GB1592260A - Organic titanium compounds as viscosity improvers for polyol compounds - Google Patents

Description

(54) ORGANIC TITANIUM COMPOUNDS AS VISCOSITY IMPROVERS FOR POLYOL COMPOUNDS (71) We, BASF WYANDOTTE CORPORATION, a corporation organized under the laws of the State of Michigan, United States of America, of 1609, Biddle Avenue, Wyandotte, Michigan, United States of America, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following Statement: The present invention relates to the improvements of the viscosity of polyester polyols and polyether polyols.

Polyether polyols such as polyoxyalkylene ether polyols and polytetramethylene glycols, and polyester polyols are commonly used in the production of urethane polymers. These polyols are reacted with polyisocyanates in the presence of catalysts and other materials to produce urethane polymers which may be in the form of elastomers, sealants, caulking compounds, coatings, or flexible or rigid foams. These polyols in and of themselves, depending on the nature of the starting material and the molecular weight employed, may have extremely high viscosities. Additionally in the preparation of certain types of urethane polymers the polyols may have added to them inorganic fillers or pigments which contribute to the high viscosities of the system. In order that these polyols may be used for the preparation of urethanes, it is desirable to reduce the viscosities to such a level that handling of the solutions is made easier.

It has now been discovered that the addition of small amounts of certain organic titanium compounds to polyols drastically reduces the formulation viscosity which permits for rapid leveling and easier processing of these polyols upon reaction with polyisocyanates or even prior to reaction with polyisocyanates.

Accordingly, the present invention provides a process for reducing the viscosity of a polyester polyol or polyether polyol which comprises adding an organic titanate. The organic titanates which may be employed are based on tetravalent titanium and suitably have the following structure: Ti(OR)4 to 18 carbon atoms an alicyclic radical having from 1 to 3 rings, 5 or 6 carbon atoms per ring, and from 5 to 18 carbon atoms per molecule, an aromatic radical having from 1 to 3 rings and from 6 to 18 carbon atoms per molecule, or an acyl radical having from 2 to 18 carbon atoms, for example, each R may be independently alkyl, alkanoyl, cycloalkyl, aralkyl, phenyl, naphthyl or alkylaryl. Preferred titanates are tetraisopropyl titanate, tetrabutyl titanate and isopropyl triisostearoyl titanate.

It has been found that very small amounts of an organic titanate cause a pronounced decrease in polyol viscosity and as little as 0.1 percent has been found to reduce the viscosity by as much as 30 percent. Higher concentrations of titanate have still a further appreciable influence but the values do tend to plateau. Accordingly, the preferred amount of organic titanate which is added to the polyol is from 0.01 to 20 weight percent of the amount of polyol especially 0.1 to 10% and more preferably 0.5 to 5% by weight. The addition of these organic titanates has no appreciable influence on the curing rate of the polyols when reacted with polyisocyanates. As a matter of fact it appears that the addition of an organic titanate in the presence of an organomercuric catalyst such as phenylmercuric acetate has a synergistic effect in reducing the viscosity of the polyol formulation. Thus, the organic titanate may be added to the polyol to reduce the viscosity of said polyol in the presence of a catalyst for reaction of the polyol with a polyisocyanate and/or additional inorganic fillers or pigments, and a urethane polymer may be prepared therefrom.

The polyols employed include those prepared by condensing monomeric units such as ethylene oxide, propylene oxide, the isomeric butylene oxides, styrene oxide and mixtures thereof with active hydrogen compounds such as ethylene glycol, propylene glycol, water, dipropylene glycol, diethylene glycol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol, hexanetriol, glycerol, trimethylolpropane, trimethylolethane, hydroquinone, pentaerythritol, a-methylglucoside, sorbitol, sucrose, ethylene diamine, diethylene triamine, toluenediamine, aniline, methylene aniline, piperazine, triisopropanolamine, and bisphenol A.

These polyols may have molecular weights ranging from 100 to 26,000.

Included are those polyols which are characterized as being essentially hydroxyl terminated polyether polyols which have the general formula H(OR)nOH wherein R is an alkylene radical and n is an integer which in a preferred embodiment is sufficiently large that the compound as a whole has a molecular weight from 100 to 26,000.

