Benzudiazepine compound

The present invention relates to polymers, and more particularly, stubborn high molecular weight moldable oxyethylene polymers.

Solid thermoplastic oxyethylene polymers can be prepared by polymerizing a source of oxyaethylene units, such as, for example, trioxane or formaldehyde. Oxyethylene copolymers having better thermal stability can be prepared by introducing, in the polymer chains,. groups which resist detachment caused by heat, more particularly, dispersed oxyalkylene units having adjacent carbon atoms which form links in the polymer chains. These groups can be unsubstituted oxyalkylene units, for example oxyethylene units deriving from cyclic ethers, coane for example ethylene oxide or dioxolane, or they can be substituted oxyalkylene units deriving from lactones, carbonates , anhydrides of cyclic acids or of ethylenically unsaturated compounds, for example styrene, divinyl ether, vinyl acetate, vinyl methyl ketone or acrolein. The polymers and copolymers can be blocked at the ends by acylation or etherification after the polymerization or during the polymerization, using chain transfer agents chosen to increase, their thermal stability, which, in the case of the pepper shakers mentioned, can also be increased. by degradation set to remove the m oxynethylene end groups until the end groups of the polymer chains are those having adjacent carbon atoms.

The present invention relates to certain new oxymethylene copolymers of the general type mentioned above. The copolymers of the invention consist of at least 80% by weight of recurring oxymethylene groups, and contain, in the dispersed state among the oxymethylene groups, oxyalkylene groups having adjacent carbon atoms forming chain links in the polymer chains “, at least some of these latter oxyalkylene groups derived from molecules of a compound

-3 oxacyclic having coranie substituting an alkylol group, in particular by cleavage of the nucleus, between a carbon atone and an oxygen atone in a compound do formula (H₂c -0)_b

4-0- (° ¾ A

E-oa

vs.

in which n is an integer between 0 and 2, n is 1 or 2, is a hydrogen atom or an alkyl or alkylol group containing from 1 to 10 carbon atoms and IL ·, is an alkylene radical having from 1 to 10 carbon atoms.

The preferred process for manufacturing the new oxynethyleno copolymers of the invention consists in copolynerizing tÿi'oxano with a compound having the above formula in the presence of boron fluoride or a boro fluoride complex.

For certain applications, it is necessary to have polymers which have a rigidity combined with a capacity for treatment at high pressures, a combination of properties associated with a low index in the molten state and a high ratio of the indices in the state 10x / lx fade.

The melt index, as used in the present application, is determined by heating a sample of a polymer in a cylinder having a diameter of 50 mm at a temperature of 190 ° C., and by driving it back under a load of 2.16 kg applied by

-4 · a piston, having a diameter of 93.25 mm through an orifice having a diameter of 2.0525 ma and a length of 7.875 ma, and it designates the weight in grams of the polymer passing through the orifice in l space of 10 minutes. The test is described in detail in method ASTMD-1238-57T. Where in general the melt index lüx is used when the values ​​of the melt index are low, and it is determined in an identical manner except that the load is increased up to ten times its value, namely 21.5 kg.

The preparation of rigid polymers with a low melt index has hitherto required the use of exceptionally high purity fillers, since impurities tend to act as chain terminators in polymerizations and give polymers having a low molecular weight and a high melt index. In addition, prior polymers having a relatively low melt index are difficult to process, in that they usually exhibit processability in an extremely narrow temperature range. Thanks to the invention, it has proved possible to obtain, without using raw materials of exceptionally high purity, rigid copolymers which have a low index at. the molten state and a high ratio of the melt indices 10x / lx and which can be processed in a wide range of convenient temperature. Thus, one can obtain copolymers having indices in the melt state so low that they are difficult to measure with precision, for example from 2 to 5, indices with

-5 'the molten state lOx greater than 100 and ratios of the indices in the molten state 10x / lx between 35 and 90.

it is possible that the properties of the new copolymers are attributable to a limited cross-linking between the molecules of the polymer at the sites of the hydroxide groups of the alkylol substituents mentioned. Certainly, for the manufacture of such easily treatable polymers, it is necessary to limit the proportion of the groups containing an alkylol substituent to 7% by weight at most of the polymer, and preferably to less than 1, for example between 0.05 and 0 , 8% by weight of the polymer. By increasing the amount of these groups above 7%, the polymer becomes more and more intractable, and is no longer used as a thermoplastic molding material, but is useful in the role of thermosetting materials, i.e. to say to form conformed objects during the actual manufacture of the polymer.

