JPH01126327A - N-(polyoxyalkyl)-n-(alkyl)amine - Google Patents

Abstract

PURPOSE: To obtain the new compound which is constituted by directly contact- aminating polyol prepared from ethyleneoxide or alkyleneoxide, etc., by means of amine and which is useful for producing polyurethane/urea form with high reaction with an NCO group.

CONSTITUTION: Polyol which is obtained by permitting ethylenoxide or propyreneoxide, etc., to glycerine or polyalkyleneglycol, etc., is made to react to amine such as isoropylamine, etc., under pressurization so that the target compound is obtained, which is provided with a formula I (R1 is a starter radical based on the compound containing Zerewitinoff active hydrogen atom, H is the formula II (R' is 2-18C alkyl, R" is H, 1-18C alkyl; (a) and (b) are 0-175; (c) is 0-30; (n) is 1-3); P is the formula III; S is the formula IV (R''' is 2-12C alkyl); T is the formula V (R⁴' is the same kind as R'''); (h) is 0-0.7; (p) is less than 0-0.5; (s) is 0.5-1.0; (t) is 0-0.15; (z) is an integer derived from the number of Zerewitinoff active hydrogen in the starter.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel group of amines, particularly -N-(polyoxyalkyl)-N-(alkyl)amines. These amines have utility in the production of polyurea and polyurethane/urea polymers useful in the production of nidistomers and foams.

BACKGROUND OF THE INVENTION Current urethane technology offers potential end users a versatility unsurpassed by any other polymer system. Essentially solid polyurethanes ranging from very soft (40 Shore A) elastomers to very hard (80 Shore D) plastics and densities from 1 to 50 Bons) using readily available intermediates and processing equipment. It is possible to produce foamed polymers in the range of 7 ft''. These polyurethanes generally have very good properties and as a result a large market has developed around their use.

Four major categories of intermediates are used in the production of most typical urethane systems. These include:
Polyols, incyanates, chain extenders and additives (
(contains blowing agents).

Several classes of polyols have been used in the production of urethane polymers. These include polyesters based on propylene oxide and ethylene oxide, polycaprolactone, poly(1,4-butylene) oxide and polyoxyalkylene/oxides. Of these, the latter has found the greatest practical use in local chestnuts. Typically, polyols of this type are made by reacting propylene oxide (with or without ethylene oxide) with an "initiator molecule" such as glycerin under base-catalyzed conditions. When using ethylene oxide, it can be incorporated either as an internal block or random sequence in the polyol backbone or as a cap. Capping serves to convert the majority of normal secondary hydroxyl groups on the polyol to more reactive primary hydroxyl groups.

For many applications, polyurethanes based on polyols such as those described above provide adequate processing latitude and reactivity with isocyanates and impart impressive properties to the urethane polymer. However, there are more critical application rates that require - greater reactivity, - better properties, or both. These include applications such as high quality reaction injection molding (RIM) systems, new rapid release foams, and nidistomers.

Compounds with the potential to meet these stringent requirements are taught in U.S. Pat. Patent pace.

These materials are manufactured using a well-known reaction between ammonia and an alcohol (polyol) catalyzed under high temperature conditions in the presence of hydrogen to terminate amines in which the hydroxyl groups of conventional polyols are replaced with primary amine 7 groups. It is a polyether. This patent shows certain secondary aminopolyethers f4+. However, since ammonia (and not an alkyl-substituted amine) was used exclusively as the aminating agent, the tertiary amines formed must be limited to the intramolecularly reactive tertiary amines discussed in the patent. These secondary amines are the tertiary amines of the present invention;
There is a significant difference in that the amination product is formed directly from the reaction of the polyol with the anointed amine and not from the reaction of the amine-terminated polyol with the 79 itself.

and it et al.'s amines are highly incyanate-reactive and are believed to enhance the sintering reactivity of the system - generating highly stable urea groups that enhance the properties of the polymer, especially at elevated temperatures. Although primary amine terminated polyethers have found some utility, their acceptance has been limited, largely due to their very high reactivity.

