Block Polymers of Hydroquinone Di-(.Beta.-Hydroxyalkyl) Ethers or Isomers Thereof and Tetrahydrofuran/Alkylene Oxide Copolymers

This invention relates to hydroxyl-terminated block copolymers. It is more particularly directed to block polymers containing (a) as one or more of their constituent blocks, a random copolymer of tetrahydrofuran (THF) and one or more alkylene oxides and (b) as the other constituent block, hydroquinone di-(.beta.-hydroxyalkyl) ether, or one of its isomers or homologs.

The invention also relates to polyurethanes prepared using the block polymers as soft segments.

Copolymers of THF and alkylene oxides are known and are used as starting materials in the preparation of polyurethanes. Polyurethanes based on such copolymers, and on customary isocyanates and chain-extenders, can be made in a wide range of stiffnesses by properly selecting the copolymer, isocyanate and chain-extender, and the proportions used. There is, however, a limit to the stiffness which can be obtained in this way, and therein lies a disadvantage, for while polyurethanes of this type are desirable for their other properties, for some uses stiffnesses of a higher order are needed. This is especially true of polyurethanes used in automobiles, particularly for fascia around bumpers.

A need therefore exists for polyurethanes having the attributes of those made with THF/alkylene oxide copolymers, but with improved stiffnesses. This need is filled by polyurethanes made using the block polymers of the invention as soft segments.

The block polymers of the invention are linear hydroxyl-terminated block polymers represented by the structure

or

wherein the A block is a random copolymer of THF and one or more alkylene oxides, and the B block is represented by the structure ##STR1## wherein R is --CH.sub.2 CH.sub.2 --, ##STR2## or ##STR3## and

X is hydrogen when the block polymer is in the A--B configuration, and not present when the block polymer is in the A--B--A configuration.

When the block polymer is in the A--B--A configuration, and the X moiety is not present, the A block on the left side of the molecule, as represented above, is attached directly to the oxygen atom.

The block polymers have number average molecular weights of 500-20,000, preferably 1,000-10,000. The A blocks constitute 60-99% of the weight of the total polymer, and the B blocks 1-40%.

Number average molecular weight is determined by first determining hydroxyl number according to ASTM-D-1638 and then converting this number to number average molecular weight according to the formula

In the definition of the A block, "copolymer" means a block which arises from random polymerization of two, three or four monomeric components. "Alkylene oxide" means any alkylene oxide containing two or three carbon atoms in its oxide ring. It can be unsubstituted or substituted with, for example, alkyl or aryl groups, or with halogen atoms. Illustrative of such alkylene oxides are ethylene oxide, 1,2-propylene oxide; 1,3-propylene oxide; 1,2-butylene oxide; 1,3-butylene oxide; 3,3-bischloromethyl-1,3-propylene oxide; styrene oxide and epichlorohydrin.

Block polymers having the A--B--A configuration are preferred. Especially preferred in this group are those block polymers in which the B block is represented by the structure ##STR4## where R is as defined before. Even more preferred in this group are those block polymers whose B block is derived from hydroquinone di(.beta.-hydroxyethyl) ether (HQEE) and is represented by the structure. ##STR5##

Also preferred are those block polymers of the invention having A blocks which are random copolymers of THF and ethylene oxide, THF and a propylene oxide, preferably 1,2-propylene oxide, or random terpolymers of THF, ethylene oxide and a propylene oxide.

Also preferred for their physical properties are those block polymers whose A blocks have THF/alkylene oxide weight ratios of 10/90-90/10, preferably 30/70-70/30.

In the preferred block polymers, the A blocks constitute 70-90%, by weight, of the total polymer, and the B blocks 10-30%.

The most preferred block polymers of the invention are those of the A--B--A configuration, which have number average molecular weights of 1,000-5,000, whose A blocks are random copolymers of THF and ethylene oxide in which the THF/ethylene oxide weight ratio is 40/60-70/30 and which constitute 80-95%, by weight of the total polymer, and whose B blocks are represented by the structure ##STR6## and constitute 5-20%, by weight of the total polymer.

