JPH0470323B2 - - Google Patents

Description

Claim 1: Reacting an amine-functional compound having an equivalent weight of at least 400 with an excess of polyisocyanate in the substantial absence of a solvent to form an isocyanate-terminated prepolymer or quasi-prepolymer; or a quasi-prepolymer is reacted with an isocyanate-reactive material by reactive injection molding to produce a polyurea and/or
or forming a polyurea-polyurethane prepolymer and using a ratio of amine-functional compound to polyisocyanate such that the isocyanate-terminated prepolymer or quasi-prepolymer has an isocyanate content of 3 to 12% by weight. A method for producing a polyurea or polyurea-polyurethane polymer having a density of at least 0.8 g/cc.

2. The method of claim 1, wherein said amine-functional compound has an average equivalent weight of 400 to 6000 and has 1 to 4 amine groups per molecule.

3. The method of claim 2, wherein the amine-functional compound is an amine-terminated polyether.

4. The method of claim 3, wherein at least 25% of the total number of hydroxyl groups and amine groups of said amine-functional compound are amine groups.

5. The method according to claim 4, wherein the polyisocyanate is an aliphatic polyisocyanate or an aromatic polyisocyanate.

6. Said polyisocyanate is an aromatic polyisocyanate containing at least one moderately reactive isocyanate group, and said amine-functional compound is a primary amine-terminated compound having a degree of amination of 25 to 90%. The method described in item 5.

7. Claim 5, wherein the polyisocyanate is an aromatic polyisocyanate with highly reactive isocyanate groups, and the amine-functional compound is a primary amine-terminated compound with a degree of amination of 25 to 85%. the method of.

8. The method of claim 1, wherein the isocyanate-reactive material is an amine- or hydroxyl-containing compound having an equivalent weight of less than 200.

9 The isocyanate-reactive substance is 400 to 5000
A method according to claim 1, wherein the polyol or amine-terminated polyether has an equivalent weight and a functionality of 2 to 3.

10. The method of claim 3, wherein the amine-functional material is a microreaction product of a primary amine-terminated polyether and an unsaturated compound containing carbon-carbon double bonds.

Description The present invention relates to a process for making polyurea and/or polyurea-polyurethane polymers, particularly non-cellular or microporous elastic and structural polyurea-containing polymers.

Polyurethane polymers are known and used to form a wide variety of elastic, structural and foam products. These polymers are conventionally known as polyisocyanates and "polyols"
It is prepared by reacting what is commonly called a polyhydric acid group-containing compound with a moderate to high equivalent weight. Polyols provide "soft" or plastic segments that impart impact resistance, elongation, and other desirable properties to the polymer. Frequently, "chain extenders" or compounds containing low equivalent weights of polyhydroxyl or polyamine groups are also used to provide crosslinks or "hard segments" to the polymer. These chain extenders impart increased modulus and other desirable properties to the polyurethane.

It has been found that not only the different presence of hard and soft segments, but also the way they are distributed in the polymer has a large effect on the properties of the polymer. In general, it has been found that certain properties of the polymer are maximized when the hard and soft segments are well "separated". Such separation of regions refers to the existence of regions containing a high proportion of hard segments and regions containing a high proportion of soft segments at a microscopic or higher level.

This desired phase separation is achieved in polyurethane polymers by reacting the polyisocyanate with all or part of the "polyol," which is then subsequently reacted with the chain extender and the remaining polyol, if present. will be achieved. In this way, a soft segment prepolymer is produced prior to the production of the final polymer. Such an approach is described, for example, in US Pat. No. 4,297,444.

Alternatively, hard segmented prepolymers can be used by first reacting the polyisocyanate with all or part of the chain extender and then with the polyol and any remaining chain extender.

In another attempt to improve polyurethane polymers, the hydroxyl-terminated materials commonly used to make the polymers were replaced in greater or lesser amounts with amine-functional compounds, e.g., U.S. Pat.
See 4444910 and 4530941.
Amine functional materials generate urea bonds in place of urethane bonds in the polymer. These urea bonds are stronger and more thermally stable than urethane bonds.

