Abstract:
A polysulphide resin composition is cured by reacting a liquid polysulphide resin with an isocyanate curing agent in the presence of an organometallic or metal salt catalyst, preferably an organotin catalyst such as dibutyltin laurate (DBTL). The compositions have utility in thin films and coatings, and in the bonding, sealing and coating of polycarbonates. Aliphatic isocyanates are preferred for applications where clear coatings are required, the more reactive aromatic isocyanates being preferred for other applications.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to the curing of liquid polysulphide polymers and in particular to the use of isocyanate curing agents to prepare thin films, coatings, adhesives and mouldings of polysulphide polymers and compounds. 
     2. Description of the Prior Art 
     Compositions based on liquid polysulphides have a wide range of applications as sealants, strips, sheets, films, spray-on coatings and the like. Many such formulations include carbon black as a filler and reinforcing agent. 
     Liquid polysulphide resins are usually cured with an oxidising agent such as manganese dioxide, the cure mechanism being as follows: ##STR1## 
     Other mechanisms for polysulphides have been tried. For example, polymers have been made by reacting polysulphides with isocyanates using an amine catalyst. However, water isocyanate reactions were prevalent in these systems, the carbon dioxide produced resulted in a blown product. ##STR2## Subsequently, A Can react with 
     i) further isocyanate 
     ii) the reactive end of active polymer (B) 
     B Can react with 
     i) further polysulphide mercaptans 
     ii) the unreactive end of reactive polymer (A) 
     iii) moisture in the system 
     In amine catalysed systems the isocyanate reacts with water in the atmosphere in preference to the mercaptan groups. ##STR3## The amino group formed autocatalyses the reaction and an exotherm occurs. With this catalysis the reaction between isocyanate and mercaptan is preferred. 
     Nevertheless, problems still arise in the preparation of thin films and coatings. In particular the curing reaction can proceed too rapidly and exothermically and is not easily controlled. There is still a potential problem of blowing resulting from reactions between isocyanate groups and water in the system or in the air. 
     SUMMARY OF THE INVENTION 
     It is accordingly an object of that invention to produce cured polysulphides with a usefully improved range of properties, particularly in the form of thin films or coatings. 
     It is a further object of the invention to provide a method of curing liquid polysulphides which has a reduced exotherm and can be easily controlled. 
     These objects are achieved in accordance with the invention by curing a liquid polysulphide with an isocyanate curing agent in the presence of an ozganometallic or metal salt catalyst. The preferred catalyst is an organotin catalyst such as dibutyl tin dilaurate (DBTL). 
     The polysulphide compounds of the present invention are found to have greatly enhanced abrasion resistance, greater tensile strength and elastic modulus and improved adhesion to many different types of surface. 
     The preferred liquid polysulphide (LP) polymers for use in the compositions of the present invention are those of relatively high average molecular weight such as 2500 to 8000 and low degree of branching. A wide range of liquid polysulphide polymers is produced by Morton International Inc., these being formed by the condensation in aqueous suspension of sodium polysulphide with bis-(2-chloroethyl) formal. The average structure of the liquid polymer is: 
     
         HS--(C.sub.2 H.sub.4 --O--CH.sub.2 --O--C.sub.2 H.sub.4 --S--S--).sub.n --C.sub.2 H.sub.4 --O--CH.sub.2 H.sub.4 --SH 
    
     The value of the repeat unit n, which is generally in a range of 5 to 50, governs the viscosity of the LP polymer. A summary of the properties of the Morton International Inc., range of LP polymers is given in the following table: 
     
                       TABLE 1______________________________________   Av-   erage   Repeat  % Tri-  Average Average   Mole-   Unit    functional                           Mercaptan                                   Viscosity   cular   `n`     Monomer Content at 25° C.Polymer Mass    Value   (mole %)                           (moles/Kg)                                   (Pa.s)______________________________________LP-1400C   1000     6      0       2.06    1.15LP-33   1000     6      0.5     1.75    1.75LP-3    1000     6      2       2.06    1.15LP-980C 2600    15      0.5     0.91    12.5LP-977C 2600    15      2       0.91    12.5LP-541C 4000    23      0       0.53    46.5LP-12C  4000    23      0.2     0.53    46.5LP-32C  4000    23      0.5     0.53    46.5LP-2C   4000    23      2       0.60    46.5LP-31   8000    42      0.5     0.38    62.5______________________________________ 
    
