AU2015100195A4 - Low viscosity innovative moisture cured polymer compositions with improved tensile and creep properties for Industrial coatings,adhesives and sealant applications - Google Patents

Abstract

Wolantech Patent Application, STP15 dated Feb 2015 Low viscosity Innovative moisture cured polymer compositions with improved tensile and creep properties for Industrial coatings, adhesive and sealant applications. Moisture curable easy processing silane modified polymers of lower viscosity are disclosed that can use DMC and KOH catalysed polypropylene glycol polymer segments, with a combination of chain extended polymer segments, alkoxy silane adduct end caps, isocyanato silane end caps and hydrosilated alkoxy end caps, and the use of hydrogen bonding reduction additives for lower viscosity and easier processing polymers. Suitable for Industrial adhesives, sealants and coatings, which are free of unreacted isocyanate groups and crosslink in the presence of moisture with lower levels of residual metal catalysts and improved creep properties upon curing due to some content of urea and urethane hydrogen bonding.

Description

Wolantech Patent Application, STP15 dated Feb 2015 Low viscosity Innovative moisture cured polymer compositions with improved tensile and creep properties for Industrial coating, adhesive and sealant applications. PATENT DESCRIPTION 1. BACKGROUND OF THE INVENTION The field of Moisture cured one part room temperature vulcanised adhesives, sealants and coatings is well known, and all the applications depend on natural and synthetic polymers with attached or imbedded molecules that cure at room temperature with moisture, and form a cross linked matrix. The compositions also include calcium carbonates, plasticizers, catalysts, UV inhibitors and other additives well known to the practitioners of the art. This invention discloses a hybrid polymer composition, with some alkoxy silanes of various designs at the polymer terminals, which then can cure with atmospheric moisture to form useful coating, adhesive and sealant products. The first products to be introduced to the CASE markets, and still the market dominant moisture cured technology, are the Polyurethane compositions, which cure by the reaction of an Isocyanate molecule, containing nitrogen, carbon and oxygen radical, known as the NCO group. This is still the most economic and common way of producing polymers for many applications, where the terminal NCO groups attached to a polymer such as Polypropylene glycol, PPG, crosslink with atmospheric moisture. This reaction first forms an amine from the NCO group, with elimination of C02 gas, and this amine then 1 crosslinks with another NCO group on a second chain, to fully crosslink the polymer, with the production of a urea group, which then thickens the composition and forms hydrogen bonded segments in the cured matrix. The advantages of the Polyurethane cured products are well known, and cured products have good tensile, creep, and elongation properties, that can be easily modified in the compounded formulation of adhesives and sealants and coatings. The main disadvantages of the NCO group containing polymers is that the unreacted NCO groups are toxic to humans and cause long lasting immune sensitisation and other reactions to traces of isocyanates. The production of PU prepolymers with polypropylene glycol polymers (PPG) and diisocyanate molecules such as Toluene diisocyanate (TDI) result in small quantities of unreacted monomers that are very difficult to eliminate. Currently in many countries in Europe, the diisocyanate monomers such as TDI have restricted usage and specific risk labelling is required in Consumer products. The isocyanate molecules are useful reactants for Polymer compositions, and can be safely used in Factories .Thus there is a need to produce effective polymer products where the NCO groups are fully reacted if used, and there needs to be an easy method to eliminate unreacted isocyanate molecules, and the final moisture crosslinking molecule should be safer for Applicators and Consumers. Moisture curable silyated polymers, were introduced circa 1975, where the active NCO group in a PU prepolymer is reacted with an amino alkoxy silyl group as in the early US 3627722 patent. The high viscosity of these polymers was a major problem. The later introduction of isocyanato silanes went some way to reducing these high viscosity issues as most of the viscosity increase is caused by hydrogen bonding across the urea groups that are formed when the amino alkoxy composition is used. The isocyanato silanes form a urethane bond when reacted with a hydroxyl terminated polymer, and this group has much less hydrogen bonding and less viscosity build. Some viscosity reduction with these amino silane modified polyurethane polymers was achieved in US6265517 and US 6001946 where the NCO groups were reacted with a secondary amino silane where a bulky group was attached 2 to a primary alkoxy amino silane. The use of isocyanate monomer chain extension in the previous patents was a good example of using the advantages of PU process components to produce a longer Polymer chain that is needed for softer high elongation sealants in the Construction Markets. In the 20131000053 patent was disclosed the use at small levels of common chemicals used in the field that are added to the silane terminated polymers, that reduced the hydrogen bonding in the silyated polymer with urethane or urea bonds, and this innovation has been used by polymer manufacturers to reduce the viscosity of urethane and urea containing silane terminated polymer compositions. An alternate process was described at the same period circa 1975, in US 3971751, where the hydrosilation method well known to silicone polymer technology was used to terminate an allyl (vinyl) group on a polypropylene glycol polyether. The use of the platinum hydrosilation catalysts produced a good low viscosity polymer, however as efficiency of conversion of Platinum based catalysts such as Karstedt's in US 3775452, was in the range of 80 percent, polymer physical properties were affected. The unreacted double bonded ends were able to be reacted with primary amino silanes or even diisocyanate molecules in Modified Polymer formulations. These hydrosilated polymers were free of any urea or urethane components, and were of low viscosity which was not always optimal. The hydrosilation process methyl dimethoxy terminated polymers needed a large amount of tin containing catalyst to cure, in the order of 2 to 3 percent by weight of the polymer component. It was soon discovered however, the addition of an amino silane adhesion additive reduced the level of the primary catalyst addition and also aided adhesion of the adhesive and sealant formulations. The urea free adhesive formulations also needed substantial additions of urea thickener or polyamide thickening additives, to reduce slump of adhesives during application and curing. The short introduction shows that there are to date no perfect moisture cured polymers, which are available to the formulators in the adhesive, sealant and coating markets, with each technology and composition methods having some 3 benefits and some weakness. To date, the inroad of the silane modified polymer products upon the traditional Polyurethane market still remains small. The high costs of silane modified polymers and the occurrence of creep and high levels of residual metal complex catalysts, is a problem for market penetration, with what is acknowledged as a safer product for Applicators and Consumers. Thus there is still more room for safer, moisture curable polymers and the adhesive and sealant compositions where the benefits of previous innovations are skilfully combined and enhanced. SUMMARY OF THE INNOVATION Embodiments of the Polymer compositions included in this innovation, where a polymer chain is terminated by a reactive alkoxy molecule, can be described by the generic formula below: Formula 1 (alkoxy adduct)(POLYME R)(Diisocyanate)(POLYME R)(hydrosilated alkoxy) Formula 2 (alkoxy adduct)(POLYMER)(hydrosilated alkoxy) Formula 3 (alkoxy adduct) (POLYMER)(Isocyanato silane alkoxy) Formula 4 (hydrosilated alkoxy) (POLYMER)(hydrosilated alkoxy) Formula 5 (alkoxy adduct)( POLYMER)(alkoxy adduct) Formula 6 (isocyanato silane)(POLYMER)(isocyanato silane) The most important component of the above compositions is the base POLYMER, which provides the strength and flexibility to the final composition, to which are added the crosslinking molecules. The Polymers that are well suited are the polyether polyols prepared in the presence of Double Metal Cyanide (DMC) catalysts, as per US 5096993 and subsequent Patents. These longer chain PPG have low alkene content, however the residual DMC catalyst 4 at levels of about 50 parts per million (ppm) can cause chains breaking on exposure to moisture, and this hydrolysis is a problem in applications where water and moisture are high. The DMC process polypropylene glycols are available as diol or as triols and are well suited to the compositions in formula 3 to 6 above. The base POLYMER can be also be the older technology KOH catalysed polypropylene glycol polyether as per US 3829505. Our preference for some compositions is the KOH catalysed PPG, formed by the reaction of a starter molecule and addition of propylene glycol, and this mixture allowed to react longer than normal, to produce a PPG chain, terminated with both Hydroxyl (OH) groups and double bonded alkene end groups in selected amounts required for the polymer composition. This is achieved at a molecular weight of between 5000 and 10,000 grams per molecule depending on reactor conditions. The residual KOH in the PPG can then be washed out and neutralised by an organic acid such as acetic acid to produce a PPG with very low levels of metal catalyst present. We can have a PPG polymer chain with a combination of hydroxyl and alkene terminal ends, or we can have a polymer with mainly hydroxyl chain ends. We can then build the silane terminated polymers in several ways and the order is not limited. We can also use different alkoxy molecules on each end, and the benefits in viscosity and physical properties are disclosed below. With the alkene end on the PPG, we can form a alkoxy termination by reacting the alkene carbon bond with methyl triethoxy silane with about 30 ppm of a platinum catalyst such as Karstedt's catalyst, US3775452, or the new vinyl silane modified Platinum Carbene complexes which have higher efficiency disclosed in US7268233. The reaction temperature is around 70 degree C and efficiency of the reaction is between 70 and 95 percent in most cases. The reaction can also be done with methyl dimethoxy silane but not the methyl trimethoxy silane where the molecule is not stable with the catalysts. For higher strength adhesive polymers and harder paint coating polymers, it is the ratio of the chain length and the number of crosslinking groups on a chain that gives a prediction of final composition hardness and toughness properties. The effective chain length can be calculated by dividing the Molecular length of 5 the PPG chain by the number of bonds available on the chain. For example an 8000 MW PPG terminated with methyl dimethoxy silanes of formulas 5 and 6 above has an effective length of 4000. This polymer can be used to produce an adhesive composition with tensile strength of 3.0 Mpas with elongation of 250 percent which is suitable for Industrial adhesives. Hardness by Shore A method is about 50. However if the 8000 MW PPG is terminated with trimethoxy silanes, the effective chain length