Although these amine-functional materials have the advantages mentioned above, there are some severe problems when using them. Because amines react rapidly with isocyanate groups, their use is generally limited to reactive injection molding (RIM) processes. Even in the RIM process, it has been found that it is generally necessary to use a sterically hindered amine chain extender such as diethyltoluenediamine (DETDA) to slow the polymerization reaction sufficiently to make a molded article. ing.
Additionally, amines are known to undergo various secondary reactions with isocyanates at room temperature resulting in undesirable crosslinking and gel formation in polyurea-containing polymers. It would be desirable to provide polyurea polymers that are also easier to process.

Additionally, it is always beneficial to provide polymers with improved physical properties and processability.

Accordingly, there is provided a method for producing polyurea containing polymers that affords greater processing flexibility, and a polymer product having physical properties equal to or superior to those exhibited by conventionally produced polyurea polymers. It would be desirable to do so.

The present invention involves reacting an amine-functional compound having an equivalent weight of at least 400 with an excess of polyisocyanate to form an isocyanate-terminated prepolymer or quasi-prepolymer, and then converting the isocyanate-terminated prepolymer or quasi-prepolymer into an isocyanate-reactive material. and reacting the amine-functional compound and the polyisocyanate with an isocyanate-terminated prepolymer or quasi-prepolymer in an amount of from 3 to 12% by weight of the isocyanate-terminated prepolymer or quasi-prepolymer.
It is directed to a process for producing polyurea and/or polyurea-polyurethane polymers, characterized in that they are used in proportions having an isocyanate content of .

Several surprising advantages are obtained by the method of the invention. The reaction of an isocyanate-terminated prepolymer or quasi-prepolymer with an isocyanate-reactive material is unexpectedly slow, even when the isocyanate-reactive material is a primary or secondary amine. This long curing time provides greater processing flexibility for the polymers according to the invention. When glycols or relatively slowly reactive amines are used as isocyanate-reactive materials,
It is even possible to mix or cast reactive substances by hand. Of course, catalysts can also be added to the reaction mixture to speed up curing, as is often desired in RIM processing. The process of the present invention also allows the use of highly reactive amines such as ethylenediamine and toluenediamine as isocyanate-reactive materials. Such highly reactive amines are generally too reactive for use by conventional processing, even in RIM systems. However, according to the invention, such amines can be used for the production of molded articles, especially molded articles by the RIM process.

Polymers produced according to the invention exhibit unexpected properties. The polymer produced according to the present invention is
Generally, they exhibit glass transition temperatures 5 to 20 degrees Celsius lower than similar polymers made in one shot processes. This advantage is particularly evident when using aliphatic polyisocyanates. Also,
The heat distortion temperatures of these polymers, as measured by heat sag tests, are usually significantly higher than urea-containing polymers of similar flexural modulus made by conventional techniques. Thus, the present invention provides polymers that can be used and processed over a wider temperature range than similar polymers made by one-part processes.

According to the present invention, an isocyanate-terminated prepolymer or quasi-prepolymer is reacted with an isocyanate reactant to form a urea-containing polymer. Preferably, the polymer is non-porous or microporous. The term "isocyanate-reactive material" as used herein is defined by the Journal of the American
Chemical Society, Vol. 49, page 3181 (1927)
refers to compounds containing 2 or 3 hydrogen atoms, or mixtures thereof, that are active according to the Zelewitinoff test as described by Kohler in 1996. Preferably, the isocyanate-reactive material consists of a low equivalent weight polyol or polyamine (sometimes referred to herein as a "chain extender").