     Of these, the preferred polymer is LP32, which has an average molecular weight of 4000 and a low degree of branching. LP polymers with a high concentration of trifunctional monomer may have a tendency to cyclise, i.e., isocyanate groups tend to react with branched mercaptan groups on the same chain, giving a ring structure and preventing further chain extension. The trifunctional monomer content preferably does not exceed 1 mole %. 
     The isocyanates used may be aliphatic or aromatic. Aliphatic isocyanates which may be used include hexamethylene diisocyanate (HDI). Among the most widely available aromatic isocyanates are diphenyl methylene, 4,4&#39;, diisocyanate (MDI) and toluene diisocyanate. : ##STR4## 
     Aromatic isocyanates are preferred owing to their greater reactivity. As in the case of the LP polymer a linear compound with a low degree of trifunctionality is preferred. One particularly suitable MDI formulation meeting this criterion is available from Imperial Chemical Industries Plc under the trade mark Suprasec ® VM021. 
     The preferred catalysts for the mercaptan/isocyanate reaction are organotin catalysts which favour this reaction rather than that between isocyanate groups and water in the system. The preferred catalyst is dibutyl tin dilaurate (DBTL). 
     Metal salts which can be used as catalysts in accordance with the invention are usually salts of organic acids such as C 2  to C 8  carboxylic acids, typically those of tin and those of Group Ia, IIa and IIb metals such as sodium, potassium, calcium and zinc. Those of lead and mercury could also be used, but are regarded as less desirable for reasons of toxicity. Typical examples of metal salt catalysts which can be used include stannous octoate, potassium acetate and calcium and zinc naphthenates. 
     The compositions of the invention have also been found to be of particular utility in conjunction with polycarbonates, and in particular for coating polycarbonate members such as sheets, bonding such members together or sealing around them. 
     Polycarbonate sheet is increasingly being used in building applications, in particular for covering or even replacing glass windows. There are relatively few compositions having suitable properties for use as sealants, adhesives and coating compositions for polycarbonate sheet, and there is therefore a need for improved compositions for these purposes having the following properties: 
     i) high shear strength 
     ii) high resilience to withstand impact 
     iii) ease of application 
     iv) transparency or translucence 
     v) non stress-crazing of polycarbonate 
     vi) durability to the environment 
     Polysulphide resins have not hitherto been considered suitable for use in such applications since, although thin films of polysulphides are intrinsically transparent, the conventional curing of liquid polysulphides with inorganic catalysts such as manganese dioxide renders them opaque, with insufficient bond strength. 
     We have now found that the isocyanate-cured polysulphides of the present invention are particularly suitable for bonding, coating and sealing polycarbonates since they impart good physical properties and form bonding layers which are transparent, or at least translucent, without apparent stress crazing of polycarbonate sheet. 
     LP32-C is particularly suitable for use with polycarbonates. For faster curing, such as in spraycoating applications, a higher molecular weight polysulphide such as LP-31 can be used. 
     Aliphatic isocyanates are preferable for polycarbonate applications where adhesives, coatings and sealants are subjected to direct ultra violet light and colour fast properties are required. Where black adhesives, coatings and sealants are specified, where colour-fast properties are non critical of where the product is not subject to direct ultra violet light, an aromatic isocyanate is preferred. 
     A silane coupling agent may be added to the composition to assist bonding to the polycarbonate. 
     The composition may be formulated as a one- or two-part composition, depending on the intended application. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     The following examples further illustrate preferred features and applications of the invention. Reference will also be made to the accompanying drawings which illustrate preferred embodiments and features of the invention. 
     In the drawings: 
     FIG. 1 is a bar chart illustrating the results of volume swell tests described in Example 3; 
     FIG. 2 is a bar chart illustrating the results of adhesion tests described in Example 3, in terms of stress at break; 
     FIG. 3 is a bar chart illustrating the adhesion test results of Example 3 in terms of cohesive failure; 
     FIG. 4 is a bar chart illustrating the results of further adhesion tests, in terms of stress at break, comparing primed and unprimed substrates; 
     FIG. 5 is a bar chart illustrating the further adhesion tests of FIG. 4, in terms of cohesive failure; 
     FIG. 6 illustrates the cure profiles of liquid polysulphide compositions using different cure accelerators; 
     FIGS. 7a to 7d respectively illustrate the effect of aging on the viscosities of four compositions in accordance with the invention; 
     FIG. 8 illustrates the effect of aging on a further composition in accordance with the invention; 
     FIG. 9 is a graph comparing the volume swell upon long-term water immersion for isocyanate-cured and conventional LP compositions; 
     FIG. 10 shows a lap shear bond illustrating the bonding of polycarbonate sheets; and 
     FIG. 11 shows a lap shear bond illustrating the use of a composition of the invention as a sealant for polycarbonate sheet. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     In the examples, the properties of the test samples were evaluated as follows, unless otherwise indicated: Work life and cure time were calculated using the time to 10% and 90% of cure respectively, as measured by a Monsanto ODR rheometer at 35° C. Tensile strength was measured using 20 mm dumb-bells, pulled at 500 mm per minute at 23° C. Tear strength was measured in accordance with BS (British Standard) 903 part A3 method B. Elongation at break was estimated by measuring elongation between set points 1 cm apart on tensile dumb-bell test pieces. Abrasion was measured using Taber Abrader H18 wheels with 1 kg top mass, recording the weight loss after 1000 cycles. Hardness was measured using a Shore A gauge. Viscosity was measured with a Haake viscometer at 20° C. P II, 16 r.p.m. 
     EXAMPLE 1 
     Tests were carried out to establish the most favorable isocyanate index for the composition. This is a measure of the molar ratio of NCO groups to SH groups in the system. A system containing the exact stoichiometric amount of NCO required to react with the available mercaptan groups is defined as having an isocyanate index of 100. 
     The LP polymer used was LP-32C, having a mercaptan content of 0.53 mole/kg. This corresponds to an SH content of 17.49g in 1000g of LP, or 1.749 wt.%. 
     The isocyanate used was Suprasec %021, having an average --NCO content of 23.0 wt.%. A system having an isocyanate index of 100 would therefore have an NCO:SH weight ratio of 13.15:1, or 7.605 g of VM021 per 100 g of LP-32C. 
     Four test samples were produced with different proportions of isocyanate, and their cured properties measured. The samples were cured at room temperature in open moulds, using undried materials. The catalyst was dibutyl tin dilaurate. The proportions used and the results obtained are set out in Table 2. 
     