is 2666,and the adhesive formed is brittle, breaks at low elongation and is not suitable for adhesive use. It can be used as a crosslinking additive. When required, the KOH catalysed PPG, is available with alkene groups and hydroxyl groups varying in percentage of total end groups from 25 percent alkene to 50 percent alkene and 50 percent hydroxyl. The molecular weights then vary in the range of 5000 to 8000 gram per mole. The alkoxy adduct termination of a hydroxyl group on a PPG is well known and described in US6265517 for example. The reaction with IPDI isocyanate at low temperature uses the different reactivity of this diisocyanate molecule to first react the faster NCO group with the PPG terminal OH group, and when this is completed to at least 90 percent, the remaining slower NCO group is safely reacted at the low temperature of about 30 degree with a secondary amino silane. The secondary amino silanes are now common, and they can be first reacted with the diisocyanate to form an isocyanate adduct first, and then use the Adduct as a single stage reaction. The preference is to use the IPDI Isocyanate and secondary amino silane at low temperatures of about 35 degree C, as at these low temperatures the vapours and hazards associated with resin production are lower. The reactions are monitored by FTIR to check that all the reactions are progressing and completed. At the low temperature of the reaction, any remaining unreacted NCO groups shown by Shimazdu FTIR at 2271 cm-1, are removed by a small addition of methanol. 6 The preference is for 8000 to 10000 MW PPG Polymer, capped with alkoxy silanes or hydrosilated silanes, as per formula 2 and 6. These STP polymers containing some urea and urethane segments have advantages in producing Hybrid adhesives, where thickening is easier, and the urea group content, results in hydrogen bonded chains upon cure. This is the same as for Polyurethane compositions, and these hydrogen bonded segments result in less creep of the adhesive composition under load. Creep in Polymers is the known and described process of chains slowly slipping over each other under periodic or constant loads or tension. The innovative process provides an outline of useful low viscosity moisture cured polymers, which are able to produce economic and useful adhesive, sealants and coating and a viable alternate to established PU systems. However the benefits of PU compositions are still maintained, while all the NCO groups are fully reacted or neutralised. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS. Embodiments of the invention illustrate useful low viscosity moisture curable silylated polymers that can be prepared from polyoxyethylene ether diols and triols, polyoxypropylene ether diols and triols, polyoxyethylene oxypropylene diols and triols, polytetramethylene ether glycols, polyacetals, polyacrylate and numerous mixtures of polyols of various structures and molecular weights and there are numerous ways of attaching hydroxyl and alkene branches to a polymer chain, known to practioners of the Art. As used herein, the term alkyl means any saturated hydrocarbon radical, and preference here is for the linear or ranched alkyl groups containing methyl, ethyl groups attached to a silicone atom. Others are available. Specific isocyanato silanes that can be used to react herein with the hydroxyl groups of the aforementioned polymers are isocyanato propyl triethoxy silane, 7 isocyanato propyl methyl dimethoxy silane, isocyanato propyl trimethoxy silane, and the like. Di-isocyanates as used herein for capping a hydroxyl terminate polymer chain are toluene di-isocyanate and isophorone di-isocyanate where advantage is taken of a faster reacting NCO group, so the reactions can be at lower and safer temperatures, and then the second reaction with a secondary amino silane are carried out at low temperature. Other di-isocyanates are available and included in the process described. Where chain extension is required, it is easier to use di-isocyanates where both NCO groups are of equal reactivity, and these are hexamethylene di-isocyanate, Methylene diphenyl di-isocyanate, Meta tetramethylenexylene di-isocyanate, and triphenylmethane triisocyanate where increased crosslinking is required. Specific secondary silanes for use herein for an adduct composition include N cyclohexyl amino propyl methyl dimethoxy silane, N cyclohexyl amino propyl triethoxy silane, N cyclohexyl amino propyl trimethoxy silane, N phenyl amino propyl methyl dimethoxy silane, N phenyl amino propyl triethoxy silane, N phenyl amino propyl trimethoxy silane, and the like. A catalyst will normally be used for the preparation of the silane terminated or modified polymer, and the preference is that this catalyst does not readily catalyse the silanol condensation of the Alkoxy silane used for the crosslinking reaction. Preferred hydroxyl and NCO group reaction catalysts are the zirconium and bismuth containing complexes such as Coscat 83 from Vertillius and K-Kat 348 from King Industries. The common dibutyl tin dilaurate and dibutyl tin acetate should not be used where the capping silane is cyclohexyl amino propyl trimethoxy silane, as the polymer stability is compromised if some moisture is absorbed during production or storage. According to the invention, the silane modified polymers of formula 1 to 6, have an addition of a stabilizer, and this agent can be a moisture scavenger such as vinyl silane, normally used in the adhesive compositions. The other stabilizer that can be added is a mono-alcohol, and methanol is the preferred embodiment described here. The combination of a small addition of vinyl silane and methanol at levels up to 1.0 percent, have the surprising result of reducing the viscosity of most of the compositions described in formula 1 to 6, 8 and