The isocyanate-terminated polymer or quasi-prepolymer consists of the reaction product of an amine-functional compound or mixture thereof and a stoichiometric excess of polyisocyanate. The term "prepolymer" is used herein to refer to the isocyanate-terminated material formed by the reaction of an amine-functional compound and a polyisocyanate. The term “quasi-prepolymer”
``prepolymer'' is used to refer to a prepolymer-containing mixture that also contains unreacted polyisocyanate. The quasi-prepolymer is prepared by reacting the amine-terminated compound with a greater amount of polyisocyanate than is required to react with its amine groups so that there is an excess of unreacted polyisocyanate in the product. Can be prepared. Alternatively, a quasi-prepolymer can be prepared by forming a prepolymer and then mixing it with additional polyisocyanate.

The term "amine-functional compound" or "amine-functional material" as used herein refers to a compound or mixture thereof that contains at least one amine group having an active hydrogen atom capable of reacting with an isocyanate group to form urea. The amine-functional compound or material contains, on average, at least two amine groups as described above, or one amine group as described above and at least one other functional group containing an active hydrogen atom. It is preferable. Also, the amine functional compound has an equivalent weight of at least 400. For purposes of this invention, the equivalent weight of an amine-functional compound or substance is calculated based on the number of amine groups (or other groups containing active hydrogen atoms) as opposed to the number of hydrogen atoms. For example, a compound with a molecular weight of 2000 containing two primary amine groups would be considered to have an equivalent weight of 1000.

Primary or secondary amine-terminated polyethers having an equivalent weight of 400 to 6000, preferably 500 to 3000 and containing on average 1 to 4 amine groups per molecule are preferred. Suitable such amine-terminated polyethers and methods for their preparation are described, for example, in US Pat. No. 3,654,376 and US Pat. No. 3,666,788. Generally, the process described in these patents consists of reacting a hydroxyl-terminated polyether with ammonia or a primary amine in the presence of a specific catalyst to reduce and aminate the polyether.

The preparation of primary amine terminated polyethers is particularly described in US Pat. No. 3,654,376. Commercially available primary amine-terminated polyethers include
Jeffamine T-5000, Jeffamine D-2000,
Jeffamine D-400 (Texaco Chemical Company product)
There is. Jeffamine is a trade name of Texaco Chemical Company.

For the production of secondary amine-terminated polyethers, US Pat.
It is described in the specification of No. 3666788. Typically,
Polyether polyols terminated with aliphatic primary amines, especially C ₁ -C ₆ aliphatic amines, and aromatic amine terminated materials, especially aniline-capped polyethers, are preferred.

In most of the above methods, amination of the polyether occurs in less than quantitative amounts. Therefore,
The product will contain compounds with only one amine group per molecule and some residual hydroxyl groups. In the present invention, the use of such substances accounts for at least 25% of the total number of hydroxyl and amine groups, preferably at least 50%, more preferably from 50 to
As long as it is 100% amine groups, it is suitable. Furthermore, a mixture of an aminated substance and a hydroxyl group-terminated substance is
Suitably, at least 25% of the total number of amine groups and hydroxyl groups are amine groups.

Other secondary amine-terminated polyethers may be prepared by subjecting the above-mentioned primary amine-terminated polyethers to Michael addition reactions with unsaturated compounds such as acrylic esters, methacrylic esters, acrylonitrile, or primary amine-terminated polyethers. It is advantageously prepared by reacting with other compounds having carbon-carbon double bonds that are sufficiently active to . Of particular interest are the reaction products of acrylonitrile and _C1 - _C6 alkyl or hydroxyalkyl esters of acrylic or methacrylic acid. Also useful are secondary amine-terminated polyethers formed by reacting the corresponding primary amine-terminated polyethers with formaldehyde and hydrogen cyanide adducts. The reactions described in this step are advantageously carried out by heating the reactants in the presence of a suitable diluent such as a lower alcohol. Suitable reaction conditions are described in US Pat. No. 3,666,788.