The block polymers of the invention are made by catalytically and cationically copolymerizing THF and the desired alkylene oxide or oxides in the presence of HQEE or one of its following homologs or isomers: ##STR7##

HQEE itself is available commercially. Compounds 1-8 can be made by the reaction of ethylene oxide or propylene oxide with hydroquinone, resorcinol or catechol.

The THF and the alkylene oxides used can be any of those commercially available.

The catalyst used in preparing the block polymers of the invention can be any proton-donating cationic polymerization catalyst. Illustrative are boron trifluoride, boron trifluoride etherate, acid-activated montmorillonite clays such as that sold by Sud-Chemie of Munich Germany, as Catalyst K-10, and strongly acidic cationic ion-exchange resins.

Strongly acidic cationic ion-exchange resins are preferred for their activity and the ease with which they can be removed from the reaction mass. Preferred among such resins are those which are homopolymers of ethylenically unsaturated monomers, (a), containing groups such that the final catalyst polymer will contain groups of the formula ##STR8## where represents the catalyst polymer chain or a segment thereof;

D is hydrogen, an aliphatic or aromatic hydrocarbon radical of 1-10 carbon atoms, a halogen atom or a segment of the catalyst polymer chain;

X and Y are hydrogen, halogen, an aliphatic or aromatic hydrocarbon radical of 1-10 carbon atoms, but at least one must be fluorine;

R is a linear or branched linking group having up to 40 carbon atoms in the principal chain, and

Z is hydrogen, halogen or an aliphatic or aromatic hydrocarbon radical of 1-10 carbon atoms,

or copolymers of any of the monomers in (a) with at least one other copolymerizable ethylenically unsaturated monomer (b).

The linking group defined by R in formula (B) can be a homogeneous one such as an alkylene radical, or it can be a heterogeneous one such as an alkylene ether radical. In the preferred catalyst polymers, this linking radical contains 1-20 carbon atoms in the principal chain. In the especially preferred catalyst polymers, R is a radical of the structure ##STR9##

Illustrative of monomer (a) are such monomers as trifluorovinyl sulfonic acid, linear or branched chain vinyl monomers containing sulfonic acid group precursors and perfluoroalkylvinyl ethers containing sulfonic acid group precursors.

Illustrative of monomer (b) are such monomers as ethylene, styrene, vinyl chloride, vinyl fluoride, vinylidene fluoride, chlorotrifluoroethylene (CTFE), bromotrifluoroethylene (BTFE), vinyl ethers, perfluoroalkyl vinyl ethers, butadiene, tetrafluoroethylene (TFE) and hexafluoropropylene (HFP).

Homopolymerization and copolymerization to prepare the catalyst polymers can be done according to the procedures described in U.S. Pat. No. 3,784,399 to Grot, and the patents cited therein. Monomer ratios are selected to give the resulting catalyst polymers the proper equivalent weights.

The catalyst polymers have equivalent weights of 950-1,500, preferably 1,100-1,300. Equivalent weight of a catalyst polymer is that weight in grams which contains one gram equivalent weight of sulfonic acid groups, and can be determined by titration.

The catalyst polymers should be effectively free of functional groups, other than --SO.sub.3 H groups, which might interfere with the principal polymerization reaction. "Effectively free" means the catalyst polymers may contain a small number of such groups, but not so many that the reaction is affected adversely or the product contaminated. Illustrative of such groups are carboxyl groups, hydroxyl groups and amino groups,

Catalyst polymers whose polymer chains are of perfluorocarbon monomers are most preferred for use. Illustrative of such monomers the TFE, HFP, CTFE, BTFE and perfluoroalkyl vinyl ethers. Mixtures of monomers can also be used.

Even more preferred as catalyst polymers are copolymers of TFE or CTFE and a perfluoroalkyl vinyl ether containing sulfonic acid group precursors. Most preferred in this case are copolymers of TFE or CTFE and a monomer represented by the structure ##STR10## These catalyst copolymers are prepared in the sulfonyl fluoride form and are then hydrolyzed to the acid form as described in U.S. Pat. No. 3,692,569.

Most preferred as catalyst polymers are copolymers of TFE and monomers of formula (C) in which the respective monomer unit weight ratios are 25/75-50/50. Such copolymers having equivalent weights of 1,100, 1,197, 1,500 and 1,900 are sold by E. I. du Pont de Nemours and Company as Nafion.RTM. perfluorosulfonic acid resin.