this is the result if interfering with the hydrogen bonding that occur in the polymer where urea or urethane or both are present. This discovery was described in US patent applications 14220115 and 14160232 lodged in 2014. The innovative low viscosity silane terminated polymers described herein, are used as a binder to produce sealants, adhesives and coatings, and are normally compounded in planetary Trishaft mixer equipment with a high speed disperser, vacuum, heating jacket, and a Nitrogen blanket facility. A press is used to extrude the finished adhesive or sealant or membrane or coating into cartridges or sausage packs, and this equipment is also available for laboratory development in sizes from 3 kg up to 20 Kg contents by weight. The moisture cured polymers described herein are normally compounded with treated and untreated calcium carbonates, as the main volume addition, and the precipitated calcium carbonates of small particle size, improve the strength and elongation of the polymers, and are normally added from 20 percent to 80 percent by weight of the adhesive or sealant composition. Other inert minerals are available and include clays, talc aluminium silicates, metal oxides and the like. Coated precipitated calcium carbonates (PCC) are preferred for adhesive compositions as they introduce high strength and significant thixotropy. These PPC products are of particle size from 0.05 to 2.0 microns, and preference is for Winnofil SPT, Ultra Pflex, and Hakuenka CCR .These and other numerous PCC minerals can be used in combination with other minerals to balance needed thixotropy, viscosity and tensile strength of the composition containing the Silane terminated polymer. The Compositions using the innovative polymers described herein can be reinforced with carbon black to increase tensile strength and provide the high sag resistance that is achieved with the alternate Polyurethane compositions available to Customers. As the calcium carbonates and precipitated calcium carbonates do contain some moisture at levels of up to 0.5 percent, the polymers need to be not sensitive to this contamination, and this is achieved with the Polymers terminated with propyl methyl dimethoxy silanes or the propyl triethoxy silanes described herein. The composition of adhesive or sealant or coating, is normally compounded in the initial step with Polymer, 9 precipitated calcium carbonate, carbon black or titanium dioxide, or both. At higher carbon black addition levels, some plasticizer is needed, and these additions are commonly the phthalate containing chemicals, although there are numerous suitable alternates. A big advantage of the silane terminated polymers is that PPG diols and triols can be used as a plasticizer; as the hydroxyl end groups on the polyol have no function with the silane curing process. In one embodiment of the invention, the moisture curable silane terminated polymers are compounded with moisture containing precipitated calcium carbonate, carbon black, titanium dioxide, other mineral pigments, and some plasticizer chemicals. Some of the moisture present can be removed in the mixer with heat, shear and vacuum. However it is also necessary to add a moisture scavenging chemical, and the water scavenger can be a fast reacting isocyanate, like para toluene sulfonyl isocyanate, or an alkoxysilane, for example vinyl trimethoxy silane and similar fast silanes. Once the first stage of the compounded adhesive formulation is dispersed and dried, with some excess of vinyl silane giving some protection from moisture, final composition additives such as the adhesion promoters, UV stabilizers and the final addition is the sealant or adhesive catalyst. The catalyst that is used in the silane terminated polyurethane composition using the disclosed resins is normally a metal complex. The propyl trimethoxy silane terminated polymers will easily cure with small addition of tin complex catalyst, such as dibutyl tin dilaurate or dibutyl tin acetate. These trimethoxy terminated compositions are best suited to construction sealants as the low catalyst levels provide a good baseline resistance to UV degradation. Where tin catalysts are a problem the Titanium chelate catalysts can be used. The tin based catalysts do provide some fungal resistance, and the DBTDL is commonly used in construction PU sealants with this side benefit. Where the innovative polymers terminated with propyl methyl dimethoxy silane or the propyl triethoxy silane, or combinations of both alkoxy groups, there is a need to use higher tin catalyst levels, and Dibutyl tin diketonate catalyst is used, available from TIB Chemicals as TIB KAT 226, and also from Rohm & Haas is available the Metatin 740. The required levels are in the order 10 of 2.0 percent by weight of Polymer, and the use of the amino silane adhesion promoters does help the curing process with moisture. Skinning times of automotive type adhesives can be reduced to 10 minutes. These compositions are normally not exposed directly to sunlight in Construction products, and the weathering and UV resistance is limited, however UV resistance is better than PU adhesives where aromatic isocyanates are used for crosslinking. The compositions of the propyl methyl dimethoxy terminated polymers used in Industrial sealants with requirements of fast cure and good adhesion to glass and other surfaces, need an adhesion silane, and a commonly used silane is N 2 amino-ethyl 3 amino propyl trimethoxy silane, sold by Shinetsu Company as KBM603. This amine acts as a secondary catalyst with the dibutyl tin diketonate primary catalyst. There are numerous adhesion silanes available, and each has to be evaluated for a specific surface that needs adhesion. The inventive compositions will now be illustrated by the following examples of polymer and adhesive