In addition to the above, as amine-functional compounds,
It is also within the scope of this invention to use primary or secondary amine terminated materials complexed with acids, acid halides or alkyl chlorides, bromides, iodides. Particularly useful are primary or secondary amine terminated polyethers complexed with organic acid halides (eg, benzoyl chloride, acetyl chloride), phosphonic acids, halogen acids, C1 _{- C4} alkyl iodides.

The amine-functional compound reacts with excess polyisocyanate to form an isocyanate-terminated prepolymer or quasi-prepolymer. Aromatic polyisocyanates, ie, isocyanates in which the isocyanate group is bonded directly to an aromatic ring, as well as aliphatic isocyanates are useful.

Representative aromatic polyisocyanates useful in the present invention include phenyl isocyanate, 2,6
-Toluene diisocyanate, 2,4-toluene diisocyanate, ditoluene diisocyanate, naphthalene 1,5-diisocyanate, bis(4-isocyanatephenyl)methane (MDI),
Bis(3-methyl-2-isocyanatophenyl)methane, bis(3-methyl-4-isocyanatophenyl)methane, bis(3,5-diisopropyl-4-aminophenyl)methane, 4,4'-diphenylpropyl Redene diisocyanate, 4,
4'-diphenylethane diisocyanate and various polymethylene polyphenyl polyisocyanates. Of course, toluene diisocyanate, bis(4-isocyanatophenyl)methane (MDI) and polymethylene polyphenyl polyisocyanate are preferred due to their availability and generally superior performance. The polymethylene polyphenyl polyisocyanate typically used here has an average of 2.1 to
It has a functionality of 3.5 and contains 20 to 100% by weight of methylene diphenyl diisocyanate isomers, with the remainder being high molecular weight polymethylene polyphenyl polyisocyanate. Such isocyanate mixtures are commercially available and are described in U.S. Pat.
It can be prepared by the method described in No. 3362679.

Suitable organic aliphatic polyisocyanates include, in addition to the halogenated derivatives of the organic aromatic polyisocyanates mentioned above, 1,6-hexamethylene diisocyanate, isophorodiisocyanate, 1,4
-cyclohexyl diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexylisocyanate) or mixtures thereof.

The reaction between the polyisocyanate and the amine group-containing substance can be carried out as is or in a suitable solvent. Amine-functional compounds are highly reactive and produce polymers of significant molecular weight when contacted with polyisocyanates. These high molecular weight materials are insoluble in the unreacted polyisocyanate and precipitate, inhibiting the process. Also, the production of high molecular weight materials broadens the molecular weight distribution of the prepolymer or quasi-prepolymer, which also has an adverse effect on the properties of the product polymer. Therefore,
Conditions for the prepolymer formation reaction are advantageously selected to minimize the formation of such high molecular weight materials.

The formation of high molecular weight materials can be minimized by conducting the reaction in a manner that minimizes the formation of high local concentrations of amine-functional compounds in the polyisocyanate. This can be easily accomplished, for example, by adding the amine-functional material in portions to the polyisocyanate under stirring conditions. Alternatively, the reaction can be carried out in a suitable solvent, especially when using more reactive polyisocyanates and amine-functional materials.

Generally, the prepolymer formation reaction is carried out at moderate concentrations, i.e. -10 to 100 °C, preferably 15 to 55 °C.
Let's do it. It is an added benefit that the lower temperature, -10 to 30°C, slows down the reaction and inhibits the formation of high molecular weight materials. However, at elevated temperatures the reduced viscosity of the amine-containing material allows more rapid intermixing of the components, which also tends to reduce the formation of high molecular weight materials. Clearly, at high temperatures it may be difficult to control the formation of high molecular weight substances.

The reaction is carried out until substantially all of the amine groups of the amine-functional compound have reacted with the polyisocyanate. Because of the reactivity of amine-functional compounds, this reaction is almost instantaneous in most cases. When preparing prepolymers using blends of amine-functional materials and polyols, somewhat longer reaction times,
That is, 5 minutes to 2 hours may be required.