The process of preparing the block polymers of the invention ca be carried out in the batch mode or in continuous fashion. The bath method favors production of block polymers having the A--B--A configuration, while the continuous method favors production of block polymers having the A--B configuration.

In either method, the HQEE (or isomer or homolog thereof) is present in the reaction mass at a concentration of 1-25%, preferably 3-10%, by weight of the total mass. THF is present at a concentration of 25-94%, preferably 65-80%, and the alkylene oxide is present at a concentration of 5-50%, preferably 15-30%. A concentration of HQEE (or isomer or homolog) in the high portion of its range favors production of block polymers having the A--B configuration; a concentration in the low portion of the range favors the A--B--A configuration.

The weight percent concentration of the A and B blocks in the final polymer is governed by the amount of HQEE (or isomer or homolog) used in its preparation. A small amount, i.e., in the range of about 1% of the reaction mass, will give a block polymer whose B block constitutes about 2% by weight of the polymer and whose A blocks consititute about 98%. Conversely, a larger amount, i.e., in the range of about 25% of the reaction mass, will give a block polymer whose B block constitutes about 40% by weight of the polymer and whose A blocks constitute about 60%.

The THF/alkylene oxide monomer unit weight ratio in the A block is governed by the ratio of THF to alkylene oxide in the reaction mass, adjusted by the degree of conversion expected.

A block polymer having a number average molecular weight within any desired range can be prepared by properly adjusting reaction temperature, catalyst concentration and feed composition according to well-known principles of polymer chemistry.

To prepare a block polymer of the invention by the batch method, a suitable amount of HQEE, or an isomer or homolog thereof, is charged to a reactor and to this is then added the catalyst. In the case of boron trifluoride or boron trifluoride etherate, the amount used is 0.01-1%, by weight of the total feed used; in the case of clays or ion-exchange resins, the amount used is 0.5-60%, by weight of the total feed used.

To the resulting mass are then slowly added, with stirring, over a period of 4-8 hours the proper amounts of THF and alkylene oxide. The THF and alkylene oxide can be added separately or in admixture, and the temperature of the reaction mass is maintained at about 35.degree.-70.degree. C., preferably 50.degree.-60.degree. C., during the addition.

When addition of the THF and alkylene oxide is finished, the catalyst is separated from the reaction mass by filtration or decantation and residual THF and volatile byproducts are removed from the reaction mass by vacuum stripping or other suitable means. If BF.sub.3 or its etherate is used as the catalyst, it should be first neutralized by a conventional procedure such as treatment with a basic ion-exchange resin, and then removed by filtration or decantation. Preparation of the block polymer is then complete.

In the continuous method for preparing the block polymers, suitable amounts of THF, alkylene oxide and HQEE (or isomer or homolog) are mixed and continuously fed into a reactor containing an appropriate amount of catalyst, while the block polymer product is continuously withdrawn. The rates of feed and withdrawal are balanced so that a residence time of the reaction mass in the reactor of 50-360 minutes is maintained. Catalyst is held in the reactor by suitable screens. As with the product made by the batch process, residual THF and volatile byproducts are removed from the product by vacuum stripping or other suitable means, and preparation of the block polymer is then complete.

The products of the invention thus prepared are polymerizates containing polymers of the A--B--A type and polymers of the A--B type. As already described, polymerizates containing more of one type than the other can be prepared by varying the methods of preparation. All such polymerizates are useful for preparing the polyurethanes of the invention, and separation of the component block polymers from each other is not necessary. The polymerizates can be used directly, and their use frequently confers benefits when polyurethanes having blends of properties are desired. If it is essential that the block polymers be separated from each other, the separation can be made by well-known fractional extraction techniques.

The polyurethanes of the invention are reaction products of (1) a block polymer of the type just described, (2) an organic polyisocyanate and (3) an aliphatic polyol or polyamine chain extender.