These include polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and polytetramethylene glycol. Other typical polyols include block copolymers, for example, combinations of polyoxypropylene and polyoxyethylene glycols, more specifically, those having the general formula HO(C2H40)n(C3H60)m(C2H40)nH wherein n and m are together sufficient for attainment of the desired minimum molecular weight, that is about 100. Also included are block copolymers of poly-1,2- and 2,3-oxybutylene and polyoxyethylene glycols and poly-1 ,4-oxybutylene and polyoxypropylene glycols and random copolymers, glycols prepared from blends of two or more alkylene oxides as well as glycols as described above capped with the ethylene oxide units. The polyols may contain arylene or cycloalkylene radicals together with the alkylene radicals as for example in the condensation products of a polyoxyalkylene ether glycol with a,a'-dibromo-p-xylene in the presence of a catalyst. In such products, the cyclic groups inserted in a polyether chain are preferably phenylene, naphthalene, or cyclohexylene radicals or those radicals containing alkyl or alkylene substitutents are in the tolylene, phenylethylene or xylylene radicals. Also included are the polyols prepared by the reaction of hydroxy compounds with acids or anhydrides to form hydroxy terminated esters.

Representative polycarboxylic acids and anhydrides which may be employed include oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, brassylic, thapsic, maleic, fumaric, glutaconic, a-hydromuconic, ss-hydromuconic, a -butyl-a-ethyl-glutaric, a-ss-diethyl-succinic, isophthalic, terephthalic, hemimellitic, and 1,4cyclohexanedicarboxylic. Any suitable polyhydric alcohol including both aliphatic and aromatic may be used such as ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,4tetramethylene glycol, 1,2-butylene glycol, 1,3-butane diol, 1,4-butane diol, 1,3-pentane diol, 1,6-hexane diol, 1,7-heptane diol, glycerol, 1,1,1-trimethylolpropane, 1,1,1trimethylolethane, hexane,-1,2,6-triol, neopentyl glycol, dibromoneopentyl glycol, 1,10decanediol, and 2,2-bis(4-hydroxycyclohexyl) propane.

The fillers or inorganic pigments which are sometimes employed as additives to the polyols may be conventional materials and are generally inert. Typical examples of fillers which may be employed in polyol compositions include attapulgite, kaolin, talc, bentonite, haloysite, aluminum silicate, calcium silicate, magnesium trisilicate, zinc oxide, barium sulfate, titanium dioxide, calcium carbonate and iron oxide. Mixtures of these and other fillers may be used also.

The amount of filler employed can be varied over broad ranges and certainly depends upon the particular properties and characteristics which are desired in the final product.

Generally the filler can be added in amounts of between 10 to 150 percent by weight of the polyol component.

Examples of organic polyisocyanates include such aliphatic diisocyanates as hexamethylene diisocyanate, cyclohexyl-2, 4-isocyanate, 4,4-methylene bis cyclohexyl isocyanate. Included in the aromatic polyisocyanates are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4 and 2,6-toluene diisocyanate, 4,4'-methylene bis phenylisocyanate, 1,5-naphthalene diisocyanate, 4,4' ,4"-triphenylmethane triisocyanate, and polyalkylene polyaryl polyisocyanate.

The organic titanates which can be employed include tetramethyl titanate, tetraethyl titanate, tetraallyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetracyclopentyl titanate, tetrahexyl titanate, tetracyclohexyl titanate, tetrabenzyl titanate, tetraoctyl titanate, tetraethylhexyl titanate, tetranonyl titanate, tetradecyl titanate, and tetraoleyl titanate.

Mixed alkyl titanate compounds include trimethylbutyl titanate, dimethyldibutyl titanate, triethylbutyl titanate, propyl tributyl titanate, ethyl tricyclohexyl titanate, diisopropyl dioctadecyl titanate, dibutyl dioctadecyl titanate, isopropyl triisostearoyl titanate.

Included among the aromatic titanates are methyl triphenyl titanate, tetraphenyl titanate, o- and m-tetramethylphenyl titanate, and 1- and 2-tetranaphthyl titanate.

The following Examples are provided to further illustrate the invention. In these Examples the polyols and additives designated by letters A, B, etc., are as follows: Polyol A is a sorbitol propylene oxide adduct of about 600 molecular weight.

Additive B is tetrabutyl titanate.

Polyester polyol C is a polyester of adipic acid and diethylene glycol of about 2900 molecular weight.

