JPS62500666A - Method for producing polyurea and/or polyurea-polyurethane polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Made of polyurea-polyurethane polymer and/or polyurea-polyurethane polymer at 3℃ The present invention relates to polyurea and/or polyurea-polyurethane polymers, particularly non-cellular The present invention relates to a method for producing elastic and structural borourea-containing polymers that are porous or microporous.

Polyurethane polymers are used to form a wide range of elastic, structural and foam products. It is known and actually used.

These polymers are commonly referred to as polyisocyanates and "polyols." In other words, it reacts with a medium to high equivalent amount of polyhydric acid group-containing 6 substances. It is prepared accordingly. Polyols are “soft” or visible segments. 1, and this segment provides the polymer with impact resistance, corrosion resistance, and other desired properties. give gender. Often "chain extenders" or low-strength polyhydroxyl or poly- Min group-containing compounds are also used to provide crosslinking or “hard segments” to polymers. Served. These chain extenders give polyurethane increased modulus and other desired properties. Grant.

It is not just the mere existence of hard and soft segments, but also their polymorphism. It was discovered that the properties of polymers are greatly influenced by the way they are distributed in polymers. It was done. In general, hard and soft segments are well “separated” and certain properties of the polymer were found to be maximized.

Separation of such regions requires microscopic or sub-microscopic hard segmentation. It refers to the existence of a region containing a high proportion of soft segments and a region containing a high proportion of soft segments. Ru.

This desirable phase separation occurs between polyisocyanates and polyurethane polymers. After reacting with all or part of the "polyol", it is subsequently chain-spread. This is achieved by reacting with the preservative and the remaining polyol if present. Ru. In this way, the soft segment prepolymer is pre-polymerized prior to the formation of the final polymer. is generated. Such an approach is described, for example, in U.S. Pat. No. 4,297,444. It is listed.

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

In another attempt to improve polyurethane polymers, The hydroxyl-terminated materials used in the I got it. For example, U.S. Pat. Nos. 4,444,910 and 4,530,9 No. 41 is not referred to. Amine-functional materials can replace urethane bonds in polymers. and produce urea powder. These urea bonds are stronger than urethane bonds 6. It is also more thermally stable.

Although these amine-functional materials have the above advantages, when using them There are some serious problems. Amines react rapidly with isocyanate groups. However, its use is generally limited to reactive injection molding (RIM) processes. In the RIM method Even if the polymerization reaction is slow enough to make a molded article, it is common to Ethyltoluenediamine sterically hindered amine chain extender may need to be used. It has been discovered. Additionally, amines can react with isocyanates at room temperature in various secondary reactions. may cause undesired crosslinking and gel formation in polyurea-containing polymers. is known. It would also be desirable to provide polyurea polymers that are easier to process. It would be nice.

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

Therefore, producing polyureas containing polymers that give higher processing flexibility method, and polyurea polymers produced by conventional methods exhibit a It would be desirable to provide polymeric products with superior physical properties.

The present invention comprises adding an amine functional compound having an equivalent weight of at least 400 to an excess of polyimide. React with isocyanate to form isocyanate-terminated prepolymers or quasi-prepolymers and then its isocyanate-terminated prepolymer or quasi-prepolymer. is reacted with an isocyanate-reactive substance to form a polyurea and/or a polyurea polymer. The process consists of producing a polyurethane polymer and combining an amine-functional compound with a polyurethane polymer. The isocyanate is divided into three or more isocyanate-terminated prepolymers or quasi-prepolymers. It is characterized by being used in portions having an isocyanate content of 12% by weight. A process for producing polyurea and/or polyurea-polyurethane polymers. I'm being kicked.

The method of the invention provides several surprising advantages.

Isocyanate-terminated prepolymer Mana quasi-prepolymer and isocyanate reaction The reaction with a isocyanate-reactive substance is a primary or secondary amine. Even when it does, it's slower than expected. This long curing time is due to the Provides greater flexibility in processing the marketer. Glycols or relatively slow reactive When amines are used as -f-isocyanate reactive materials, the reactive materials are typically removed by hand. It is even possible to mix and cast. Of course, if you touch the reaction mixture, A medium can also be added to speed up curing as is highly desired in RIM processing. Also, The method of the present invention uses highly reactive amino acids such as ethylenediamine and toluenediamine. Allows the use of carbon as an isocyanate-reactive material. Such high opposition Reactive amines are generally too reactive for use by conventional processing, even in RIM systems. Too responsive. However, in this invention, such amines are used in molded products, especially It can be used to manufacture molded products by the RIM method.