                       TABLE 2______________________________________TEST 1        TEST 2    TEST 3     TEST 4______________________________________LP-32C  100       100       100      100Suprasec   15        7         10       8VM021DBTL    0.5       0.7       1.0      2.0INDEX   200       92        130      105CURED   FOAMED,   DID NOT   GOOD     GOODAPPEAR- FLEX-     CURE RE-  FILM A   FILM. NOANCE    IBLE      SIDUAL    SMALL    BLOW-             LP        AMOUNT   ING.             ODOUR     OF       SLIGHT-                       BLOWING. LY SOFT.                                RE-                                SIDUAL                                LP                                ODOURWORK    OVER 2    --        20 mins  15 minsLIFE    HOURS(100 g)CURE    OVER-     --        21/2 hours                                21/2 hoursTIME    NIGHTCOLOUR  AMBER→             →  → →BROWN______________________________________ 
    
     The results suggest a preferred isocyanate index of between 100 and 135 for an unfilled film, more preferably between 110 and 125 and most preferably about 118. This is somewhat higher than is commonly used in polyurethane formulations, but this may be accounted for by moisture in the system. 
     EXAMPLE 2 
     Two test formulations were prepared using as the LP polymer vehicle a 100% solids Morton International LP-R base formulation containing a silane coupling agent and a medium thermal carbon black filler. The silane A187 used is available from Union Carbide Corp. The composition of the LP-R base was as follows: 
     
         ______________________________________LP-32C              100 wt. partsMT Black             25 wt. partsSilane A 187         2.5 wt. parts______________________________________ 
    
     The proportions used and the results obtained are shown in Table 3. 
     
                       TABLE 3______________________________________      TEST 5     TEST 6______________________________________LP-R base    127.5        127.5Suprasec VM021        9            12DBTL         1.0          1.0INDEX        118          158*POT LIFE (hrs)        2            13/4on 100 gCURE TIME (hrs)        21/2         21/2for 2 mm thick sheetPROPERTIES   GOOD         GOOD        ELASTOMER    ELASTOMER                     SLIGHT BLOWING______________________________________ *Higher isocyanate because moisture in LPR ingredients. 
    
     EXAMPLE 3 
     Standard tests were carried out on an isocyanate cured LP-R polymer system in accordance with the invention and a conventional manganese dioxide cured system, to compare their mechanical properties. The composition of the isocyanate cured system was that of Test 5 in Example 2. A catalyst level of 1.0 phr DBTL was found to give equivalent properties to a standard manganese dioxide cure paste. An isocyanate index of 118 corresponds to an LP:NCO ratio of 100:9. 
     The test formulations and the results obtained are set out in Table 4. 
     
                       TABLE 4______________________________________      Isocyanate       STD      system (1)       LP-R systems______________________________________Part ALP-32C         100              100MT Black       25               25Silane AP187   0.5              0.5DBTL           1.0              --Part BSuprasec VM201 9                --Manganese dioxide          --               10Plasticiser HB40          --               10TMTD           --               0.5% polysulphide 75               69polymer contentElongation at break          283%             473%Tensile Strength          2.95    MPa      2.04  MPaModulus at 200%          1.5     MPa      0.66  MPaTear Strength  7.8     KNm      7.6   KNmAbrasion Resistance          0       gs       0.187 gsH18 Wheel1000 g Top mass/100 cyclesAbrasion CS10  0.033   gs       0.645 gs1000 g Top mass/1000 cyclesCompression set          52.8%            96.5%25% compression,72 hrs @ 70° C.(ES 903 Pt. A6)______________________________________ 
    
     It can be seen from the table that the formulation of the invention has improved mechanical properties in several respects, notably in tensile strength and abrasion resistance. 
     The following further tests were carried out to compare the formulations of Example 3. 
     Volume swell tests were carried out on both formulations in a variety of solvents. The tests were carried out for one month at 25° C. in accordance with British Standard 903 Part A16. The results are shown in FIG. 1 of the accompanying drawings. These results show that isocyanate cure of liquid polysulphide give widely different values compared to conventional manganese cured systems. 
     WATER--The swell in the manganese cured systems is commonly believed to be due to the solubility of manganese salts. The results obtained would appear to support this theory as very little swell in distilled water was apparent in the isocyanate cured system. 
     TOLUENE--Volume swell of standard LP-R products appear to be quite large in dry toluene, but using an isocyanate cure system the amount of swell can be reduced by approximately 50%. 
     METHYLETHYL KETONE (MEK)--Polyurethanes generally swell badly in MEK and similarly with the LP-R/isocyanate system. It may be because of the urea linkages and the methane groups that this product swells more than the equivalent manganese dioxide cured system. It might be possible to reduce this swell by using an aliphatic isocyanate in place of the aromatic (MDI) used. 
     ASTM FUEL B--Slightly worse results were experienced for the isocyanate cured LP-R, probably for the same reasons given for MEK. 
     ASTM OIL 3--Resistance to oil appears to be similar for isocyanate and manganese dioxide cured systems. 
     
         ______________________________________PEEL ADHESION TEST ON CONCRETE (BS4254)PEEL TEST (Pull at 50 mm/min)      MANGANESE ISOCYANATE      DIOXIDE   CURE______________________________________Average      80N         65NPeel StrengthMode of      Thin        ThinFailure      film adhesive                    film adhesive______________________________________ 
    
     The manganese dioxide cured material appeared to adhere better to aggregate in the concrete whilst the isocyanate cured system appears to adhere better to the mortar. Both surfaces were unprimed, but were cleaned free of dust. 
     Adhesion to different substrates 
     The adhesion of the manganese dioxide cured LP-R and isocyanate-cured LP-R to various substrates was studied. FIG. 2 shows the results for mortar in various states of preparation in terms of stress at break (BS4254). The results in terms of percentage cohesive failure are shown in FIG. 3. It can be seen that the results are in most cases comparable for the two cure systems. The isocyanate cured system was somewhat inferior in the case of unprimed mortar at 70° C., but there was some improvement for primed, water-immersed mortar. The adverse result at 70° C. for the isocyanate system may be due to an increase in the modulus with heat aging. This is supported by a cohesive failure rate of 100%. 
     The poorer performance for the manganese dioxide cured system in the case of a primed mortar immersed in water may be due to the swell in water observed with manganese-cured systems, leading to a reduction in strength. 
     The concrete primer used was baser on an isocyanate system, which might be expected to enhance compatibility with the isocyanate cured system. 
     FIGS. 4 and 5 of the drawings slow, in terms of total load and percentage cohesive failure respectively, comparisons of the adhesion of the standard and isocyanate cured systems to primed and unprimed glass and aluminium. It can be seen that in all cases the isocyanate cured system gave some improvement in total load. The cohesive failure rate was either the same or much reduced. 
     EXAMPLE 4 
     Higher strength LP compositions ccmprising 50 parts by weight of Printex 25 carbon black per 100 parts by weight of LP were made. One sample was cured with Suprasec VM021 isocyanate (isocyanate index 118) and one with manganese dioxide. The composition of the invention was found to have higher tensile strength, as can be seen from Table 5: 
     