Preferably, the copolymers of the invention contain, in addition to oxynethylene groups, and groups deriving from oxacyclic compounds having as substituents one or more alkylol groups, other oxyalkylene units having adjacent carbon atoms which form chain links in the polymer chains such as those mentioned above, and in particular, oxyethylene units.

The oxacyclic compound having one or more preferred alkylol substituents is trimethylol propane oxetane, also called 3-ethyl-3 (hydroxymethyl) oxetane, which corresponds to the following formula:

• 6CH.

CH₅CH₂-VS.

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CH₂0H

As other suitable oxacyclic compounds having one or more alkylol substituents, which can be used, mention may be made of triraethylolethane oxetane, 5-propyl-3 (hydroxy methyl) oxetane, 9butyl-3 (hydroxy methyl) oxetane, 3-pentyl-3 (hydroxy nethyl) oxetane, 3-n-octyl-3 (hydroxy ethyl) oxetane,

3-ethyl-3 (hydroxy pentyl) oxetane, 3-hydroxy nethyl oxetane, 3-ethyl-3 (hydroxy propyl) oxetane, 3-ethyl-3 (hydroxy butyl) oxetane, hydroxypropyl and glycidyl ether, pentaerythritol- monofornai, 3,3-dihydroxyethyl oxetane, 5 ~ ethyl-3 (hydroxy ethyl) 1,5-dioxane and p-ethyl-3 oxide (hydroxy nethyl) tetranethylene.

The copolymers are preferably prepared, as already indicated, by nopolymerizing the trioxane and the oxacyclic compound having, as substituents, one or more alkylol groups in the presence of boron fluoride or a boron fluoride complex. The proportions of the comonomer used to obtain easily treatable copolyneres can generally be equal to the proportion of the groups of the polymer which it is desirable to introduce by means of the comonomer. When the copolymer is prepared from trioxane, and from the oxacyclic compound having as substituent one or more alkylol groups alone, it is preferable that this proportion is capable of giving a polymer of which a proportion of 93 to

I

-799.5% by weight consists of oxymethylene groups, stretched with that of ternary polymers, it is preferable to use proportions of the monomers which give a polymer containing at least 7θ% θη weight of oxymethylene groups. Preferred ternary polymers contain from 96.1 to 97% 9% by weight of oxymethylene groups, from 2.0 to 2.9% by weight of oxyethylene groups, and from 0.05 to 0.80 % by weight of groups deriving from the oxacyclic compound having one or more alkylol substituents.

Although the coordination complexes of boron fluoride with compounds in which oxygen or sulfur is the donor atom, for example complexes with ethers, esters, phenols and dialkyl sulfides, are generally satisfactory, prefers the complex with the dibutyl ether catalyst catalyst. However, any other means can be used to catalyze the polymerization of the trioxane to promote cepolymerization. As examples of substances which have been proposed to catalyze the polymerization of trioxane, mention may be made of antimony trifluoride, antimony fluoroborate, bismuth trifluoride, bismuth oxyfluoride, nickel fluoride, aluminum trifluoride, titanium tetrafluoride, manganous fluoride, manganic fluoride, mercuric fluoride, silver fluoride, zinc fluoride, ammonium bifluoride, phosphorus pentafluoride, hydrofluoric acid, thionyl chloride, fluorosulfonic acid, methane sulfonic acid, phosphorus trichloride, titanium tetrachloride,

-8 ferric chloride, zirconium tetrachloride, trichloride d¹aluminum, stannic chloride and stannous chloride.

When a catalyst containing boron fluoride is used, it is usually present in the polymerization zone in an amount such that its boron fluoride content is between 0.0002 and 1.0% by weight relative to the weight of the monomers contained in the polymerization zone. Preferably, quantities of between 0.00 $ and 0.03% by weight are used during a continuous operation, and between 0.0002 and 0.02% during a process by individual charges.

The monomers contained in the reaction zone are preferably substantially anhydrous. Small amounts of moisture such as those which may be present in commercial grade reagents or which may be introduced by contact with atmospheric air, do not prevent polymerization, but must be removed to obtain the best yields.

The temperature prevailing in the reaction zone can be, for example, between 0 ° and 100 ° 0., And the reaction time can be between 5 minutes and 72 hours. Any desired pressure can be used, for example between a pressure below atmospheric pressure and 100 atmospheres or more.

To adjust the molecular weight of the polymer produced, it is possible to incorporate into the reaction mixture a

Low quantity, for example from 100 to 3000 parts by weight per million parts by weight of trioxane, of a chain transfer agent, for example methylal.