The polyisocyanates used in preparing the polyurethanes of the invention can be any of the aliphatic or aromatic polyisocyanates ordinarily used to prepare polyurethanes. Illustrative are

2,4-toluene diisocyanate

2,6-toluene diisocyanate

hexamethylene-1,6-diisocyanate

tetramethylene-1,4-diisocyanate

cyclohexane-1,4-diisocyanate

naphthalene-1,5-diisocyanate

diphenylmethane-4,4'-diisocyanate

xylylene diisocyanate

dicyclohexylmethane-4,4'-diisocyanate

1,4-benzene diisocyanate

3,3'-dimethoxy-4,4'-biphenyl diisocyanate

m-phenylene diisocyanate

isophorone diisocyanate

polymethylene polyphenyl isocyanate

4,4'-biphenylene diisocyanate

4-isocyanatocyclohexyl-4'-isocyanatophenyl methane

p-isocyanatomethyl phenyl isocyanate

Mixtures of isocyanates can also be used.

The isocyanates preferred for use because of the desirable properties they confer on the polyurethane products are diphenylmethane-4,4'-diisocyanate and the toluene diisocyanates.

The chain extenders used in preparing the polyurethanes of the invention can be any of the aliphatic polyols, or any of the aliphatic or aromatic polyamines ordinarily used to prepare polyurethanes.

Illustrative of the aliphatic polyols which can be used as chain extenders are

1,4-butanediol

ethylene glycol

1,6-hexanediol

glycerine

trimethylolpropane

pentaerythritol

1,4-cyclohexane dimethanol

phenyl diethanolamine

Diols like hydroquinone bis(betahydroxyethyl)ether, tetrachlorohydroquinone-1,4-bis(betahydroxyethyl)ether and tetrachlorohydroquinone-1,4-bis(betahydroxyether)sulfide, even though they contain aromatic rings, are considered to be aliphatic polyols for purposes of the invention.

Aliphatic diols of 2-10 carbon atoms are preferred. Especially preferred is 1,4-butanediol. Mixtures of diols can also be used.

Illustrative of the polyamines which can be used as chain extenders are

p,p'-methylene dianiline and complexes thereof with alkali metal chlorides, bromides, iodides, nitrites and nitrates

4,4'-methylene bis(2-chloroaniline)

dichlorobenzidine

piperazine

2-methylpiperazine

oxydianiline

hydrazine

ethylenediamine

hexamethylenediamine

xylylenediamine

bis(p-aminocyclohexyl)methane

dimethyl ester of 4,4'-methylenedianthranilic acid

p-phenylenediamine

m-phenylenediamine

4,4'-methylene bis(2-methoxyaniline)

4,4'-methylene bis(N-methylaniline)

2,4-toluenediamine

2,6-toluenediamine

benzidine

3,3'-dimethylbenzidine

3,3'-dimethoxybenzidine

dianisidine

1,3-propanediol bis(p-aminobenzoate)

isophorone diamine

The amines preferred for use are 4,4'-methylene bis(2-chloroaniline), 1,3-propanediol bis(p-aminobenzoate) and p,p'-methylenedianiline and complexes thereof with alakli metal chlorides, bromides, iodides, nitrites and nitrates. Mixtures of amines can also be used.

The polyurethanes of the invention are prepared in two steps, the first of which is conducted under nitrogen at ambient pressure to prevent oxidation of the reactants and product, and to prevent exposure of the reaction mass to atmospheric moisture. In the first step, the block polymer starting material is dried by heating it at a temperature of 80.degree.-100.degree. C. under vacuum, and is then heated to 60.degree.-125.degree. C., preferably about 70.degree.-90.degree. C., and held there while a stoichiometric excess, preferably twofold to tenfold, of organic diisocyanate is added, with stirring. The actual amount of isocyanate used depends on the molecular weight of the block polymer, as is well-known in the art. The reaction mass is held for about 1-4 hours at 60.degree.-125.degree. C., with stirring, and the free isocyanate content of the mass is then determined by titrating it with di-n-butylamine, as described in Analytical Chemistry of the Polyurethanes, Volume XVI, Part III, D. J. David and H. B. Staley, Wiley-Interscience, 1969, pages 357-359.

In the second step, an amount of polyamine or polyol chain extender calculated to give an isocyanate/hydroxyl or amine mole ratio of about 0.9-1.1 to 1 in the reaction mass, preferably 1.05/1, is degassed at about 30.degree.-120.degree. C. and 10-50 mm Hg pressure and quickly added to the reaction mass.