                       TABLE 5______________________________________     Isocyanate system (2)                  Std LP-R system (2)______________________________________LP-R 32C    100                100Printex 25  50                 50Silane      0.5                0.5Suprasec VM021       9                  --TMTD        --                 0.5Plasticiser --                 10Manganese dioxide       --                 10Tensile Strength       5.4      MPa       4.8    MPa______________________________________ 
    
     EXAMPLE 5 
     The curing of three formulations of isocyanate cured LP-R, having different contents of DBTL catalyst, was monitored and compared with that of the conventional manganese dioxide cured LP-R. The two formulations in accordance with Example 3 were compared with two additional isocyanate cured polymers having DBTL contents of 0.2 and 0.5 phr respectively. 
     The results are shown in FIG. 6 of the drawings. For the purpose of this experiment, it is assumed that the composition being cured ceases to be workable when its viscosity reaches 2500 Pas. The time taken for this viscosity to be reached is known as the work life. 
     It can be seen from FIG. 6 that the work life can bs varied considerably by varying the amount of DBTL used. A DBTL content less than 0.2 phr does not give a satisfactory cure since the isocyanate tends to react with moisture in the system, leaving too few --NCO groups to react with mercaptan groups. This minimum content of DBTL gives a work life of just over 1 hour 30 minutes. The work life can also be lengthened by using lower molecular weight polymers or by using a less reactive isocyanate. 
     Increasing the content of DBTL will increase the cure rate, but levels higher than 1.0 phr have been found not to give a commensurate increase in the rate. 
     EXAMPLE 6 
     Samples of the standard and isocyanate cured systems of Table 4 (Example 3) were subjected to dynamic mechanical thermal analysis (DMTA), their modulus being monitored over a temperature range from -70 to +170° C. at frequencies of 1 and 10 HZ. 
     A first isocyanate cured sample was tested 3 days after initial curing. The result suggested a glass transition temperature Tg of -28° C. at 10 Hz, but further activity was noted as the product passed through the range from 30 to 80° C., where an increase in modulus was noted. This suggested some post-curing. 
     A further sample tested approximately 5 weeks after initial curing also showed a Tg of -28° C. at 10 Hz, but thereafter showed a constant in-phase dynamic modulus (E&#39;) if about 6.5 PA from 10 to 130° C., suggesting that curing was complete. 
     The sample cured with manganese dioxide was also tested approximately 5 weeks after initial curing and showed a Tg of -32° C. at 10 Hz, and a substantially constant dynamic modulus of about 6.5 PA over a range from 10° to 130° C., again suggesting complete curing. 
     EXAMPLE 7 
     The following formulation was made up to test its adhesion to glass: 
     
         ______________________________________            pbw______________________________________Part APolysulphide LP-32C              100Catalyst DBTL      1Part BIsocyanate (MDI) VM021              8______________________________________ 
    
     A relatively low level of isocyanate was used to reduce blowing. The LP/catalyst mixture was found to be stable for 3 months or more. This was thoroughly mixed with the MDI and the mixture applied onto clear glass with a spatula as a thin film. A second piece of glass was then applied as quickly as possible, being pressed from the center outwards to avoid entrapment of air. 
     Lap shear adhesion tests were carried out using pinch overlap specimens on unprimed glass. Also tested were a sample of thermoplastic polyurethane (TPU) and a further sample of the isocyanate cured polymer to which 0.5 pbw of a silane coupling agent was added. The results for the lap shear adhesion were as follows: 
     
         ______________________________________                       Isocyanate curedTPU          Isocyanate cured LP                       LP + Silane______________________________________Average  0.461 MPa 0.475 MPa      0.64 MPa                           glass broke______________________________________ 
    
     Samples of thermoplastic polyurethane, isocyanate cured LP and isocyanate cured LP plus silane were applied to glass plates and subsequently subjected to a ultra-violet light (Q.J.V.) test for 168 hours at 70° C., with an intermittent water cycle. 
     After this period the plates were examined visually and no sign of deterioration to the clear films was noted. 
     The plates were submitted to a further 1000 hours at 70° C. (with water cycle) and after this period all products had developed a brown tint. 
     The isocyanate cured polymer showed no thermoplanticity (ie would not flow between the pieces of glass) at 160° C. The TPU sample displayed melt flow at this temperature. 
     Although the inclusion of a silane coupling agent improved the adhesion it had the disadvantage of making the system cloudy. 
     EXAMPLE 8 
     To test the use of another aromatic isocyanate in the composition of the invention, a formulation was produced using toluene diisocyanate (TDI), Desmodur L67. 
     Desmodur L67 has 11.6 wt% of isocyanate groups in the dry polymer, so 7.77% in the solvented system. LP-32C has 1.75 wt% of SH groups, so 1.75 wt parts Desmodur L67 would be the stoichiometric amount required to cure 7.77 wt parts LP-32C, 22.5 wt parts Desmodur L67 to 100 wt parts LP-32C would give an isocyanate index of 100, so 26.55 wt parts are required to give an isocyanate index of 118. 
     The formulation was as follows: 
     