Polymers produced according to the invention exhibit unexpected properties.

Polymers made according to the present invention are generally manufactured using a one-shot process. glass transition 5-20°C lower than that exhibited by similar polymers produced in Indicates temperature. This advantage is particularly evident when using aliphatic polyisocyanates. Ru. Additionally, the heat distortion temperatures of these polymers measured in heated flow tests are Usually significantly higher than urea-containing polymers of similar flexural modulus produced. Therefore, the book The invention can be used and processed over a wider temperature range than similar polymers made using a one-component process. The present invention provides a polymer capable of

According to the present invention, an isocyanate-terminated prepolymer or a textile prepolymer is Reacts with cyanate-reactive materials to produce urea-containing polymers. This polymer is Preferably, it is non-porous or microporous. The term “Incyane” used here The reactive substance J is local of the A+nerican Cb e+n1cal Society, Vol. 49, p. 3181 (1927 ) is active according to the Zelewiddinoff test described by Kohler. or a compound containing three hydrogen atoms, or a mixture thereof. Isocyanene The reactive substance is a low equivalent amount of polyol or polyamine (here "chain extender"). It is preferable that it consists of two fingers.

Incyanate-terminated polymers or quasi-prepolymers are amine-functional compounds or It consists of the reaction product of the mixture and a stoichiometric excess of polyisocyanates 1 to 1.

As used herein, the term "prepolymer" refers to the reaction mixture of an amine-functionalized compound and a polyisocyanate. It is used to bind the isocyanate-terminated substances produced in the reaction. The term “quasi-pro Repolymer (quasi-prepoly+ner) J is unreacted polyisocyanate It has been used to mold prepolymer-containing mixtures that also contain esters. Semi-prepo The remer is necessary to react the amine-terminated product with its amine groups. Excess unreacted polyisocyanate may be present in the product by reacting with a large amount of polyisocyanate. It can be prepared by allowing the presence of Alternatively, prepolymer A quasi-prepolymer is prepared by mixing the resulting polymer with additional polyisocyanate. You can also.

As used herein, the term ``amine-functional compound'' or ``amine-functional substance'' refers to At least one having an active hydrogen atom capable of reacting with the aho group to produce urea A compound containing an amine group or a mixture thereof. This amine functional compound or the substance has on average at least two amine groups as described above, or one at least one other functional group containing an amine group and an active hydrogen atom, as described above. It is preferable to include. The amine-functional compound also contains at least 400 equivalents of have For purposes of this invention, an equivalent amount of amine-functional compound or substance is a hydrogen source. Based on the number of amine groups (or other groups containing active hydrogen atoms) relative to the number of children Calculate. For example, a molecule JL! containing two primary amine groups! 000 compounds is considered to have an equivalence of 1000.

400 to 6000, preferably 500 to 3000, on average per molecule] , primary or secondary amine terminated polyethers containing ~4 amine groups are preferred. stomach. Suitable such amine-terminated polyethers and methods for their preparation are described, for example, in U.S. Pat. No. 3,654,376 and No. 3,666.788 . Generally, the processes described in these patents produce water in the presence of a specific catalyst. Polyethers are produced by reacting acid group-terminated polyethers with ammonia or primary amines. It consists of reducing and aminating.

For the preparation of primary amine terminated polyethers, in particular U.S. Pat. It is described in the specification of No. 76. Commercially available primary amine terminated polyethers include Jef famine T-5000, Jeffamine D-2000, Jeffa There is mine D-400 (a product of Texaco Chemical Company).

Jeffa+n1ne is a trade name of Texaco Chemical Company.

Specifically, U.S. Pat. No. 4,152,35 for the preparation of secondary amine-terminated polyethers No. 3, No. 4,153,581, and No. 3,666.788. ing. Generally, aliphatic primary amines, particularly C1-C6 aliphatic amines, are terminated. added polyether polyols, and aromatic amine-terminated substances, especially aniline Preference is given to blockaded polyethers.