laboratory mixtures, which are not to be considered as limiting in any manner. Tensile strength is measured according to ASTM standard D1708. Shore A, hardness is a measure of the elastic modulus, and to ASTMD2240. Viscosity is measured in Mpa-s by Brookfield instrument, and described in ASTM D2196. EXAMPLE 1 A polymer composition according to Formula 6 . A Diol polypropylene glycol polyol manufactured using DMC catalyst process was sourced in China from Sinopec, with a Molecular weight of approx 8000 and a hydroxyl value of 14.1. The PPG was dried under vacuum and heat over 8 hours to reduce the moisture content to 48 ppm. In a laboratory glass reactor with an oil bath to avoid hot spots, with good stirring, vacuum and nitrogen purge, was loaded 2000 grams of the polyol, and this was heated to 75 degree C under light vacuum and good stirring. The vacuum was broken and under a blanket of nitrogen, 125 grams of isocyanato propyl triethoxy silane was added and the mixture was stirred for 10 minutes. After the initial mixing, 0.25 grams of Coscat 83 bismuth catalyst was added and the reaction was monitored by 11 Shimazdu FTIR to see reaction progress where the NCO peak at 2272cm -1 was reducing, and at a similar rate the C=O peak at 1720 cm-1 was seen to increase as the polyol capping reaction proceeded. At the same time the smaller OH peak at 3500 cm-1 reduced and the NH peak at 3301 cm-1 increased at the same rate. The reaction was finished at approx 2.5 hours, and then the mixture was cooled down to 30 C. When the mixture was at 30 degree Centigrade, an addition of 21 grams dry methanol and 21 grams vinyl silane were added with stirring and an immediate reduction in polymer viscosity was observed. The addition of methanol ensured that any unreacted NCO groups were capped so the polymer is isocyanate free and there was no trace at 2272 cm-1 of this group. The viscosity at 25 degree C of the polymer was then measured and was 3500 Mpa-s, which is the same approximate viscosity as the starting polyether. A Polymer sample was then cured with 2 percent addition of TIB KAT226 and 1 Percent KH792 amino silane, and the cured sheet had a shore A hardness of 42 after 5 days of cure. This low viscosity polymer with cured shore A 42 hardness is suitable for industrial adhesive compositions and demonstrates the inventive addition of methanol and vinyl silane to reduce the urethane groups hydrogen bonding, and produce an extremely low viscosity polymer, that can be compounded with high levels of precipitated calcium carbonate for high strength adhesive and coating and membrane compositions. During compounding under vacuum and heat of shear, the methanol and vinyl silane content is reduced as both these additions are used to remove the water content of the precipitated calcium carbonate, or other minerals. This extremely low viscosity polymer can also be used in combination with other higher viscosity polymers. EXAMPLE 2 A Polymer composition according to formula 3 , and a black Industrial adhesive composition using the Polymer. 12 A Japanese manufactured low monol content diol polypropylene glycol polyol manufactured by the latest DMC process catalysts was sourced, with MW of approx 12000 and an OH value of 9.6 . The diol was dried as described in example 1 and 4000 grams of the dried diol was loaded into a laboratory reactor as above, and heated under vacuum to 40 degree Centigrade. The vacuum was broken and under nitrogen blanket was added 81 grams of Isophorone diisocyanate (IPDI) and mixed for 10 minutes. 1.0 grams of K-Kat 226 bismuth catalyst was added and the reaction monitored by FTIR. When nearly half the NCO groups of the IPDI were reacted with half the OH groups available, cyclohexyl amino propyl methyl dimethoxy silane was then added at 40 Centigrade and a very fast reaction occurred with the remaining NCO groups to cap half the PPG polymer with the alkoxy adduct described in formula 3. The mixture was the heated to 75 degree C and Chinese made FC25 isocyanato propyl triethoxy silane from HSC Corporation, was added and allowed to react over the next 3 hours, until there was very little NCO showing at 2272 CM-1 and very few OH groups at 3500 cm-1. The mixture was of higher viscosity than example 1, and allowed to cool to 30 degree C and then an addition of 40 grams dry methanol and 40 grams vinyl silane was added. Over the next 12 hours the viscosity of the Polymer reduced, as the hydrogen bonding of the urea groups takes some time to develop. The viscosity next day of this mixture was 19000 Mpas at 25 degree C, and subsequent batches varied in viscosity by up to 3000 Mpas. This inventive polymer of example 2 was then compounded into an industrial adhesive. In a laboratory trishaft mixer, 1000 grams of the Polymer, 1200 grams of Ultra P Flex precipitated calcium carbonate and 50 grams of carbon black powder were compounded in stage 1 under high shear and high vacuum to disperse the polymer in the powders and remove some moisture. In stage 2 the vacuum was released and under nitrogen blanket, 50 grams of vinyl silane was added to chemically dry the adhesive mixture. In stage 3 was added 20 grams KH792 adhesion silane, 10 grams Tinuivin 765 UV absorber and 10 grams 1076 antioxidant. Finally under nitrogen was added 20 grams of KRA-1 dibutyltin diketonate catalyst, and the mixture was pressed into sausage packaging and cure samples were made. 13 After 5 days of cure the laboratory samples of the adhesive composition were tested by standard ASTM methods, and Tensile strength was 3.4 Mpa at break with 250 percent elongation. The tack free time was 15 minutes at 25 C, shore A Hardness was 62 and residual tack level was low. The adhesive composition using this alkoxy capped polymer is suitable as an automotive windscreen replacement adhesive or a general industrial adhesive used in Trains, caravans and many other applications needing a solvent free and isocyanate free adhesive. EXAMPLE 3 A polymer composition according to formula 5 , and a white adhesive composition using the polymer. A diol polypropylene glycol manufactured by the MMC metal catalyst process was sourced from Sinopec in China, with a molecular weight of approx 8000 and an OH value stated at 14.0. The diol was of medium unsaturation and wet, so the diol was dried under vacuum and heat to reduce the moisture content to 36 ppm as measured by Carl Fischer instrument. 