         ______________________________________LP-32C               100 wt partsDBTL                  2 wt partsDesmodur L67        26.5 wt parts______________________________________ 
    
     After curing overnight and for a further 3 hours, a non-aerated product was obtained with little smell of polysulphide. Some residual solvent from the Desmodur L67 was present in the cured film, but this would not adversely affect its physical properties. 
     A rheometer trace for this composition at 35° C. for 90 minutes showed slight increase in modulus but not a full cure. At 110° C. the trace showed a sharp increase in modulus, reaching a maximum after about 4.5 minutes. 
     For comparison, a trace for the MDI isocyanate cured composition showed a substantially full cure after 90 minutes at 35° C. 
     EXAMPLE 9 
     To test a liquid polysulphide of lower molecular weight, a composition was made up using Morton International&#39;s Lp-3 (see Fable 1). 
     LP-3 has a mercaptan content of 2.06 mole/kg, or 6.8 wt%. Using Suprasec VM021 isocyanate with an average NCO content of 23%, 34 wt part of VM021 to 100 wt parts LP-3 give the required isocyanate index of 118. 
     
         ______________________________________The composition was as follows:          Phr______________________________________Polysulphide LP-3            100DBTL             1.5VM021            34______________________________________ 
    
     A rheometer trace shows an increase in modulus to a maximum after about 70 minuets, although some mercaptan smell was noticed. The film had a tear strength superior to that of a manganese dioxidu-cured LP-3 film. These results indicated that little &#34;back-biting&#34; was occuring. 
     The isocyanate cured compositions of the present invention have been found to have properties which are in several respects superior to those of the standard manganese-dioxide cured LP&#39;s. A full comparison of the manganese dioxide and isocyanate cured LP-R&#39;s of Example 3 are shown in the following summary (Table 6). 
     
                       TABLE 6______________________________________        manganese        dioxide    isocyanate cured        cured system                   system______________________________________Elongations at break          473%             283%Tensile strength          2.04     MPa     2.95   MPaModulus @ 200% 0.66     MPa     1.5    MPaTear Strength  7.6      KNm     7.8    KNmAbrasion Resistance          0.187    gs      0      gsH18 Wheel 1000 gmsCS10 100 gms   0.645    gs      0.033  gsHardness Shore A          45               61Concrete Peel Strength          80N              65N(no primer)Tg, DMTA 10 Hz -30°                   C.      -24°                                  C.Work life range          3 hrs    30 min  3 hrs  30 minVolume Swell 1 month25° C.WATER          7.5%             0.5%TOLUENE        30%              15%MEK            7.5%             28%ASTM FUEL B    1%               3%ASTM OIL 3     1%               1%Tensile Adhesion (BS4254)GLASS UNPRIMED 290N             310NGLASS PRIMED   320N             410NALUMINIUM      190N             200NUNPRIMEDALUMINIUM PRIMED          240N             260NMORTAR UNPRIMED          500N+            500N+MORTAR UNPRIMED          500N+            300N70° C.MORTAR PRIMED  500N+            500N+MORTAR UNPRIMED          260N             250NWATERMORTAR PRIMED  410N             500N+WATER______________________________________ 
    
     EXAMPLE 10 
     To study the effect of variations in isocyanate functionality, LP functionality and LP molecular weight, a series of compositions was made up using different liquid polysulphides, and different isocyanates, as well as a series of reference compositions cured with manganese dioxide. 
     1. LP molecular weight was varied by using LP32C, LP980C and LP33C (which are 4000, 2600 and 1000 molecular weight respectively), and contain 0.5% Trifunctional monomer. 
     2. LP functionality was varied by using LP541C, LP32C and LP2C (which contain 0, 0.5 and 2.0 percent trifunctional monomer respectively) and are 4000 molecular weight. 
     3. Isocyanate functionality was varied by using Suprasec VM021, DND and VM90 (which have functionalities of 2.0, 2.7 and 2.9 respectively). 
     The polymers were formulated into LP-R products by compounding in 25pphr of Sevarcarb MT carbon black. 
     Curatives and accelerators were arded in the proportions as outlined in Table 7, wherein the compositions are designated from 1/A to 5/D, according to the LP and curative used. The properties of the LP&#39;s are set out in more detail in Table 1 above. 
     
                                           TABLE 7__________________________________________________________________________    1/A       1/B          1/C             1/D                2/A                   2/B                      2/C                         2/D                            3/A                               3/B__________________________________________________________________________BASE1 LP541C 100       100          100             100                -- -- -- -- -- --2 LP32C  -- -- -- -- 100                   100                      100                         100                            -- --3 LP2C   -- -- -- -- -- -- -- -- 100                               1004 LP980C -- -- -- -- -- -- -- -- -- --5 LP33C  -- -- -- -- -- -- -- -- -- --MT Carbon Black    25 25 25 25 25 25 25 25 25 25DBTL     1  1  1  -- 1  1  1  -- 1  1CURATIVEA VM90   8  -- -- -- 8  -- -- -- 9  --B VM 021 -- 10 -- -- -- 10 -- -- -- 11.2C DND    -- -- 8  -- -- -- 8  -- -- --D MnO.sub.2    -- -- -- 10 -- -- -- 10 -- --HB 40    -- -- -- 10 -- -- -- 10 -- --TMTD     -- -- -- 0.5                -- -- -- 0.5                            -- --__________________________________________________________________________    3/C       3/D          4/A             4/B                4/C                   4/D                      5/A                         5/B                            5/C                               5/D__________________________________________________________________________BASE1 LP541C -- -- -- -- -- -- -- -- -- --2 LP32C  -- -- -- -- -- -- -- -- -- --3 LP2C   100       100          -- -- -- -- -- -- -- --4 LP980C -- -- 100             100                100                   100                      -- -- -- --5 LP33C  -- -- -- -- -- -- 100                         100                            100                               100MT Carbon Black    25 25 25 25 25 25 25 25 25 25DBTL     1  -- 1  1  1  -- 1  1  1  --CURATIVEA VM90   -- -- 12 -- -- -- 24 -- -- --B VM 021 -- -- -- 16 -- -- -- 32 -- --C DND    9  -- -- -- 12 -- -- -- 24 --D MnO.sub.2    -- 10 -- -- -- 10 -- -- -- 10HB 40    -- 10 -- -- -- 10 -- -- -- 10TMTD     -- 0.5          -- -- -- 0.5                      -- --    0.5__________________________________________________________________________ 
    