In most of the above methods, polyether amination occurs in less than quantitative amounts. Wear. Therefore, the product contains only one amine group and some residual hydroxyl groups per molecule. This would include compounds having the following. In the present invention, the use of such substances is at least 25%, preferably at least 50%, of the six counts of acid and amine groups; More preferably, it is suitable as long as 50 to 100% is amine groups. Furthermore, a A mixture of a minated substance and a hydroxyl group-terminated substance has a minimum of the total number of amine groups and hydroxyl groups. It is suitable that 25% of the total amount is amine groups.

Other secondary amine-terminated polyethers may be substituted with the above-mentioned primary amine-terminated polyethers. , six unsaturated compounds, such as acrylic esters, methacrylic esters, acrylic esters, Perform Michael addition reaction with lonitrile or primary amine-terminated polyether It is advantageous to react with other compounds having sufficiently active carbon-carbon double bonds to It is prepared in C5~ of acrylonitrile and acrylic acid or methacrylic acid Reaction products of C6 alkyl or hydroxyalkyl esters are of particular interest. .

Additionally, the corresponding primary amine-terminated polyethers were treated with formaldehyde and hydrogen silica. Secondary amine-terminated polyethers formed by reaction with anide adducts are also useful. Ru. The reactions described in this step are carried out in the presence of a suitable diluent such as a lower alcohol. It is advantageous to carry out the reaction by heating the reactants. Suitable reaction conditions are described in U.S. Patent No. 3. No. 1366.788, ti.

In addition to the above, as amine-functional compounds, salts of acids, acid halides or alkyls Using primary or secondary amine-terminated substances complexed with oxides, bromides, or iodides It is also within the scope of the invention. Particularly useful are organic acid halides (e.g. salts) benzoyl chloride, acetyl chloride), phosphonic acid, halogen acid, C1-C iodide, acetyl chloride), phosphonic acid, halogen acid, primary or secondary amine terminated polyether complexed with alkyl.

The amine-functional compound reacts with excess polyisocyanate to form incyanato-terminated polymers. Produce repolymers or quasi-prepolymers. Aromatic polyisocyanate, sand In other words, if the inocyanate group is directly bonded to the aromatic ring, then and aliphatic isocyanates are useful.

Representative aromatic polyisocyanates useful in the present invention include phenyl isocyanate. ate, 2, 6-toluene diisocyanate, 2.1-) toluene diisocyanate ditoluene diisocyanate, naphthalene 1,5-diisocyanate, ditoluene diisocyanate, bis(4-incyanatophenyl)methane (MDI), bis(3-methyl-2- isocyanatophenyl)methane, bis(3-methyl-4-isocyanatopheny) methane, bis<3.5-diisopropyl-4-aminophenyl)methane, 4 ．． 4'-Diphenylbropylidene diisocyanoate, 4,4'-diphenyleth Various polymethylene polyphenyl polyisocyanes There is a route. Of course, toluene diiso cyanate, bis(4-isocyanatophenyl)methane (MDI) and polymer Styrene polyphenyl polyisocyanate is preferred. Polymers typically used here Methylene polyphenyl polyisocyanate has an average number of functional groups of 2.1 to 3.5. and contains 20 to 100% by weight of methylene diphenyl diisocyanate isomer, The remainder is high molecular weight polymethylene polyphenyl polyisocyanate. Ru. Such isocyanate mixtures are commercially available and are described in U.S. Pat. No. 3,362. , No. 679.

Suitable organic aliphatic polyisocyanates include the organic aromatic polyisocyanates listed above. In addition to the above halogen derivatives, 1゜6-hexamethylene diisocyanate, Inphorone diisocyanate, 1,4-cyclohexyl diincyanate, 1° 4-bisisocyana (1-methyl) cyclohexane, methylenebis-4-cyclo hexyl isocyanate) or their inclusions.

The reaction between the polyisocyanate and the amine group-containing substance can be carried out as is or with an appropriate solution. Amine-functional compounds are highly reactive and can be carried out in polyisomers. Contact with cyanates produces polymers of significant molecular weight. In this way, polymer A large amount of material is insoluble in the unreacted polyisocyanate and will precipitate and inhibit the process. harm In addition, the production of high molecular weight substances is based on prepolymer or quasi-prepolymer molecules. This also has an adverse effect on the properties of the product polymer, as it widens the quantity distribution.