Polyol D is an adduct of glycerol, tetrachlorophthalic anhydride, propylene oxide having a molecular weight of about 600.

Additive E is isopropyl triisostearoyl titanate.

Polyol F is an adduct of glycerol, allyl glycidyl ether and propylene oxide having a molecular weight of about 6500, capped with 15% by weight ethylene oxide, then treated with 20% by weight acrylonitrile.

Polyol G is an ethylene diamine-propylene oxide-ethylene oxide adduct having a molecular weight of about 500 and containing about 10% ethylene oxide.

Polyol H is an adduct of trimethylolpropane, propylene oxide, ethylene oxide having a molecular weight of about 25,000 containing about 19% propylene oxide.

Example I The runs depicted below in Table I were made by adding the designated quantities of Additive B to 272 grams of Polyol A in a lined container and dispersing the mixture with a "Cowles Dissolver" (Registered Trade Mark) at 2500 rpm for 60 seconds. The samples were degassed at 1 to 10 mm mercury pressure at ambient temperatures to remove any trapped air. The viscosities were determined at 80"F. using a Brookfield RVF viscosimeter using a No. 7 spindle at the 2.5 rpm. These results indicate the polyol viscosity reductions achieved by the increased additions of Additive B.

TABLE I Run 1 2 3 4 5 % Addi tive B - 0.1 1.5 5.0 10.0 Viscos ity, cps. 912,000 656,000 456,000 240,000 68,800 Example 2 The procedure of Example 1 was employed in this Example. The effect of Additive E on the viscosity of Polyester polyol C is shown in Table II below.

TABLE II Run 1 2 % Additive E - 1.0 Vicosity, cps 13,500 11,900 Example 3 Employing the procedure of Example 1, a viscosity reduction of Polyol D was achieved employing Additive E as shown in Table III below.

TABLE III Run 1 2 % Additive E - 1.0 Viscosity, cps 840,000 312,000 Example 4 The effect of Additive E on the viscosity of Polyol F was determined using the procedure of Example 1. A substantial reduction in viscosity was achieved as shown in Table IV below.

TABLE IV Run 1 2 % Additive E - 1.0 Viscosity, cps 16,240 11,900 Example 5 Additive B was added to Polyol G and the viscosities were determined using the procedure of Example 1. The reduced viscosity is shown in Table V below.

TABLE V Run 1 2 % Additive B - 1.0 Viscosity, cps 3696 3280 Example 6 Additive E was added to Polyol H and the viscosities were determined using the procedure of Example 1. The reduction of viscosity is shown in Table VI below.

TABLE VI Run 1 2 % Additive E - 1.0 Viscosity, cps 77,200 68,800 Example 7 A mixture of 272 grams of Polyol A was mixed with 128 grams of calcined aluminum silicate, 0.8 grams of phenyl mercuric acetate and 24.4 grams of toluene diisocyanate and 1% by weight Additive B based on the weight of polyol using a Cowles Dissolver at 2500 rpm for 60 seconds. After degassing, the viscosity was measured using a Brookfield RVF viscosimeter at two minutes intervals for 25 minutes at 78"F. An identical mixture without the titanate compound was prepared in the same manner and the viscosity was determined at two minute intervals for 25 minutes at 78"F. A plot of the viscosities versus time revealed that both samples increased in viscosity at the same rate indicating that the titanate compound did not appreciably influence the cure rate.

WHAT WE CLAIM IS: 1. A process for reducing the viscocity of a polyester polyol or polyether polyol which comprises adding an organic titanate.

2. A process as claimed in claim 1 wherein the organic titanate has the formula Ti(OR)4 where the radicals R are identical or different and each is an aliphatic radical having from 1 to 18 carbon atoms, an alicyclic radical having from 1 to 3 rings, each of 5 or 6 carbon atoms and a total of 5 to 18 carbon atoms per molecule an aromatic radical having from 1 to 3 rings and from 6 to 18 carbon atoms, or an acyl radical having from 2 to 18 carbon atoms.