     
                                           TABLE 8__________________________________________________________________________The cure profiles and physical properties of the cured compositions wereevaluated,and the results are shown in Table 8 below.__________________________________________________________________________PROPERTY        1/A 1/B 1/C 1/D 2/A 2/B 2/C 2/D 3/A 3/B__________________________________________________________________________WORK LIFE Minutes           29  25  25  70  25  25  25  30  25  25CURE TIME Minutes           100 85  100 120 95  85  100 75  60  60TENSILE STRENGTH MPa           1.3 2.9 1.8 1.6 1.6 2.0 1.7 1.6 1.2 2.4TEAR STRENGTH KN/m           2.4 8.2 3.3 8.9 2.7 6.2 3.6 7.3 3.2 7.9ELONGATION %    50  150 100 400 50  150 50  300 30  100ABRASION WEIGHT LOSS           0.8 0.8 1.0 5.0 2.0 0.8 1.0 3.6 1.2 0.6VOLUME SWELL WATER %           0.4 0.6 0.6 18  1.0 1.8 1.2 17  0.3 0.8VOLUME SWELL    62  70  59  130 61  78  57  123 54  55TOLUENE %HARDNESS SHORE A           53  40  52  15  50  50  54  21  59  53VISCOSITY PaS   100 100 100 110 105 105 105 95  105 105__________________________________________________________________________PROPERTY        3/C 3/D 4/A 4/B 4/C 4/D 5/A 5/B 5/C 5/D__________________________________________________________________________WORK LIFE Minutes           22  25  58  48  55  10  100 60  100 10CURE TIME Minutes           70  60  180 152 170 60  190 180 210 25TENSILE STRENGTH MPa           1.4 1.4 1.3 2.2 1.5 1.6 1.1 1.4 1.4 1.2TEAR STRENGTH KN/m           2.5 5.8 2.4 8.2 2.6 7.9 2.1 9.5 3.1 7.9ELONGATION %    50  200 25  100 50  500 50  400 100 500ABRASION WEIGHT LOSS           1.1 2.7 1.4 0.5 1.4 2.9 0.8 0.3 0.8 3.4VOLUME SWELL WATER %           0.5 19  0.2 0.7 0.4 18  0.1 0.5 0.2 29VOLUME SWELL    61  80  51  56  52  121 58  44  39  157TOLUENE %HARDNESS SHORE A           54  30  61  49  59  26  47  41  47  20VISCOSITY PaS   105 100 33  33  33  32  4   4   4   4.5__________________________________________________________________________ 
    
     EXAMPLE 11 
     To evaluate the effect of variations in the content of curative, isocyanate-cured compositions A to C were made up using different amounts of curative, and their cure profiles and physical properties were compared to those of M n  O 2  -cured reference compositions D to F, in which the amount of curative was also varied. The formulations and results are shown in Table 9. 
     
                       TABLE 9______________________________________  A     B       C       D     E     F______________________________________BaseLP32C    100     100     100   100   100   100MT Black 50      50      50    50    50    50DBTL     1       1       1     --    --    --CurativeIsocyanate    10      8       12    --    1     --M.sub.n O.sub.2    --      --      --    10    8     12HB40     --      --      --    10    8     12TMTD     --      --      --    1     0.8   1.2Work life    24      35      20    12    22    8(minutes)Cure time    120     150     99    37    60    20(minutes)Tear     14      7       12    9     10    11StrengthNmm.sup.-1Tensile  3.6     0.7     3.4   2.4   2.9   2.5StrengthMPaElongation    300     600     200   400   200   300at Break %Abrasion 0.8     1.2     0.9   1.9   1.9   2.0MgWeightLoss______________________________________ 
    
     EXAMPLE 12 
     To study the effect of heat aging on the compositions of the invention and on the catalysts used, compositions were made up using five different liquid polysulphides, using isocyanate and conventional curatives as shown in Table 10. The compositions are heat aged for five months at 45° C. and their viscosities monitored. The results are shown graphically in FIGS. 7a to 7d for the compositions based respectively on LP541C, LP32C, LP33C and LP2C, and in FIG. 8 for the composition based on LP980C. 
     
                                           TABLE 10__________________________________________________________________________    LP33C        LP33C            LP980C                 LP980C                      LP32C                          LP32C                              LP541C                                   LP541C                                        LP2C                                            LP2C    LP-Rm        LP-Ri            LP-Rm                 LP-Ri                      LP-Rm                          LP-Ri                              LP-Rm                                   LP-Ri                                        LP-Rm                                            LP-Ri__________________________________________________________________________BASELP33C    100 100 --   --   --  --  --   --   --  --LP980C   --  --  100  100  --  --  --   --   --  --LP32C    --  --  --   --   100 100 --   --   --  --LP541C   --  --  --   --   --  --  100  100  --  --LP2C     --  --  --   --   --  --  --   --   100 100MT Carbon Black    25  25  25   25   25  25  25   25   25  25DBTL     --   1  --    1   --   1  --    1   --   1 CURATIVESHB40     10  --  10   --   10  --  10   --   10  --MnO.sub.2    10  --  10   --   10  --  10   --   10  --TMTD       0.5        --    0.5                 --     0.5                          --    0.5                                   --     0.5                                            --VMO21    --  10  --   10   --  10  --   10   --  10__________________________________________________________________________ 
    
     For the conventional and isocyanate-cured compositions based on LP980C, the cure time and work life were measured at monthly intervals. The results are shown in Table 11. 
     