The polymerization can be carried out in a solvent medium, for example cyclohexane, and the mixture of monomers can advantageously be subjected to constant shear during the polymerization. When boron fluoride or one of its complexes is used as the catalyst, it is desirable to neutralize the catalyst when the polymerization is complete, since prolonged contact with the catalyst degrades the polymer. The polymerization product can be treated with an aliphatic amine, for example tri-n-butylamine in an amount stoichiometrically in excess relative to the amount of free catalyst contained in the reaction product, and preferably , in an organic Ravage liquor which is a solvent for the unreacted trioxane. According to a variant, if it is dosed /. the reaction product can be washed with water which neutralizes the activity of the catalyst.

The new copolymers, as well as other oxymethylene copolymers having dispersed carbon-carbon bonds, can be stabilized by removing the oxymethylene end groups until a stable end group having a carbon-carbon bond is reached by degradation. thermal or hydrolytic.

The rate of thermal degradation of the copolymers can also be reduced by incorporating conventional chemical stabilizers, for example a combination

-10cAn antioxidant ingredient, for example a substituted bisphenol and an ingredient capable of preventing chain splitting, for example a compound containing trivalent nitrogen.

In the table which follows, we will give the conditions used and the results obtained in the three examples which are given by way of illustration but not limiting of the invention. In the examples, trioxano, ethylene oxide and trimethylol propane oxetane are loaded or the quantities indicated on the state in a reaction vessel equipped with a paddle mixer having the form of the Greek letter sigma¹. Cyclohexane and the boron trifluoride and dibutyl ether complex used as catalyst (34.4% by weight of BF 4) are also charged in the proportions indicated. The reactions are started at 65 ° C., and the temperatures vary during the reaction, as indicated, the values ​​given for the maximum and final temperatures.

In Example 2, a second part of the catalyst is added in the dissolved state in cyclohexane, thereby reducing the ratio of trioxane to cyclohexane from 20 to 16.

The catalyst concentration figures indicate parts of boron fluoride per million parts of trioxane by weight.

Before determining its properties, the washed and dried polymer is stabilized by grinding it with 0.1% cyanoguanidine and 0.5% 2,2'-methylene bis-4- (methyl6-tertiary butyl phenol) for one hour at 21O ° C.

-11in a nitrogen atmosphere in a plastograph.

Kp 2 ^ o ^es^ -'- θ ^^{to of} degradation, i.e. the percentage of loss in. weight per minute when

<td colspan="4">heats the polymer in an air circulation oven</td>

<td colspan="4">at 230 ° C. BOARD</td>

<td>Example No.</td><td> 1</td><td> 2</td><td> 1</td>

<td>Trioxane (parts by weight)</td><td> 100</td><td> 100</td><td> 100</td>

<td colspan="4">Relationship of trioxane to cyclo-</td>

<td>hexane Ethylene oxide (parts in</td><td> 20:1</td><td> 20-16:1</td><td>16: 1 t</td>

<td>weight)</td><td> 2,0</td><td> 2,0</td><td> 2,0</td>

<td colspan="4">Trimethylolpropane oxetane</td>

<td>(parts by weight)</td><td> 0,25</td><td> 0,50</td><td> 0,50</td>

<td>Catalyst concentration</td><td> 75</td><td> 75-100</td><td> 75</td>

<td colspan="4">Reactive temperature range</td>

<td>tional (° C.) ¹</td><td> 91-27</td><td> 83-30</td><td> 92,5-35</td>

<td colspan="4">Duration from start to start</td>

<td>-7 maximum temperature (minutes)</td><td> 8,5</td><td> 19</td><td> 19</td>

<td>Duration of operation (minutes)</td><td> 22</td><td> 40</td><td> 32</td>

<td colspan="4">Yield (%) compared to</td>

<td>all of the monomers</td><td> 85</td><td> 82</td><td> 85</td>

<td colspan="4">Weight loss during</td>

<td>stabilization (%) '</td><td> 13</td><td> 20</td><td> 19</td>

<td>Molten index (dg / minute)</td><td> 5,3</td><td> 13,9</td><td> 2,66</td>

<td colspan="4">Lx melt index</td>

<td>(Dg / min)</td><td> 210</td><td> 770</td><td> 178</td>

<td>10x / lx ratio</td><td> 40</td><td> 56</td><td> 67</td>

<td>^KD 230</td><td> 0,027</td><td> 0,049</td><td> 0,019</td>

Copolyeas easily treatable like them.

-12i-- ·.