In US Pat. No. 2,629,740, all the alkyl groups on the amine-terminated polyether are functionalized with hydroxy groups.

Ami/
The polyethers terminated with are tertiary amines, so that they are not reactive in the direction of incyanate.

In US Pat. No. 5,666,788, all of these amine-terminated polyethers are functionalized with cyano groups.

U.S. Pat. No. 4,374,204 discloses “Polyoxypropylene 1
Polyethers terminated with monoalkylamines, which are considered to be 0 sorbitol, are being considered. The molecular weight of these derivatives was limited to only 2550 (approximately 583 equivalents). U.S. Pat.
The isolated amine described in the molecule farMWJ2000) was not characterized and was made using a process different from that described in the present invention, but the process yields good results. This required the pre-presence of a primary amine-terminated substance with a MW of 2000. No other examples of alkylamino-substituted substances are mentioned and no efficacy of use has been demonstrated for this compound.

US Pat. No. 4,417,075 describes di(secondary and tertiary alkylaminoalkoxy)alkanes with equivalent weights limited to about 400.

U.S. Pat. No. 4,588,840 describes aromatic amine-terminated polyethers made from amines and polyols. Aliphatic amines were not considered.

US Pat. No. 4,605,775 describes secondary amine-containing polyethers that are monoamino alcohols. Diamines are not presented.

Reaction of textile amines with alcohols is a known approach. However, USPN 4.686.242 teaches that this approach actually produces amine-terminated polyethers where the amine groups are primarily primary amines.

French Patent No. 1,466.708 describes secondary amines made by reacting epoxy-terminated polyethers with primary amines. These reaction products yield alkanolamines rather than pure secondary amines.

West German Patent No. 5.142756 discusses polyurea articles made from glazed amine-containing polyethers. The amine polyethers exemplified are primary amine containing products. Certain secondary amine-functionalized polyethers have been considered (i.e., as described in the above-mentioned French patent t466.70).
No. 8) They are in fact alkanolamines Object of the invention An object of the invention is to provide a new group of amines which can be used to react with incyanates to form polyureas and polyurethanes/ureas. Another object of the present invention is to provide an amino acid having a reactivity with incyanate that is slow enough to give a well-controlled reaction and fast enough to be commercially acceptable.

Other objects of the invention will become apparent from the following description and examples.

SUMMARY OF THE INVENTION The present invention provides a novel family of amines specifically designed for reaction with isocyanates to form polyureas and polyurethanes/ureas. These amines are generally N-(polyoxyalkyl)-N- formed by reacting alcohols such as mono- or polyols with substituted amines in the presence of a suitable catalyst such as nickel. (alkyl)amine.

DETAILED DESCRIPTION OF THE INVENTION According to present invention v4, there is provided N-(polyoxyalkyl)-N-(alkyl)ami/ of the following general formula: R[HJ(h, )((P)t ■3 ωt 'z-(
hz) where R is an initiator radical based on a compound containing a Zelewitinoff active hydrogen atom.

Such compounds can initiate polymerization with mono-alkylenoxides when used with a suitable catalyst (eg, potassium hydroxide, zinc cyanocopaltate).

Examples of such compounds include, but are not limited to, ni-functional compounds such as methanol, butanol, phenol, nonylphenol, lauryl alcohol, 2
- methoxyethanol; difunctional compounds such as ethylene glycol, propylene glycol, water, $4-butanediol, diethylene glycol; trifunctional compounds,
For example trimethylolpropane, glycerin; other polyfunctional compounds thereof, such as be/taerythritol, sorbitol, anomonia, ethylenediamine, isomers of i,3-diaminopropano, t6-hexanediamine, phenylenediamine and toluenediamine, 4 .4'-diphenylmethanecyamino and its isomers, jetanolamine, ethanolamine, dimethylethanolamine N
- methylethanolamine, triethanolamine/, triisopropanolamine, ethylmercaptan, triphenol and propylene disulfide. Additional examples of compounds suitable for initiating the polymerization of alkylene oxides are the various oligomers known in the art. It is a polyol. These include poly-(t4 butylene oxide) polyether, hydrothousyl and amine-terminated poly-(butadiene). When polyols (or other oligomers) are used to initiate the polymerization of alkylene oxides, their molecular weights range from 400 to about 3000.
can be in the range of When using conventional initiators such as those mentioned above (ie, glycerin, water, etc.), their molecule i can range from about 18 (for water) to about 400. Preferably R contains 2 to 6 carbon atoms, most preferably 3 to 6 carbon atoms.