It is often desirable to store prepolymers for extended periods of time (ie, from hours to months) before using them to make polymers. In such cases, it is desirable to prepare prepolymers that are stable, ie, do not undergo substantial amounts of secondary reactions during storage. Such stability is conventionally determined by measuring the -NCO content of the prepolymer over a period of time. Generally, the prepolymer -
It can be said that there is adequate stability when the NCO content decreases by less than 2% by weight.

In general, the stability of a polyurea isocyanate-terminated prepolymer or quasi-prepolymer depends somewhat on its composition, and more specifically on the degree of amination of the particular polyisocyanate and amine-functional compound used. . Generally, stability is improved by the use of less reactive polyisocyanates and by the use of less than quantitative amounts of aminated amine-functional compounds. Additionally, secondary amine-terminated amine-functional compounds and such amine-functional materials complexed with acids, acid halides, or other halides as described above are generally more stable precursors than primary amine-terminated materials. Produces polymers. Secondary amine-terminated polyethers, prepared by reacting the corresponding primary amines with unsaturated compounds in a Michael addition reaction, react with highly reactive polyisocyanates to form particularly stable prepolymers.

Aliphatic polyisocyanates readily react with primary amine terminated compounds having a degree of amination of up to 100 percent to form stable prepolymers.
Particularly stable prepolymers are formed at all degrees of amination when reacted with secondary amine-terminated compounds.

Moderately reactive aromatic polyisocyanates or aromatic polyisocyanates having at least one moderately reactive isocyanate group and one or more highly reactive isocyanate groups, such as 2,
4-Toluene diisocyanate and 2,4'-methylene diphenyl diisocyanate are generally primary amine-terminated compounds having a degree of amination of 25-90%, preferably 25-75%, more preferably 25-50%. reacts with to form a stable prepolymer. These polyisocyanates, when reacted with arylamine terminated materials, typically produce stable prepolymers with a degree of amination between 25 and 100%, preferably between 25 and 75%. When alkylamine terminated materials are used with these compounds to make prepolymers, 25-80%, preferably 25-80%
It is advantageous to have a degree of amination of 65%. Moderately reactive isocyanates, for purposes of the present invention, are those having a reactivity intermediate between the less reactive aromatic polyisocyanates and the highly reactive polyisocyanates, MDI.

Highly reactive polyisocyanates, such as methylene diphenyl diisocyanate and its polymer derivatives, typically contain 25 to 85%, preferably 25%
a primary amine-terminated compound with a degree of amination of ~50% and a second with a degree of amination of 25-100%, preferably 25-70% and more preferably 40-70%.
Reacts with amine-terminated materials to produce stable prepolymers.

Such prepolymers or quasi-prepolymers are reacted with at least one isocyanate-reactive material to form a polymer that is preferably non-cellular or microporous. A polymer is considered non-cellular or microporous if it has a density (in the unfilled state) of at least 0.8 g/cc. Preferably, the polymer has a density (unfilled) of at least about 0.9 g/cc, more preferably from 0.95 to 1.2 g/cc.

Isocyanate-reactive materials useful in the present invention include Kohler, Journal of The American
Chemical Society, Vol. 49, page 3181 (1927)
Included are such compounds that have multiple moieties that contain active hydrogen atoms according to the Zelewitnov test described in . Examples of such moieties include mercaptan groups, hydroxyl groups, primary amine groups, secondary amine groups, and acid groups. Amine and hydroxyl group-containing compounds are preferred. Suitable isocyanate-reactive compounds include relatively low equivalent weight compounds, relatively high equivalent weight compounds, and mixtures thereof. Preferably, relatively low equivalent weight compounds have an equivalent weight of less than 200, more preferably between 30 and 150.

