 Tensile Strength kg/cm Elongation % 2 Tear Strength (Crescent) kg/cm o Extension Set (70 C) o Compression Set (70 C) o Cold Flex ( C)
2

69.73 25 5.27 80 33 -

62.74 30 7.26 90 42 1.18

58.54 33 8.46 95 46 1.19

48.74 40 11.26 96 57 -

66 77 19 40 113 458 400 55 2 27 -35

62 76 35 65 200 535 420 91 2 21 -39

55 71 80 101 177 538 430 110 7 20 -30

170 355 500 420 160 15 -17

Table 6 Formulations using Ethane Diol (65-90 Shore A)

% CAPA % MDI % Ethane Diol Hardness Shore A Modulus kg/cm 100% 300% Tensile Strength kg/cm Elongation %
2 2

2200

77.78 20 2.22 66 14 38 368 510

72.69 24 3.31 75 29 94 483 510

67.61 28 4.39 83 54 174 527 460

61.25 33 5.75 90 80 211 452 460

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CAPROLACTONES Table 7 Formulation using Diethylene Glycol 75-90 Shore A MDI Elastomers
% CAPA % MDI % Diethylene Glycol Hardness Shore A Modulus kg/cm
2

2200

70.21 24 5.79 74 29 74 319 490

2

65.73 27 7.27 78 31 75 510 550 79

61.18 30.5 8.32 85 49 124 519 520 83

56.12 34 9.98 91 70 203 508 470 98

100% 300%
2

Tensile strength kg/cm Elongation % Tear Strength kg/cm (Crescent)

62
o

Lupke resilience % 25 C o 70 C

57 66

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CAPROLACTONES APPENDIX I METHODS OF CAST MDI ELASTOMER PREPARATION

Summary a) A total prepolymer is prepared by reacting polyol and MDI at 80oC for one hour. The prepolymer at 80oC is mixed with the chain extender at room temperature, degassed and the mixture poured into heated moulds. After curing the moulded elastomers are removed from the mould and post cured for 16 hours at 110oC and 14 days at room temperature.

b)

c)

ELEMENTS OF PROCESS 1. Prepolymer Preparation The total prepolymer that is required can easily be made in small quantities for laboratory or small scale plant evaluation. Quantities of less than one kilo can be made by mixing molten MDI and polyol in a glass bottle and placing this, sealed under nitrogen in an oven at 80oC for one hour with occasional shaking. 5 kg quantities can be made in a glass vessel equipped with a heating mantle, stirrer, thermometer and nitrogen inlet. The isocyanate should be added to the polyol and the mixture maintained at 80oC for an hour, under nitrogen or vacuum. There are no definite upper limits on the scale on which this process can be carried out, other than the need for efficient mixing, close control of the addition of the polyol and the temperature of the process. If the temperature exceeds 80oC significantly, then there is a risk of undesirable branching leading to poor performance in the finished elastomer. The prepolymer once made can be stored for significant periods (up to six months) provided it is kept in sealed containers desirably under dry nitrogen. Water and oxygen must be excluded. Storage should be at ambient temperatures and preferably above freezing. Once the prepolymer has been removed, the reaction vessel can be cleaned out by filling with toluene or acetone, boiling up and discarding the washings.

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CAPROLACTONES 2. Processing The prepolymer, freshly made or reheated to 80oC after storage, is weighed out in the appropriate quantity into either a disposable vessel or a steel vessel that can be cleaned by heating to 5-600oC after use. The prepolymer is then degassed until gas evolution stops. Conveniently, a vacuum pump can be used with an outlet tube carrying a flange and a soft rubber seal to seal on to the vessel containing the prepolymer. If an electric vacuum pump is not available, a water pump suitably protected against suck back with traps has been found to be satisfactory since the vacuum requirements are only 20-25 mm. Some producers of cast elastomers who store prepolymers prefer to degas the materials in bulk and then to maintain it at the appropriate temperature under nitrogen and use it in small quantities without further degassing. If machines are used the tanks of these machines are usually fitted with degassing facilities. After degassing, the chain extender (normally butane 1,4 diol) is added cold to the prepolymer at 80oC and mixed thoroughly but avoiding excessive air entrapment. Many cast elastomer producers prefer to redistill the chain extender or to heat it under vacuum to ensure that it is perfectly dry before use. After casting, the container can either be discarded or reused after allowing the residual contents to cure, or if made of steel (mild steel or preferably stainless) the vessel can be heated in an adequately ventilated oven to a high temperature to burn off the residual elastomer. The mixed gas free system is carefully poured into a mould coated with a suitable mould release agent (see appendix) and preheated to 110oC. The working time available for pouring the system after mixing is typically 3-7 minutes, dependant on the hardness of the ultimate elastomer. This mould is then placed in an oven, or on a hot-plate at 110oC and maintained at this temperature for the requisite time (see below) and the moulded item is then removed. Cure Requirements (uncatalysed)
%MDI Pot Life Demould 20 6 mins 120 mins 30 6 mins 45 mins 40 3 mins 15 mins

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CAPROLACTONES 3. Moulds

For production purposes, aluminum or steel moulds (preferably the latter) are required. For prototype work metal filled epoxy resins, or polyurethane elastomers can be used. It is desirable that the material of construction should be thermally conductive where thick sections are to be moulded, thus avoiding excessively high temperatures in the curing process. Attempts have been made to avoid the use of mould release by coating the surface of the mould with PTFE. However, results are conflicting, probably depending on the porosity of the surface left after coating with the PTFE.

For further information please contact: Solvay Caprolactones Baronet Road Warrington Cheshire WA4 6HB United Kingdom Telephone: Fax: E-mail: Website: +44 (0) 1925 651277 +44 (0) 1925 232207 contact.capa@solvay.com www.solvaycaprolactones.com

The information given in this data sheet is given as a general guide and should not be taken to cover all cases. Each customer should ensure that the product concerned is suitable for the specific purpose and the manner in which it is intended to be used. The information given must not be taken in any way to form a specification. This data-sheet does not form part of the Conditions of Sale of our products and is of a general nature.

FREEDOM FROM PATENT RIGHTS SHOULD NOT BE ASSUMED

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