The alkylene oxides and salts that find utility in this invention are well known in the art. These include propylene oxide, ethylene oxide, alpha olefin oxides such as 1,2-epoxybutane and 1,2-epoxyoctadecasoxetane, tetrahydrofuran.

H is a group represented by the following formula: CcH2CH
2-0 )t (CH2-CH-0)t CCH,CH
-0)t-(C)I2). αi■; P is a group represented by the following formula: S is a group represented by the following formula: T is a group represented by the following formula: where the letter raJ is N-(polyoxyalkyl) - Specify the propylene oxide content of the N-(alkyl)amine and 0
The value can range from 175 to 175. The preferred range for "a" is 0-90. When b or C is not equal to zero, the most preferred range for aJVc is 0-50.

The letter "b" defines the propylene oxide content of the N-(polyoxyalkyl)-N-(alkyl)amine and can range from a value of zero to 175. Preferably rbJ is 20-115, most preferably 25-98
should be in the range of

Letter rcJ ij N -(Polyoxyalkyl)-N
- Can be an alpha olefin oxy of an (alkyl)amine. Preferably, "C" can range from zero to 15, most preferably from 0 to 2.

The letter "n" is equal to 1 to 5, preferably equal to 1.

Two aspects of aSb and C are important and must be noted. The first is when n equals 1, a+b+c
The sum of must always be greater than or equal to 2. Second, 51% b and C are ethylene oxide, propylene oxide and al7 which can be added to the product backbone in any sequence, block or random sequence, and in any configuration. Indicates aolefin oxide.

R' is an alkyl group containing from 2 to 18 carbon atoms depending on the alpha olefin oxide used in the preparation of the amine. OR' can contain up to 18 carbon atoms, but 2 carbon atoms is most preferred. .

R' is hydrogen or an alkyl group containing up to 18 carbon atoms. Preferably R' is hydrogen or an alkyl group containing up to 2 carbon elements, most preferably a methyl group.

W″ and ni″ independently contain 2 to 12 carbon atoms;
Preferably it is an alkyl group containing 2 to 6 carbon atoms, most preferably an isopropyl group.

The letters rhJ indicate the relative hydroxyl content remaining after amination and are between 0 and 0.7, preferably between 0 and 0.3, and most preferably between 0 and 0.15. As mentioned above, “h
” relates to the percent amination.

That is, 30% amination results in a hydroxyl content of 70%
N) t is equal to 0.7.

The value is calculated by measuring the total amine number in milliliter fit/gram, dividing by the initial hydroxyl number (meq/l), and subtracting the quotient from 10.

The letter "p" represents the primary amine content relative to the total amine content formed during amination and is between 0 and 0.5, preferably between 0 and 0.4.

The letter "3" represents the tertiary amine/content relative to the total amine content formed during amination and from 0.5 to 10
, preferably 0.70 to 1.0.

The letter rtJ represents the tertiary amine/content relative to the total amine content formed during amination and from 0 to 0.15
, preferably 0 to 0.05. The sum of p, s and t must equal to.

The letter rzJ is an integer derived from the number of Zelewitinoff active hydrogens attached to the initiator. The letter rzJ is preferably between 2 and 6, most preferably between 3 and 6, provided that rzJ is 2. Provided that when , a and C are zero, b must be greater than 22.