1500 grams of the dried diol was loaded into a laboratory reactor as above and heated under nitrogen to 30 C. 83 grams of isophorone diisocyanate was then mixed in and allowed to mix for 10 minutes. 0.3 grams of Coscat 83 catalyst was then added and the reaction was allowed to proceed until about half the NCO groups were reacted with all the diol OH groups. The reaction was monitored by FTIR as in above examples. When the NCO was approximately half of the initial level, 83 grams of cyclohexyl amino propyl methyl dimethoxy silane was added to quickly form the alkoxy adduct at both ends of the diol polymer. Some NCO groups were present and some OH hydroxyl groups were not capped by intention and to the mixture was then added 17 grams methanol and 25 grams vinyl silane. No NCO peaks were detected at 2272 cm-1 and the viscosity of the polymer at 30 C was 17000 Mpas the next day. Samples of the polymer were cured with 1 percent KH792 amino silane and 2 percent TIB Kat 226 dibutyltin diketonate catalyst. The shore A hardness of the cured Polymer after 5 days was 30. 14 The Polymer 5 in this example was then compounded into a white industrial adhesive and sealant composition. In a laboratory 4 litre trishaft mixer as described above, 750 grams of the polymer, 1600 grams of Chinese sourced PCC, 380 grams of DIDP, and 50 grams of Titanium dioxide paste were dispersed and compounded under high shear and high vacuum. In stage 2 the vacuum was reduced and under nitrogen blanket 60 grams of vinyl silane drying agent was added to dry the mixture. In the final mixing stage, 6 grams Tinuivin B75 UV stabilizer, 20 grams KH792 amino silane adhesion promoter and 12 grams TIB Kat 226 curing catalyst were added. The white adhesive was loaded into sausages and samples taken and cured for 5 days. The white sealant open time before skin curing occurred with atmospheric moisture was 15 minutes at 25 C, Shore A hardness after 5 days cure was 55, Tensile at break was 3.6 Mpas and elongation was 510 percent at break. This is a good general purpose industrial adhesive. EXAMPLE 4 A polymer composition according to formula 2 , and a black adhesive composition using the Polymer. A diol polypropylene glycol polyol was sourced from a Partner Company, where the 8000 MW PPG was made using mainly the older style KOH catalyst process, where the growth of the alkene monol was allowed to develop and produce a polymer of approximately equal hydroxyl end groups and alkene end groups. The diol was dried to reduce the moisture content to less than 50 ppm and residual KOH was neutralised with acetic acid anhydride, to produce a low residual catalyst diol. 1500 grams of the diol was then loaded into a laboratory reactor as described above, and heated to 70 degree C with vacuum. 34.Ograms of methyl dimethoxy silane was then added to the mixture along with 40 ppm of a proprietary platinum vinyl silane complex and hydrosilation was initiated over a 3 hour period, and monitored with Shimazdu FTIR. Nearing completion of the hydrosilation reaction, the diol mixture was cooled to 30 C, and 42 grams of Isophorone diisocyanate was added and the 15 reaction proceeded with the IPDI reacting with the hydroxyl groups of the diol. When the NCO content reduced by approximately half, cyclohexyl amino methyl dimethoxy silane was added, and this secondary amine quickly reacted with the remaining NCO groups to form the Alkoxy adduct. When the NCO peak was very small, 20 grams of methanol and 20 grams of vinyl silane were added to stabilise the Polymer and block the viscosity due to urea hydrogen bonding. The viscosity of the polymer composition the next day was 14000 Mpas at 25 degree C, and a cure sample of the polymer using 1 percent KH792 amino silane and 2 percent TIB KAT 226 dibutyl tin diketonate catalyst, was after 5 days 36 Shore A Hardness. This hybrid composition Polymer was then compounded in the 4 litre laboratory mixer as described above. 1000 grams of polymer above, 1200 grams of Ultra Pflex Precipitated calcium carbonate, and 50 grams of carbon black were compounded with high shear and high vacuum to disperse the powders in the polymer, until smooth. After the shear stage was completed, the vacuum was broken and under Nitrogen 50 grams of vinyl silane was added to chemically dry the adhesive mixture. When this stage was completer, 20 grams of KBM603 adhesion silane, 10 grams Tinuivin UV stabilizer and 10 grams of 1076 antioxidant were added and mixed. Finally under Nitrogen blanket the 20 grams TIB KAT 226 dibutyl tin diketonate curing catalyst was added, and the adhesive mixture was filled into sausages and cure sample were taken for testing. The results for the cured composition above after 5 days, was a Shore A hardness of 64, and a tensile strength at break of 4.2 Mpa with a elongation at break of 325 percent . The open time was 10 minutes and shear strength using methanol cleaned stainless steel was 3.1 Mpa. These examples are to be taken as a guide to polymer and adhesive construction methods and do not limit or constrain the appended claims. Persons skilled in the art would easily see obvious variations and combinations, and these are intended to be covered by the claims of this document. 16 17 18