• k '.:

• .. k / i kkf • 1

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"Ό /.

hi obtained according to the Examples, apart from being thermoplastic, are soluble in common solvents for oxymethylene polymers. For example, the finely divided polymers are dissolved in para-chlorophenol in a proportion of at least 0.1% by weight at 60 ° C., and are substantially completely soluble in a solvent containing 60% by weight of methanol and 40% by weight of water, when heated with the solvent to a temperature of 160 ° 0. The copolymers have melting points of at least 150 ° C., and can normally be ground at a temperature of 200 ° C. They have an average molecular weight of at least 10,000, and, apart from their high thermal stability as indicated by the figures given by the examples, they exhibit great stability with respect to alkaline media. For example, if the chemically stabilized copolymers are heated to reflux at a temperature of 145 ° 0. about in a% sodium hydroxide solution in water for 45 minutes, the decrease in their weight is less. at 1%.

These copolymers also have great elasticities in the molten state, and therefore they are exceptionally suitable for blow molding or vacuum conformation. High elasticity in the molten state of a polymer causes it to thicken and contract as it is extruded by subjecting it to heat and pressure from a small orifice. During blow molding, this tendency to thicken and contract in a downward parison partially compensates for the effect of gravity on

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k ..

·· '. ··% h,

r. / ί

kk p - B k

k

!. '/ rkq' wSk

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-13parison and allows to maintain a larger parison without increasing the internal tensions caused by the increase in weight. It is convenient to express the elasticity in the molten state as a percentage increase in the diameter of the extrusion product relative to the diameter of the orifice when the polymer is extruded under the conditions used to determine the index at l melt as described in method ÄGTMD-1238-57I · Copolymers according to the invention are commonly obtained ayani / elasticities in the molten state greater than 20% and even greater than 30%. For an oxymethylene homopolymer having a comparable melt index, or for a comparable copolymer not containing groups derived from oxacyclic compounds, having as substituents one or more alkylol groups, the elasticity in the melt is usually less than 10%. ^r

The copolymers have a high resistance

J mechanical in the molten state, and therefore, lend themselves to processing in operations, such as for example blow molding of relatively large bottles, and the extrusion of complicated and large profiles, especially when a good setting dimensions is important. Thus, during the extrusion of a pipe it is possible to maintain a perfect adjustment of the vibrations of the surface and of the thickness of the wall.

In a typical blow molding operation, round Boston-type bottles with a capacity of 113.4 g can be prepared using a 30 mm extruder having a ratio of length to

-14 14: 1 diameter, a die with an internal ui / 14.05 ram, a mandrel with an external diameter of 5 mm, a cord length of 11.5 min, a die temperature of 171 ° C., a temperature of the melt of 193 ° C., a temperature of the mold of 110 ° 0. and a cycle of 20 to 22 seconds.

During a typical extrusion, a pipe having an internal diameter of 25 mm and having a wall of 2 mm can be extruded through a normal Davis extruder of 62.65 mm having a die having an internal diameter of 30 Dim and a mandrel having an external diameter of 25.875 mm, an external sleeve with a length of 225 mm and having an internal diameter of 30.875 mm being located in the vicinity of the die and concentrically with respect thereto. The sleeve adjusts the outside diameter of the pipe, while the inside diameter is adjusted by the drawing speed. A temperature of u04 ° 0 can be maintained. at the die and a temperature of 80 ° C. to the sleeve. An air pressure can be maintained in the extruded line corresponding to a gauge pressure of 1.61 kg / cm 2 and the line is removed at a speed of 1.95 meters / minute.

By copolymerizing trioxane with an amount greater than 7% by weight of the oxacyclic compound having as substituents, one or more alkylol groups, it is possible to obtain intractable apparently crosslinked copolymers, the oxacyclic compound having, as substituents, one or more alkylol groups, being used in amounts up to 20% by weight relative to the total weight of the monomers. In these copolymers, f '

As in easily treatable copolymers, it is preferable to incorporate, as a third monomer component, a compound having at least two adjacent carbon atoms, such as for example ethylene oxide or dioxolane. According to this aspect of the invention, the copolymers preferably comprise from 70 to 98.5% by weight of oxymethylene groups, from 0.5 to 10% by weight of the groups having adjacent carbon atoms and more than 7%, and up to 20% by weight of groups deriving from the oxacyclic compound having, as substituents, one or more alkylol groups.

The substantially untreatable copolymers can be given the desired shape before the completion of the polymerization process. One can heat, for example, the polymerization mixture and subject it to a shearing action for a limited period of time sufficient to guarantee a complete mixture, and then, one can lo transfer from a mold to conform it ot