Therefore, the conditions for the prepolymer production reaction should be set to minimize the production of such high molecular weight substances. It is advantageous to choose

The production of high molecular weight materials is due to the high local concentration of amine functionality in polyisocyanates. Minimize by conducting the reaction in such a way that the formation of the compound is minimized. can be done.

This can be done, for example, by adding an amine-functional substance to a polyisocyanate in portions under stirring conditions. This can be easily done by adding one. In particular, higher reactions In case 6, where a polyisocyanate and an amine-functional material are used, the reaction is carried out in a suitable solvent. It can be done inside.

Generally, the prepolymer formation reaction is carried out at moderate temperatures, i.e. -10 to 100° C1 Preferably carried out at 15-55°C. Low temperature, i.e. -10~30℃, will cause reaction. Slowing down and inhibiting the formation of high molecular weight substances is an additional benefit. But long However, at high temperatures the reduced viscosity of amine-containing materials allows for more rapid intermixing of the components. However, this also tends to reduce the formation of high molecular weight substances. Obviously, at high temperatures It may be difficult to control the production of high molecular weight substances.

The reaction is such that substantially all of the amine groups of the amine-functional compound react with the polyisocyanate. Continue until the answer is met. Because of the reactivity of the amine-functional compound, this reaction is not possible in most cases. The match is completed instantly. pre-prepared using a blend of amine-functional materials and polyols. When preparing polymers, somewhat longer reaction times are required, i.e. 5 minutes to 2 hours. Sometimes it's important.

The prepolymer is processed for a long time (usually several hours) before it is used to create the polymer. It is often desirable to store the product (for several months). In such cases, Prepolymers are prepared that are stable, i.e., do not undergo substantial amounts of secondary reactions during storage. It is desirable to manufacture Such stability is conventionally determined by the prepolymer over a period of time. -NCO content of - is measured and investigated.

In general, a reduction in the -NCO content of the prepolymer of less than 2% by weight indicates adequate stability. It can be said that there is.

Generally, the safety of polyurea isocyanate-terminated prepolymers or quasi-prepolymers is The quality depends in part on its composition, and more specifically on the particular polyisocyanate used. Depending on the degree of amination of the anate and amine functionalization species. In general, stability The use of low-reactivity polyisocyanates and quantitatively less aminated Improved by the use of amine-functional compounds. Additionally, secondary amine-terminated amine groups functional compounds and complexes with acids, acid halides or other halides as described above. Such amine-functional materials are -m-wise more stable than primary amine-terminated materials. produces a stable prepolymer. The corresponding primary amine is unsaturated by Michael addition reaction. (The secondary amine-terminated polyether created by reacting with H6 is a highly reactive polyether. Reacts with isocyanates to form particularly stable prepolymers.

Aliphatic polyisocyanates have a degree of amination of up to 100%. Easily reacts with amine-terminated compounds to produce stable prepolymers. Secondary amine powder Particularly stable prepolymers are formed at all degrees of amination when reacted with end compounds do.

a moderately reactive aromatic polyisocyanate or at least one moderately reactive aromatic polyisocyanate; Aromatic polymers containing a reactive isocyanate group and one or more highly reactive incyanate groups. diisocyanates, such as 2,4-toluene diisocyanate and 2.4' - methylene diphenyl diisocyanate, generally 25 to 90%, preferably is a primary amino acid having a degree of amination of 25 to 75%, more preferably 25 to 50%. reacts with a polymer terminated to form a stable prepolymer. These polyisocyan When the nate reacts with the arylamine terminated material, the degree of amination is typically 25. ~100%, preferably 25-75%, produces a stable prepolymer. a Prepolymers are made using rukylamine powder 1jfA substance together with these monsters. When formed, it has a degree of amination of 25 to 80%, preferably 25 to 65%. It's advantageous. Moderately reactive isocyanates are considered to be low reactive for the purposes of this invention. aromatic polyisocyanate and MDI, which is a highly reactive polyisocyanate. It has a reactivity between .

Highly reactive such as methylene diphenyl diisocyanate and its polymer derivatives The polyisocyanate typically contains 25-85%, preferably 25-50% and a primary amine-terminated compound having a degree of amination of 25 to 100%, preferably is a secondary amine having a degree of amination of 25 to 70%, more preferably 40 to 70%. reacts with end-of-line materials to form a stable prepolymer.