Claims (13)

1. A moisture curable polymer composition described below by the general formula of 3 components, (Alkoxy endcap structure)(Polymer)(Alkoxy endcap structure) Wherein: The Polymer has a backbone of polypropylene glycol diol or triol and is produced by double metal cyanide process (DMC) where the hydroxyl terminal ends are at a level of 90 percent to 97 percent of total end groups, and the Alkene double bonded chain ends are restricted to 5 percent or less of the diol or triol polypropylene glycol chains .The Polymer can also be a KOH polypropylene glycol polymerisation process, the alkene double bonded terminals that are produced at the same time as hydroxyl groups, are allowed to develop to at least 25 percent of all polymer chains and preferably up to 55 percent of the terminal chains .Both catalyst systems can be combined. The alkoxy endcap structure attached to the reactive terminals of the Polymer can be a mixture of an alkoxy adduct formed by a diisocyanate and a secondary amino silane reacted with the polymer hydroxyl end groups, can be an isocyanato propyl alkoxy silane with 2 or 3 alkoxy groups and reacted with Polymer hydroxyl end groups, and can be a hydrosilated methyl dimethoxy silane or methyl triethoxy silane reacted with alkene terminals on the Polymer using a platinum complex catalyst. 1

2. The composition of claim one where the DMC process polypropylene glycol polyether can have a molecular weight between 5000 and 25 000 .