The conditions for the polymerization reaction depend somewhat on the composition of the isocyanate-reactive material and prepolymer or quasi-prepolymer used in the reaction mixture. If relatively reactive isocyanate groups are present in the prepolymer or quasi-prepolymer, or if particularly reactive isocyanate-reactive materials are used, reaction conditions that promote rapid mixing of the components and slow reaction may be used. It is desirable to adopt it. In such cases, a mechanical mixing device capable of mixing and reacting the components at temperatures between -10 and 40°C in the presence or absence of a small amount of catalyst, as well as rapidly mixing the components and transferring the mixture into the mold, is used. It is preferable to use Preferably, a RIM type device is used. After the material is transferred into the mold, higher temperatures can be used to complete the curing reaction.

Greater flexibility in reaction conditions is possible when the prepolymer or quasi-prepolymer contains low-reactivity isocyanate groups and/or the isocyanate-reactive material is relatively low-reactivity.
In such cases, the reactants can be at elevated temperatures from ambient temperature (ie, -10 to 100°C), can be catalyzed if desired, and can be mixed by hand or machine. The more rapid reactions desired for RIM processing are easily achieved by using catalysts and higher reaction temperatures (30-100°C).

Suitable low equivalent hydroxyl group-containing chain extenders include, for example, ethylene glycol, propylene glycol, trimethylolpropane, 1,4-butanediol, diethylene glycol, dipropylene glycol, bisphenol, hydroquinone, catechol, resorcinol, triethylene glycol, These include tetraethylene glycol, glycerin, low molecular weight ethylene and/or propylene oxide derivatives of glycerin, ethylene diamine, diethylene triamine, and mixtures thereof.

Suitable low equivalent weight aliphatic amine-containing compounds include, for example, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, isophoronediamine, diethylenetriamine, ethanolamine, aminoethylethanolamine, diaminocyclohexane, hexamethylenediamine, These include aminoethylpiperazine, bis(aminopropyl)piperazine, 1,2-diaminocyclohexane, poly(oxyalkylene)amine, bis(p-aminocyclohexyl)methane, triethylenetetramine, and mixtures thereof. Particularly suitable are aminated polyoxypropylene glycols having an average weight of 60 to 110, but these materials are usually used in conjunction with another amine or glycol chain extender.

Suitable low equivalent weight aromatic amines that can be used in the present invention include, for example, 2,4-bis(p-aminobenzyl)aniline, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,3- phenylenediamine, 1,4-phenylenediamine,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, naphthalene-1,5-
Diamine, 1-methyl-2-methylamino-4-
Aminobenzene, polyphenylpolymethylene polyamine, 1,3-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6
-diaminobenzene, 1,3,5-triethyl-
2,6-diaminobenzene, and mixtures thereof. The above aromatic amines substituted with an amine group at each ortho position are significantly blocked by stearic acid and react more slowly than the above aromatic amines which are not substituted with an amine group at one or more ortho positions. .

Suitable relatively high equivalent weight compounds include, for example, polyether polyols, polyester polyols,
so-called polymer or copolymer polyols,
There are hydroxyl group-terminated acetal resins, polyhydroxyl group-containing phosphorus compounds, and amine-terminated polyethers. Most preferred are equivalents of 400 to 5000 and 2 to 4, especially 2 to 3.
A polyol or amine-terminated polyether as described above having an average functionality of .

In addition to the above ingredients, it is often desirable to incorporate various other ingredients into the reaction mixture. It was mentioned above that catalysts for polymerization reactions can be used in certain cases. Suitable such catalysts commonly include tertiary amines and organometallic compounds. Organometallic catalysts include, for example, carboxylic acid primary
A lead, mercury or stannous compound such as tin, trialkyltin oxide, dialkyltin dihalide, or dialkyltin oxide, where the organic group or hydrocarbon group of the organic part of the tin compound is 1 to 8.
carbon atoms are suitable. for example,
Dibutyltin dilaurate, dibutyltin diacetate, diethyltin diacetate, monooctanoic acid
Tin, di(2-ethylhexyl)tin oxide, stannous oleate, or mixtures thereof can be used. Tertiary amine catalysts include trialkylamines, heterocyclic amines such as alkylmorpholines, 1,4-dimethipiperazine, triethylenediamine, and aliphatic polyamines such as N,
There is N,N',N'-tetramethyl-1,3-butanediamine.