Such prepolymers or quasi-prepolymers contain at least one incyanate. Reacts with a reactive substance to form a polymer, which is preferably non-porous. porous or microporous. The polymer has a density (unfilled) of at least O,E3g/cc. It is considered non-porous or microporous. less polymer Both have a density of about 0.9 g/cc - more preferably 0.95 to 1.2 g/cc It is preferable to have a degree (unfilled).

Isocyanate-reactive materials useful in the present invention include Kot+Ier. nal of TI+e American Chemical 5ociet y, Vol. 49, p. 3181 (1927). According to the Nof test, such compounds with multiple moieties containing active hydrogen atoms are included. be caught. Examples of such moieties include mercaptan groups, hydroxyl groups, primary amine groups, and secondary amine groups. There are amine groups and acid groups. Amine and hydroxyl group-containing compounds are preferred. appropriate iso Cyanate-reactive compounds include relatively low-isomerized 6-components, relatively high-isomerized 6-components, and Mixtures of these are preferred. Those with relatively low isoquantity are less than 200, more preferably Preferably it has an equivalent weight of 30 to 150.

The conditions for the heavy reaction depend on the isocyanate-reactive material and pre- It depends somewhat on the composition of the polymer or quasi-prepolymer. relatively reactive When incyanate groups are present in the prepolymer or quasi-prepolymer, there are or rapid mixing of components, especially when using reactive isocyanate-reactive substances. 6, it is desirable to adopt reaction conditions that promote slow reactions. In such a case, The components are mixed at a temperature of -10 to 40°C in the presence or absence of a slight catalyst. A mechanical system that can react and quickly mix the components and transfer the mixture into the mold. It is preferable to use a mixing device. Preferably, a RIM type device is used. material After the material is transferred into the mold, a higher temperature is used to complete the curing reaction. Can be done.

The prepolymer or quasi-prepolymer contains low-reactivity isocyanate groups and/or or isocyanate-reactive materials have relatively low reactivity, flexibility in reaction conditions is possible. can be larger. In such cases, the reactants are heated above ambient temperature. i.e. -10 to 100°C), and a catalyst may be used if desired. It can be mixed by hand or by machine.

The more rapid reactions desirable for RIM processing can be achieved by using catalysts or by using higher reaction temperatures (3 0 to 100'C).

Suitable chain extenders containing low amounts of hydroxyl groups include, for example, ethylene glycol, propylene glycol, lene glycol, trimethylolpropane, 1,4-butanediol, diethyl glycol, dipropylene glycol, bisphenol, hydroquinone, categorical Cole, resorcinol, triethylene glycol, tetraethylene glycol , glycerin, low molecular weight ethylene and/or propylene oxy of glycerin derivatives, ethylenediamine, diethylenetriamine, and mixtures thereof. be.

Suitable low weight aliphatic amine-containing compounds include, for example, ethylenediamine, ]5, 3-diaminopropane, 1,4-diaminobutane, inphoronediamine, diethyl Lentriamine, ethanolamine, aminoethylethanolamine, diamino Cyclohexane, hexamethylene diamine, aminoethylpiperazine, bisquarium minopropyl) and perazine, 1,2-diaminodiclohexane, poly(oxia alkylene)amine, bis(p--aminocyclohexyl)methane, triethylene Tetramine, and a mixture of these? There is something. Particularly suitable ones have an average of 60 to 11 0, but these The materials are commonly used with amine or glycol chain extenders.

Suitable low weight aromatic amines that can be used in the present invention include, for example, 2,4- Bis(p-aminobenzyl)aniline, 2,4-diamino I-luene, 2,6- Diamittoluene, 1゜3-phenylenediamine, 1,4-phenylenediamine , 2゜4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane , naphthalene-1,5-diamine, 1-methyl-2-methylamino-4-amine Benzene, polyphenylpolymethylene polyamine, 1,3-diethyl-2,4- Diaminobenzene, 1'-methyl-3,5-diethyl-2,6-diaminobenze 1,3,5-)-liethyl-2,6-diamitbenzene, and mixtures thereof. There is a compound. The above aromatic amines substituted with amino groups at each ortho position are Blocked with stearic acid and not substituted with an amine group at one or more ortho positions Reacts more slowly than aromatic amines such as those mentioned above.