3. The composition of claim 1 where the Polymer can be a polypropylene glycol polyether chain extended with a diisocyanate.

4. The composition of claim 1 where the Polymer can be any of polypropylene glycol, polytetramethylene glycol, polycarbonate polyol, polyacrylate polyol and any combinations of these polymer chains described.

5. The composition of claim 1, where the alkoxy end cap structure can use methylene diphenyl diisocyanate, Meta tetra-methylene diisocyanate, Isophorone diisocyanate, and hexamethylene diisocyanate reacted with a secondary amino silane.

6. The composition of claim 1 where the secondary amino silane in the alkoxy end cap structure can be cyclohexyl amino propyl triethoxy silane, cyclohexyl amino propyl trimethoxy silane, cyclohexyl propyl methyl dimethoxy silane, phenyl propyl triethoxy silane, phenyl propyl methyl dimethoxy silane, reacted with the diisocyanate.

7. The composition of claim 1 where the alkoxy end cap structure can be isocyanato propyl triethoxy silane, isocyanato propyl trimethoxy silane, isocyanato propyl methyl dimethoxy silane, reacted with the Polymer hydroxyl groups.

8. The composition of claim 1 where the alkoxy structure can be formed by hydrosilating the terminal alkene groups of the polymer with methyl triethoxy silane, methyl dimethoxy silane.

9.The catalyst used for the alkoxy structure with the reactive silanes in claim 8 are the platinum containing vinyl silane complexes described as Karstedt's catalyst and the like.

10.The composition of claim 1 where polymer viscosity is reduced by small addition of up to 1.5 percent of methanol and vinyl silane, and the terminal alkoxy end structures can be composed of 2 or more of the alkoxy structures disclosed. 2

11. The compositions of claims 1-10 where in the innovative polymers are compounded with described additives for a moisture curing adhesive product.

12. The compositions of claims 1-10 where in the innovative polymers are compounded with described additives for moisture curing sealant or a membrane product.

13. The compositions of claims 1-10 where in the innovative polymers are compounded with described additives and other components for Coating products. 3