                       TABLE 11______________________________________LP980C        LP980C    LP980C     LP980C(LP-Ri)       (LP-Ri)   (LP-Rm)    (LP-Rm)WORK          CURE      WORK       CURELIFE/Min      TIME/min  LIFE/min   TIME/min______________________________________Initial  48         152       10       601 month  54         165       10       852 months  60         180       14       853 months  65         195       14       855 months  70         215       15       90______________________________________ 
    
     EXAMPLE 13 
     Two compositions, designated LP-Ri and LP-R m , were made up to test the effect of long-term water immersion or manganese dioxide-cured (LP--R m ) and isocyanate cured (LP-Ri) compositions. The formulations were as follows: 
     
         ______________________________________          LP-Ri LP-Rm______________________________________BaseLP32C            100     100MT Black         25      25Silane A187      0.5     0.5DBTL             1.0     --CurativeMnO.sub.2        --      10HB40             --      10TMTD             --      0.5VM021            10      --______________________________________ 
    
     The cured compositions were immersed in water for 458 days, after which their physical properties were compared. The results were as follows: 
     
         ______________________________________          LP-Ri     LP-Rm______________________________________1.  Mass Loss    3 hours in vacuum at 70° C.                0.8           7.0    % Mass Loss2.  Hardness Shore A    Initial          61            45    Wet after 458 days                61            31    Dried after 458 days                61            48    Change Initial → Wet                0%            -31%    Change Initial → Dried                0%            +7%3.  Specific Gravity    Initial          1.34    kg/ltr                              1.36  kg/ltr    Wet after 458 days                1.34    kg/ltr                              1.22  kg/ltr    Dried after 458 days                1.35    kg/ltr                              1.40  kg/ltr    Change Initial → Wet                0%      kg/ltr                              -14%  kg/ltr    Change Initial → Dry                +0.7%   kg/ltr                              +3%   kg/ltr    Lost material    1.43    kg/ltr                              0.986 kg/ltr4.  Manual Observations    Both systems evaluated were still elastomeric when wet,    but LP-Ri compared more favourably with the dry control.    The dried system LP-Ri appeared to be identical to the dry    control.5.  Volume Swell    After 458 days   3.2%          62%______________________________________ 
    
     The degree of volume swell was measured at intervals during the immersion. The results are shown in FIG. 9, wherein it can be seen that while there is very considerable volume swell in the conventional composition, that exhibited by the composition of the invention is almost negligible. 
     The significant loss of mass in the LP--R m  sample is thought to be due to loss of the HB40 curative, the specific gravity of which is close to that measured for the lost material. 
     EXAMPLE 14 
     Rectangular box section polycarbonate tubing was fixed mechanically around existing windows to form frames to which polycarbonate sheets were adhesively bonded, using a two-part polysulphide composition formulated as follows: 
     
         ______________________________________                pbw______________________________________Part APolysulphide LP32C     100Stanclere DBTL catalyst                  1Part BIsocyanate curative Suprasec VM021                  8______________________________________ 
    
     The two components were mixed thoroughly. A thin adhesive film of the mixture was applied &amp;o the face of the polycarbonate box section. Soon afterwards a clean section of polycarbonate sheet was placed onto the adhesive film. After initial consolidation the material as allowed to cure with no further clamping of the polycarbonate sheet. The bond cured to handling strength in 11/2 hours. 
     The adhesive composition of the invention was found to give a good bond, resulting in cohesive failure when tested for bond strength. The bond had sufficient flexibility to accommodate the polycarbonate movement, and there was no stress crazing of the polycarbonate sheet. The adhesive composition was clear and gave a translucent layer between the bonded components. 
     Being a two-part composition, the adhesive of this example has a very long shelf life. 
     EXAMPLE 15 
     A one-part composition was made up for application to a polycarbonate window covering system similar to that of Example 14. The composition was made up as follows: 
     
         ______________________________________          pbw______________________________________LP-32C           100Stanclere DBTL   1Isocyanate VM 021            16______________________________________ 
    
     The polysulphide had been dried by the addition, several days earlier, of molecular sieve. The above components were mixed together under nitrogen and stored in a sealed container. The mixture had a shelf life of about two weeks. 
     A sample was taken from the container and a thin film was applied with a spatula to a face of the polycarbonate box section tubing. The adhesive was left for 10 minutes and a clean section of polycarbonate sheet was then placed onto it. After initial consolidation the material was allowed to cure with no further clampinq. It cured to handling strength overnight. 
     The system gave a rigid bond, with cohesive failure, but had enough flexibility to accommodate the polycarbonate movement. The adhesive was clear and the bonding layer translucent. There was no stress crazing of the polycarbonate. 
     EXAMPLE 16 
     Four compositions were made up to test the bonding properties of the compositions of the invention. Composition 1 was a conventional manganese dioxide-cured composition while compositions 2 to 4 were in accordance with the invention. The compositions were as shown in Table 12: 
     
                       TABLE 12______________________________________Com-         Compositionponent Description            1 (Ref)  2      3      4______________________________________LP32C  Liquid    100 Pbw  100 Pbw                            100 Pbw                                   100 Pbw  poly-  sulphideL2550  aliphatic --       8      --     8  isocyanateVM021  aromatic  --       --     8      --  isocyanateMnO.sub.2  catalyst  10       --     --     --HB40   plasticiser            10       --     --     --TMTD   accelerator            0.5      --     --     --Silane adhesion  --       --     1.6    1.6A187   promoterDBTL   catalyst  --       1.0    1.0    2.0______________________________________ 
    