Suitable relatively high quantity compounds include, for example, polyether polyols, polyester polyols, so-called polymer or copolycopolyols, hydroxyl-terminated acetic acid There are tar resins, polyhydroxyl group-containing phosphorus compounds, and amine-terminated polyethers. most Preferably have an equivalent weight of 400 to 5000 and an average functionality of 2 to 4, especially 2 to 3. A polyol or amine terminated polyether as described above.

In addition to the above ingredients, it is desirable to include various other ingredients in the reaction mixture. There are many bad things. It has been mentioned before that heavy reaction catalysts can be used in specific places 6. Stated. Suitable such catalysts commonly include tertiary amines and organometallic compounds. It will be done. Organometallic catalysts include, for example, stannous carboxylates, trialkyltin oxides, lead, mercury, or dialkyltin sybarides or dialkyltin oxides or a stannous tin compound, in which the organic group or hydrocarbon group of the organic part of the tin compound is 1 to Those containing 8 carbon atoms are suitable. For example, dibutyltin dilaurate, dibutyltin dilaurate, Butyltin diacetate, diethyltin diacetate, octanoic acid, di(2- ethylhexyl) tin oxide, oleic acid 1st. tin or a mixture of these Can be used. Tertiary amine catalysts include trialkylamines and heterocyclic amines. , e.g. alkylmorpholine, 1,4-dimethibiverazine, triethylenediamide and aliphatic polyamines such as N, N, N', N'-tetramethyl-1 , 3-butanediamine.

Producing a cellular polymer using a blowing agent Can also be done. However, the formation of cellular polymers is undesirable. But long If the polymer has a density of at least 0.8 g/eC, A blowing agent may be used to cause slight expansion and create a microporous structure. Appropriate Blowing agents include low-boiling halogens such as trichloromonofluoromethane and 1 methylene salt. Volatilizes under the conditions of hydrogenated hydrocarbons, carbon dioxide, nitrogen, water, or polymerization reactions. There are other known substances that produce gases in other ways.

Other conventional formulation ingredients such as stabilizers, swelling agents, inert fillers (e.g. Glass fibers, carbon fibers) or pigments can also be used. European Patent Publication No. 1 No. 19,471 and International Publication No. WO 367121,5. Partial mold release agents may also be suitably used in the present invention.

The polymers produced according to the invention can be used, for example, in the production of fascias for automobile bumpers. Used as a static or dynamic elastic body, or as an automobile partition plate and safety pillow It is useful as a foam cushion such as those used in

Example The following examples are intended to illustrate the invention, but are not limiting. vinegar All parts and percentages are on a weight basis unless otherwise specified.

anus Into a resin reaction kettle equipped with a stirrer, heating lamp and nitrogen atmosphere, add 1.8.9 g of Added xamethylene diisocyanate (I (MDI). IIMDI was heated to 40°C. Heat to. While stirring, 50% primary amine groups, 37% methylamine groups, Aminated polyoxypropylene containing 10% dimethylamine groups and 3% hydroxyl groups 50 g (0.05 mol) of diol was added over a period of 2 hours. U.S. Patent No. 4, In a tubular reactor according to the general method described in No. 152,353, ft. Amine 1-hydiol is similarly prepared by reacting methylamine and diol. Mail The weight ratio of thylamine to diol is 0.35. The reaction takes place at a temperature of 265°C and 11 00 psi (7,58 Mr'a) pressure and 2 cubic feet of hydrogen into the reactor. It was fed at a rate of 1-/h (0,057+n2/h). Adding an amine causes reaction The viscosity of the reaction mixture increased, indicating that a prepolymer was formed.

Following addition of the amine, a clear colorless viscous liquid is obtained.

A prepolymer with an -NCO8- content of 8.9% is obtained. This prepolymer is reacted with diethyltoluenediamine (DETDA) with an index of 1.05. child For the reaction, mix the ingredients by hand and preheat the reaction mixture to 300°F (149°C). This is done by pouring it onto a mold. The gel time for this reaction is 30 seconds.

The polymer cures at 300°F (149°C) for 60 minutes. The resulting elastomer - The glass transition temperature of -55℃ compared to the expected value of -40℃ was added to a suitable flask with nitrogen. Charge 99 grams of hexamethylene diisocyanate under bare atmosphere. This hula Amine polyoxypropylene as described in Example 1 under constant stirring Drop in 300 grams of diol. Prepoly with -NGO content of 9.25% You can get mer.