Blowing agents can also be used to produce cellular polymers. However, the formation of cellular polymers is undesirable. However, provided the polymer has a density of at least 0.8 g/cc, a blowing agent can be used to slightly expand the polymer into a microporous structure. Suitable blowing agents include low boiling halogenated hydrocarbons such as trichloromonofluoromethane and methylene chloride, carbon dioxide, nitrogen, water, or other gases that volatilize or otherwise produce gases under the conditions of the polymerization reaction. There are known substances.

Other conventional formulation ingredients, such as stabilizers,
Bulking agents, inert fillers (eg glass fibers, carbon fibers) or pigments may also be used. European Patent Publication No. 119471 and International Publication No. WO86/
Internal mold release agents, such as those described in US Pat. No. 1,215, may also be suitably used in the present invention.

The polymers produced according to the invention are useful, for example, as static or dynamic elastomeric bodies used in the manufacture of fascias for automobile bumpers, or as intumescent cushions such as those used in automobile partitions and stability pillows.

EXAMPLES The following examples are intended to illustrate the invention, but are not limiting. All parts and percentages are by weight unless otherwise specified.

Example 1 16.9 g of hexamethylene diisocyanate (HMDI) is placed in a resin reaction kettle equipped with a stirrer, heat lamp, and nitrogen atmosphere. Heat HMDI to 40 °C. While stirring, add 50% primary amine groups,
50 g (0.05 mol) of aminated polyoxypropylene diol containing 37% methylamine groups, 10% dimethylamine groups and 3% hydroxyl groups are added over a period of 2 hours. The aminated diol is prepared by reacting methylamine and a diol in a tubular reactor according to the general method described in US Pat. No. 4,152,353. The weight ratio of methylamine to diol is 0.35. The reaction was carried out at a temperature of 265℃ and 1100psi
(7.58MPa), hydrogen was added to the reactor at 2
It was fed at a rate of cubic feet/hour (0.057 m ² /hour). Upon addition of the amine, the viscosity of the reaction mixture increases, indicating that a prepolymer has been formed. Following addition of the amine, a clear colorless viscous liquid is obtained. A prepolymer is obtained with an -NCO content of 8.9%. This prepolymer is reacted with diethyltoluenediamine (DETDA) at an index of 1.05. The reaction is carried out by mixing the ingredients by hand and pouring the reaction mixture onto a mold preheated to 300°C (149°C). The gel time for this reaction is
It is 30 seconds. The polymer cures at 300°C (149°C) for 60 minutes. The resulting elastomer has the expected value -40
It had a glass transition temperature of -55°C.

Example 2 Place 99 grams of hexamethylene diisocyanate in a suitable flask under a nitrogen atmosphere. Add 300% of the amine polyoxypropylene diol as described in Example 1 to this flask with constant stirring.
Drip grams. A prepolymer is obtained with an -NCO content of 9.25%.

After overnight storage, the prepolymer was degassed and DETDA
was added, degassed again at room temperature, and the mixture was reduced to 100%
By pouring it onto a mold preheated to (37.8℃),
209 g of prepolymer and 41 g of DETDA were reacted. Molded product is 300〓 (149℃) 10000psi
(68.95MPa) Cures in 30 minutes. The properties of the molded product obtained are as follows. Flexural modulus 11900psi
(82.05 MPa), tensile strength 1180 psi (8.14 MPa), die “C” tear strength 405 lb/linear inch (70.9 KN/m), elongation 163%, heated sag (325〓 (163 ℃) 30 minutes) 0.16
inch (4.1mm), Tg≒-55℃.