     Each composition was mixed and a film of it was applied as shown in FIG. 10, to a polycarbonate strip 10 to form a 25.4mm (1 in.) square film 12. A second polycarbonate strip 14 was placed over the adhesive film and consolidated to form a lap shear bond. Each bond thus formed was allowed to stand for one week at 23° C. and 50% relative humidity. 
     The bonds were tested by pulling at 5mm/min. on a universal tensile testing machine. The results, together with other physical properties of the adhesive and of the bonds made by them, are shown in Table 13: 
     
                       TABLE 13______________________________________  FormulationProperty 1 (Ref)   2         3       4______________________________________Pot Life 30 mins   60 mins   30 mins 60 minsShear    0.416 MPa 0.512 MPa 0.504 MPa                                0.549 MPastrengthMPAElongation    12%       15%       35%      30%at breakCohesive  0%       80%       75%     100%failureColour   opaque    trans-    trans-  trans-              parent    lucent  lucentstress crazing    none      none      none    none______________________________________ 
    
     It can be seen from the table that all three compositions in accordance with the invention offer a number of advantages over the conventional composition 1. While the latter gives an opaque film, composition 2 gives a transparent one with good stability to UV light owing to the use of an aliphatic isocyanate, and in compositions 3 and 4 the transparency is only slightly reduced by the inclusion of a silane coupling agent. Furthermore, all three compositions of the invention have much improved adhesive properties. 
     EXAMPLE 17 
     A polysulphide composition was made up as follows, to provide a non-slip coating on polycarbonate sheets: 
     
         ______________________________________Component              Pbw______________________________________Liquid Polysulphide: LP-31                  100Catalyst: DBTL (Anchor Chemicals Ltd)                  2Curative: MDI (pba 2271, ICI)                  8.5Solvent: Methyl ethyl ketone (MEK)                  27.5______________________________________ 
    
     The LP-31 had a mercaptan content of 1.46% and the MDI curative had an isocyanate content of 23%. Stoichiometric proportions of these components would be 100 wt. parts LP : 8.1 wt. parts MDI. In practice however a slight excess of MDI was used, giving an isocyanate index of 105, to enhance adhesion to the polycarbonate and to allow for reaction with any moisture within the system. The higher molecular weight LP and relatively high DBTL content were selected with a view to achieving a cure within 3 minutes at 110° C. The MEK solvent was dried over molecular sieve. 
     The liquid polysulpyhide, catalyst and MDI were thoroughly mixed. The pot life of the mixture was measured by the cup and stick method and found to be 20 minutes at 23° C. and 50% relative humidity. 
     A spray coating composition was made up by adding the MEK solvent and sprayed onto polycarbonate sheets using a Binks BBA gun fitted with an AS17 air cap and suction feed cup, at a spray pressure of 310 kPa (45 psi). This gave a desirable &#34;orange peel&#34; effect, giving better anti-slip properties than &#34;flat&#34; coatings. Three coatings were sprayed to the thicknesses shown: 
     
         ______________________________________Coating     A            0.005 mm       B            0.015 mm       C            0.027 mm______________________________________ 
    
     The film thickness of coating A was found not to give adequate anti-slip properties, and this coating was not tested further. Coatings B and C were tested, as described below, for cure, transparency, blocking and anti-slip properties. 
     Two further coatings were prepared by casting the above mixture of LP-31, DBTL catalyst anti MDI curative, without the solvent onto polycarbonate sheets, using an adjustable doctor knife applicator. The coating thicknesses were as follows: 
     
         ______________________________________  Coating        D            0.1 mm        E            0.4 mm______________________________________ 
    
     The cure was evaluated for coatings B to E, using the standard &#34;crosshatch&#34; (sellotape) text, immediately after curing at 110° C. for 3 minutes. There was no transfer with any of the samples. 
     Further samples of coating C were submitted to a 5 minutes boiling water test and examined for delamination (samples were tested at 40 minutes, 20 minutes, 10 minutes, 5 minutes and 1 minute after heat cure). No delamination was found with any sample. 
     A sample of the unsolvented mixture was subjected to D.S.C. testing to determine the extent of the cure. The sample was heated between 25° C. and 110° C. in two minutes and maintained isothermally at 110° C. for a further 10 minutes. Most curing activity appeared to be finished within 21/2 minutes from the start of the cycle and all activity appeared to be complete after 2 minutes at 110° C. 
     20 x 30 cm polycarbonate sheets with cured coatings B, C, D and E were also tested for blocking by taking them directly from the 110° C. oven after curing and stacking them with a 5 kg weight force applied. The sheets were found to be non-blocking. 
     Coatings B, C and D were transparent, while the thicker coating E was translucent. 
     EXAMPLE 18 
     The formulation shown in Table 14 was mixed and applied to a lap shear bond as shown in FIG. 11. A seal 16, having a thickness of 8mm and a width of 12mm, was formed between two 24mm wide polycarbonate sheets 18, 20. 
     
                       TABLE 14______________________________________Ingredient Description    quantity by weight______________________________________LP 980C    Polysulfide polymer                     100MT Carbon Black      Filler          25DBTL       Catalyst        1PRA 2271 (MDI)      Isocyanate curative                      10______________________________________ 
    
     Physical properties were recorded as follows using a standard tensometer with a shear rate of 50 mm/min. 
     
         ______________________________________Average Shear Strength =               0.833 MPaAverage elongate at Break =                50%Cohesive failure =  100%______________________________________ 
    
     While DBTL has been used as the catalyst in the exemplified compositions, it will be appreciated that other organometallic catalysts can be used, and in particular other alkyltin laurates such as tributyltin laurate.