After one-part storage, degas the prepolymer, add DETDA, degas again at room temperature, 2 by pouring hot material onto a mold preheated to 100°F (37.8°C). 09 g of prepolymer and 41 g of DETDA were reacted. The molded product is 300' Cured at F (149° C.) 10,0OOpSi (68,95 MPa) for 30 minutes.

The properties of the molded product obtained are as follows. Flexural modulus 11900psi (82, 05HPa), tensile strength t180psi (8,14HPa), Gui "C" tear Strength 405 bond/linear inch (70,9K N, /+n), depth 1634 , heated sag (325°F (163°C) with 4 inch (102mm) overhang) 30 0.16 inches per minute (4.1 man), Tg #55°C.

Salmon 1 Following the general procedure described in Example 2, 4,4'-methylene diphenyl diisocy Polyoxygenate (MDI N6.65g and aminated molecular weight 2000) 23.3 g of propylene glycol was reacted to form a precipitate with a -NCO content of 10.1%. Produces polymers. Aminated materials are described in U.S. Pat. No. 4,152,353. Reacting aniline with a polyol of molecular weight 2000 according to the general method described. Let me create it. 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 600 psi (4, IMPa). water in reactor The raw material is fed at a rate of 10 cubic feet per hour (78,7c...3/sec). can get The aminated polyol contained 40% primary amine, 39% saturated secondary amine end groups, 4 % aniline groups, and about 1-1% residual hydroxyl groups. This prepolymer approx. 0.6g was mixed with 4.41g of DETDA by hand and reacted to form a moldable elastomer. Generate a mer. The resulting polymer has a glass transition temperature of -53°C.

Salmon tip Using 14.6 g of toluene diisocyanate and 35.4 g of the aminated material of Example 3 A prepolymer is made as in Example 3.

A prepolymer with an -NGO content of 9.23% is obtained. This prepolymer 20 g are reacted with 3.82 g of DETDA as described in Example 2. Polymer obtained has a glass transition temperature of -46°C.

Yesterday Σ According to the method described in Example 3, isopropylamine terminated polyolefins having a molecular weight of 2000 were prepared. 36.7 g of xypropylene glycol and hexa, methylene diisocyanate 13.3 g were reacted to produce a prepolymer with a -NGO content of 9.5%. to be accomplished. Add this prepolymer to DETDA and an index of 100, and mix the ingredients by hand. Mold (12 inch x fin inch x 1/8 inch) heated to 00°F (37.8°C) (305 mm x 178 mm x 3, 2 mm) and react . The moldings were then heated to 300'F (149°C) and 10,000 psi (68,95°C). M1'a) Cure for 30 minutes. The tensile strength of the obtained molded body is 2409 ps i (16,61 MPa). Elongation is 503%, flexural modulus is 32,400p si (223,4 MPa), die “C” tear strength is 401 bond/linear inch ( 70,2I(N/+n), the glass transition temperature is -56°C. 6 inches (1 0.2 inches at 325°F (163°C) for 30 minutes with an overhang of 52111111) (5,1vn> sagging of the molded body.

Primary amine terminated polyoxypropylene, commercially available as Jeffamine T-5000 Pyrenetriol is reacted with acrylonitrile to form a terminal mono(cyanoethyl) atom. Generates a derivative containing a min group. Add this derivative dropwise to MDI at room temperature in sufficient proportions. A prepolymer having an NCO content of 122 is obtained. The resulting prepolymer is shown in Example 2. React with 1,4-butanediol according to the described shell procedure with an exponent of 1.05. tensile strength of 1270 psi (8,76 MPa), 22600 psi (155 , 82 MPa) flexural modulus, 310% elongation, 390 pli (68,3 K N / m) die “C” tear strength, 4 inch overhang 250’F (121°C) Elastomer with heat mold shrinkage of 0.15 inches (3.8 m+l+) in 60 minutes is obtained.

Examples 7, 8, 9.10 and MDI in reed methyl acetimide solution was pre-reacted with an aminated prepolymer to produce a 12%-NCO prepolymer. , a series of polyurea-polyurethane elastomers, extended with 1,4-butanediol. Create a streamer. Each polymer is precipitated in methanol and dried under vacuum. . The polymer was annealed at 120°C for 5 minutes in a pointing calorimeter (DSC) chamber. A C-scan was performed to determine the glass transition temperature of the hard and soft segments of each polymer. The thermal properties of each sample are tested by measuring the degree Tg. used for each sample Tg of aminated polyether and hard segment and soft segment is shown in Table 1 below. As shown in All aminated polyethers are polyesters with a molecular weight of 2000. Made from pheasant propylene diol.