Example 3 Following the general procedure described in Example 2, 4,4'-
Methylene diphenyl diisocyanate (MDI)
10.1% by reacting 16.65g with 23.3g of aminated polyoxypropylene glycol with a molecular weight of 2000
A prepolymer with a -NCO content of -NCO is produced. The aminated material was synthesized with aniline according to the general method described in U.S. Pat.
It is created by reacting polyols. The reaction is carried out using 0.9 parts of aniline per part of polyol.
The temperature is approximately 205°C and the pressure is 600psi (4.1MPa).
Add hydrogen to the reactor at 10 cubic feet/hour (78.7 cm ³ /
feed at a speed of 2 seconds). The resulting aminated polyol contains 40% primary amines, 39% saturated secondary amine end groups, 4% aniline groups, and about 11% residual hydroxyl groups. Approximately 20.6g of this prepolymer
Mix by hand with 4.41 g of DETDA and react to form a moldable elastomer. The resulting polymer has a glass transition temperature of -53°C.

Example 4 A prepolymer is prepared as in Example 3 using 14.6 g of toluene diisocyanate and 35.4 g of the aminated material of Example 3. A prepolymer is obtained with an -NCO content of 9.23%. This prepolymer 20
g is reacted with 3.82 g of DETDA as described in Example 2. The resulting polymer has a glass transition temperature of -46°C.

Example 5 Following the method described in Example 3, 36.7 g of isopropylamine-terminated polyoxypropylene glycol of molecular weight 2000 and 13.3 g of hexamethylene diisocyanate are reacted to form a prepolymer with an -NCO content of 9.5%. Mix this prepolymer with DETDA and an index of 100 by stirring the ingredients by hand.
Pour into a mold (12 inches x 7 inches x 1/8 inch) (305 mm x 178 mm x 3.2 mm) heated to (37.8°C) and react. Next, the molded product was 300〓(149
Cure at 10000psi (68.95MPa) for 30 minutes.
The tensile strength of the resulting compact is 2409psi (16.61MPa)
It is. Elongation is 503%, flexural modulus is 32400psi
(223.4MPa), die “C” tear strength is 401 lb/
Linear inch (70.2KN/m), glass transition temperature is -
It is 56℃. 325〓 with 6 inch (152mm) overhang
(163°C) 0.2 inch (5.1 mm) molded product sag in 30 minutes.

Example 6 A primary amine terminated polyoxypropylene triol, commercially available as Jeffamine T-5000, is reacted with acrylonitrile to form a derivative containing a terminal mono(cyanoethyl)amine group. This derivative was added dropwise to MDI at room temperature in sufficient proportion to achieve an NCO content of 12%.
A prepolymer is obtained. The resulting prepolymer was reacted with 1,4-butanediol according to the general procedure described in Example 2 at an index of 1.05 and at 1270 psi.
(8.76MPa) tensile strength, 22600psi (155.82MPa)
Flexural modulus of elasticity, 310% elongation, 390pli (68.3KN/
m) die “C” tear strength, 4 inch overhang 250
(121°C) for 60 minutes yields an elastomer with a heating sag of 0.15 inch (3.8 mm).

Examples 7, 8, 9, 10 and Comparative Experiment A MDI was pre-reacted with aminated polyether in dimethylacetimide solution to form a 12%-NCO prepolymer and chain extended with 1,4-butanediol. , create a series of polyurea-polyurethane elastomers. Each polymer is precipitated in methanol and dried under vacuum. Each sample was analyzed by annealing the polymers at 120°C for 5 minutes in a digital calorimeter (DSC) chamber and performing a DSC scan to measure the glass transition temperature, Tg, of the hard and soft segments of each polymer. Test the thermal properties of The Tg of the aminated polyether, hard segment, and soft segment used in each sample is as shown in Table 1 below. Aminated polyethers are made from all 2000 molecular weight polyoxypropylene diols.

[Table] Cap
10 Ethylamine cat −41 197
P
A Hydroxyl terminal (control) −35 190