3. A process as claimed in claim 2 wherein, in the formula of the titanate, each R is independently alkyl, alkanoyl, cycloalkyl, aralkyl, phenyl, naphthyl or alkylaryl.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (16)

**WARNING** start of CLMS field may overlap end of DESC **. Example 3 Employing the procedure of Example 1, a viscosity reduction of Polyol D was achieved employing Additive E as shown in Table III below. TABLE III Run 1 2 % Additive E - 1.0 Viscosity, cps 840,000 312,000 Example 4 The effect of Additive E on the viscosity of Polyol F was determined using the procedure of Example 1. A substantial reduction in viscosity was achieved as shown in Table IV below. TABLE IV Run 1 2 % Additive E - 1.0 Viscosity, cps 16,240 11,900 Example 5 Additive B was added to Polyol G and the viscosities were determined using the procedure of Example 1. The reduced viscosity is shown in Table V below. TABLE V Run 1 2 % Additive B - 1.0 Viscosity, cps 3696 3280 Example 6 Additive E was added to Polyol H and the viscosities were determined using the procedure of Example 1. The reduction of viscosity is shown in Table VI below. TABLE VI Run 1 2 % Additive E - 1.0 Viscosity, cps 77,200 68,800 Example 7 A mixture of 272 grams of Polyol A was mixed with 128 grams of calcined aluminum silicate, 0.8 grams of phenyl mercuric acetate and 24.4 grams of toluene diisocyanate and 1% by weight Additive B based on the weight of polyol using a Cowles Dissolver at 2500 rpm for 60 seconds. After degassing, the viscosity was measured using a Brookfield RVF viscosimeter at two minutes intervals for 25 minutes at 78"F. An identical mixture without the titanate compound was prepared in the same manner and the viscosity was determined at two minute intervals for 25 minutes at 78"F. A plot of the viscosities versus time revealed that both samples increased in viscosity at the same rate indicating that the titanate compound did not appreciably influence the cure rate. WHAT WE CLAIM IS:

1. A process for reducing the viscocity of a polyester polyol or polyether polyol which comprises adding an organic titanate.

2. A process as claimed in claim 1 wherein the organic titanate has the formula Ti(OR)4 where the radicals R are identical or different and each is an aliphatic radical having from 1 to 18 carbon atoms, an alicyclic radical having from 1 to 3 rings, each of 5 or 6 carbon atoms and a total of 5 to 18 carbon atoms per molecule an aromatic radical having from 1 to 3 rings and from 6 to 18 carbon atoms, or an acyl radical having from 2 to 18 carbon atoms.

3. A process as claimed in claim 2 wherein, in the formula of the titanate, each R is independently alkyl, alkanoyl, cycloalkyl, aralkyl, phenyl, naphthyl or alkylaryl.

4. A process as claimed in claim 2 wherein the organic titanate is tetraisopropyl

titanate.

5. A process as claimed in claim 2 wherein the organic titanate is tetrabutyl titanate.

6. A process as claimed in claim 2 wherein the organic titanate is isopropyl triisostearoyl titanate.

7. A process as claimed in any of claims 1 to 6 wherein the amount of organic titanate added is from 0.01 to 20 weight percent of the polyol.

8. A process as claimed in claim 7, wherein the amount of organic titanate is from 0.1 to 10 weight percent of the polyol.

9. A process as claimed in claim 7 wherein the amount of organic titanate is from 0.5 to 5 weight percent of the polyol.

10. A process as claimed in any of claims 1 to 9 wherein the organic titanate is added to a composition containing an inorganic filler or pigment and/or a catalyst for reaction of the polyol with a polyisocyanate.

11. A process as claimed in claim 10 wherein the composition contains an organomercuric salt as catalyst for reaction of the polyol with a polyisocyanate.

12. A process as claimed in any of claims 1 to 11, wherein the polyol is a polyoxyalkylene adduct of a polyol and has a molecular weight up to 26,000.

13. A process for reducing the viscosity of a polyol as claimed in claim 1 and carried out substantially as described in any of the foregoing Examples 1 to 7.

14. A urethane polymer when obtained by reaction of a polyisocyanate with a polyol containing a viscosity-reducing amount of an organic titanate as claimed in any one of claims 1 to 6 in the presence of a catalyst.

15. A process for the preparation of a urethane polymer which includes reacting a polyisocyanate with a polyol in the presence of a catalyst and an organic titanate effective to reduce the viscosity of the polyol.

16. A process as claimed in claim 15, wherein the polyol of reduced viscosity contains an organic titanate as specified in any one of claims 2 to 6.