Polyether Seg, India Segment 7 - NIICII□CI+, (N key) Cap -40200,210,2288 SikU-xylamine cap 7°- 472019 Isopropylamine Cuff'-4619710 Ethylamine Kit 7° -41197A Hydroxy end (control) -35190 Soft segment The Tg defines the lower limit of the polymer's useful temperature range. Tg of hard segment defines an upper limit. As can be seen from the data in Table 1, the Each polymer has a lower soft segment Tg and a higher hard segment Tg. It has g. In practical applications like car bumpers, lower soft segments The Tg of the material remains visible at lower temperatures and does not become brittle compared to the control. Contemplate. Additionally, higher hard segment Tg is achieved through in-line bake-hardening printing. It means that it can better withstand the thermal environment that it is exposed to.

Procedural amendment (formality) %formula% 1.Display of the incident PCT/US 86100591 , name of invention Method for producing polyurea and/or polyurea-polyurecne polymer 3. Person making the amendment Relationship to the incident: Patent applicant Name: The Dow Chemical Company 4, Agent Address: 8-10-5 Toranomon-chome, Minato-ku, Tokyo 105, Date of amendment order Shipping date: December 23, 1985) Toru 6. Subject of correction Translation of the description and claims 7. Contents of correction Translation of the specification and claims (No change in content) 8. List of attached documents Description and claims Translated text: 1 copy each international search report IAl, MlloMI Amuc+uw N. pcrlσS8Otsu10ossuth 10os Priority claim 0198 Cape January 3rd [Sou] United States (US) ■824407 @ Inventor Prebis, Raymond Nee Amerisas 0 shots clearer Plinister, Ralph Dee Amerizoil @R Ming Gonzalez, Manuel, Xu Amerinia Hock ○Inventor: Bushman, Kimbley Amerind 30 Narch Street, Lake Jackson, Texas 77566 8 United States, Texas? 7566 Lake Jackson, 1 Duffo Street 08 56 Holy Court, Lake Jackson, Texas 77566 United States, Texas 77531. Crude, Canon Street

Claims (10)

[Claims] 1. amine-functional compound having an equivalent weight of at least 400 and an excess of polyisocyanate react with isocyanate-terminated blepolymers or quasi-blepolymers The isocyanate-terminated or quasi-ble polymer is then isocyanate-terminated. polyurea and/or polyurea-polyurea by reacting with a cyanate-reactive substance. The process consists of producing a tumbled polymer and combining an amine-functional compound with a polyisomer. The ratio of cyanate to isocyanate-terminated blepolymer or semi-blepolymer is 3. A method characterized in that it is used to have an isocyanate content of ~12% by weight. . 2. The amine-functional compound has an average magnitude of 400 to 6000, and per molecule 2. A method according to claim 1, having 1 to 4 amine groups. 3. Claim 2, wherein said amine-functional compound is an amine-terminated polyether. Method described. 4. At least 2 of the total number of hydroxyl groups and amine groups of the amine-functional compound 4. The method of claim 3, wherein 5% are amine groups. 5. The polyisocyanate is an aliphatic polyisocyanate or an aromatic polyisocyanate. 5. The method according to claim 4, wherein the cyanate is cyanate. 6. the polyisocyanate is at least one moderately reactive isocyanate; is an aromatic polyisocyanate containing a The compound according to claim 5 is a primary amine-terminated compound having a degree of amination of 90%. the method of. 7. The polyisocyanate is an aromatic polymer having highly reactive isocyanate groups. isocyanate, and the amine-functional compound has a degree of amination of 25 to 85%. 6. The method according to claim 5, wherein the primary amine-terminated compound has: 8. The isocyanate-reactive substance has an equivalent weight of less than 200 amine groups or or a hydroxyl group-containing compound. 9. The isocyanate-reactive material contains 400 to 5000 equivalents and 2 to 3 functional Claim 1, which is a functional polyol or amine-terminated polyether Method described. 10. The amine-functional material has a carbon-carbon double bond with a primary amine-terminated polyether. Claim 3, which is a microreaction product of an unsaturated compound containing Method.