The reaction mass is held with stirring at 60.degree.-130.degree. C. until it is homogeneous, which normally takes 1-5 minutes. The mass is then poured into molds, preferably preheated to 100.degree.-120.degree. C., and then cured at about 100.degree.-120.degree. C., at a pressure of 1,700-2,000 kilopascals for from 5 minutes to several hours. The casting is then cooled, removed from the mold, aged for about one week at ambient temperature, and is then ready for use.

The polyurethanes of this invention can also be made by reaction-injection and liquid-injection molding techniques, whereby the starting materials are simultaneously injected and mixed in a mold, preferably together with such a conventional polyurethane catalyst as dibutyltin dilaurate or stannous octoate, and then subjected to pressure ranging from ambient to several thousand kilopascals and temperatures ranging from ambient to 150.degree. C. Use of a foaming agent such as a fluorocarbon or water is optional.

In the following examples, all parts are by weight.

19.8 Parts of HQEE and 29.8 parts of Nafion.RTM. perfluorosulfonic acid resin (equivalent weight 1,197), swollen and wet with THF, were charged to a reactor. To the resulting mass was slowly added, with stirring, over a six-hour period, a mixture of 250 parts of THF and 80 parts of ethylene oxide. During the addition, the temperature of the reaction mass was held at about 55.degree.-60.degree. C.

When the feed was finished, the catalyst was allowed to settle and the reaction mass was decanted. Unreacted THF and volatile byproducts were then removed from the reaction mass by first treating it in a steam-heated rotary evaporator at a pressure of about 200 mm of mercury and then holding it under a vacuum of 5-10 mm of mercury at 90.degree. C. for about 2 hours, to give a mixture principally containing a block polymer of the A--B--A configuration in which the B block was represented by the structure ##STR11## and the A block was a random copolymer of THF and ethylene oxide. The block polymer had the following characteristics:

(1) Number average molecular weight--1,494

(2) THF/ethylene oxide weight ratio in the A block--50/50

(3) Percent of total block polymer weight-A blocks--90%

(4) Percent of total block polymer weight-B block--10%.

(A) A slurry of 33 parts of "Volclay" Wyoming bentonite in 100 parts of THF was prepared in a reaction vessel.

(B) A mixture was prepared containing

THF 77.1 parts

Ethylene oxide 15.98 parts

HQEE 6.58 parts

Water 0.34 parts

(C) Enough of (B) was added to the reaction vessel to fill it to overflowing. The contents of the vessel were then held at 55.degree.-60.degree. C., with stirring, while the mixture of (B) was slowly added to it at the rate of 3-4 ml/minute, and effluent was continuously discharged at the same rate. After about two hours from the beginning of the feed, the collection of the effluent was begun.

When the addition was finished, the reaction mass was allowed to stand for 60 hours and was then decanted from the catalyst. Unreacted THF and volatile byproducts were then removed, as shown in Example 1, to give a mixture principally containing a block polymer of the configuration A--B, in which the B block was represented by the structure ##STR12## and the A block was a random copolymer of THF and ethylene oxide.

The product of Example 2, 75.2 parts, was heated to and held at 80.degree. C. for 30 minutes. Heating was then stopped and 53 parts of liquid diphenylmethane-4,4'-diisocyanate were added. The mixture was stirred for five minutes and its temperature was then brought to 80.degree. C. and held there for 2 hours, with stirring.

114.75 Parts of the resulting polymer were held at 110.degree. C. for 30 minutes and to it were then added 9.13 parts of 1,4-butanediol, preheated to 80.degree. C. The resulting mixture was stirred for three minutes at 80.degree. C. and then poured into molds preheated to 110.degree. C., which were then pressed in a platen press at 110.degree. C. and a pressure of 137,895 kilopascals for 19 hours.

The resulting polyurethane had the following physical properties:

The block polymers of the invention can be used in place of conventional polyether or polyester glycols to prepare polyurethanes having enhanced high temperature stiffness, which suits them for use in automobiles, especially bumper fascia.

The block polymers can also be used to prepare polyesters according to well-known methods in which polyols are reacted with dibasic acids or their esters.