These parameters range from about 9D to about 10D when the potency is 1 to 6. N- with an equivalent weight greater than 1250 when the ODD or higher range and functionality is 2.
Describing (polyoxyalkyl)-N-(alkyl)amines 0 The N-(polyoxyalkyl)-N-(alkyl)amines of the present invention are prepared by direct catalytic amination of the appropriate alcohol with an amine: + Representative amines useful in the RR-N)L and/or RNH2 invention are primary amines and secondary amines.

Examples of representative primary amines include, but are not limited to: ethylamine, n-propylamine, inpropylamine, cyclohexylamine, laurylamine, t-butylamino, and S-butylamine0 Representative secondary amines includes, but is not limited to, di-diethylamine, di-harp tetrapylamine, diisopropylamine, di-n-butylamine, diisobutylamine,
Di-2-ethylhexylamine, di-Bee, -butylamine, dioctylamine, n-ethyl-n-butylamine/and diphenylamine.

By using Kowara's secondary amine, the tertiary amine content is higher than expected and the tertiary amine content is higher than expected, as described in co-pending patent application D-15,85<S filed on the same day as this &1. However, it tends to produce less N-(polyoxyal)-N-(alkyl)amine than JIS. It is also envisaged that a blend of primary and secondary amines could be used in the amination process. One method for making zero-niamines is described in U.S. Pat. The base polyether is reacted with acetone, and the resulting ketimine is hydrogenated to form the product. Although Jin's method is only exemplified for materials of about 1000 equivalents, it is technically applicable to other molecular weights and functionalities. However, this approach is limited in part based on the availability of primary amine terminated polyethers.

Additionally, while the reaction of primary aminos with alcohols (polyols) is known, in U.S. Pat. It teaches the production of based polyethers.

Alcohols, particularly monols and polyols, used in the present invention are well known in the art and are commercially available from a variety of sources.

The reaction is carried out in a batch autoclave at elevated temperatures, usually 175
It is carried out at a temperature of 190° to 240°C, preferably 190° to 240°C. The reaction pressure is 250-2000 psi (18-14
0 K9. -)t preferably 500-1250psi
(35 to 87,9 K9/ctl). The reaction takes place in the presence of hydrogen. Under these conditions, the human 0"?sil-containing polymer remains in the liquid phase. The stoichiometry in terms of amine to hydroxyl ratio is 2:1~
20:1, preferably in the range of 5:1 to 10:1.

The reaction is usually carried out for 4 to 24 hours. The catalyst can be a nickel, copper or cobalt based catalyst either unsupported or on a support, with nickel being most preferred. When supporting a catalyst, the amount of catalytic acid is at least 2
Preferably it is 5%, preferably 50% or more. The amount of catalyst used is 1 to 5% by weight based on the total amount charged.
It is normal that it is about.

Amination can be performed using a liquid phase continuous amination process in addition to the patch process described above. In this process, a nickel, hacobalt cuprate catalyst, optionally deposited on a support, in pelletized or extruded form is charged into a high-pressure tubular reactor. Most preferably, a nickel catalyst is used. Heat the reactor to 175°~
At 250°C, preferably from 190 to 240°C, a mixture of amine and polyol (2:1 to 20:1, preferably 5:1 to 10:1 on an equivalent basis) is pumped into the reactor. Feed in feed/catalyst V hours with a flow rate range of about 15 to 5.02. Hydrogen is added to the feed stream at a minimum rate of 1 cc/min. The reactor pressure was adjusted by a back pressure regulator to
50-2000Psi (18-140Kf/ci)t preferably 500-1200p8i (35-841Gz/
−). The product isolated from a continuous process is similar to the product isolated from a patch process.

The N-(polyoxyalkyl)-N-(alkyl)amines of the present invention find utility in the production of polyureas and polyurethane-urea products.

When producing polyureas, polyols should not be used. When producing polyurethane-urea, the N of the present invention
-(Polyoxyalkyl)-N-(alkyl)amines are used with pace polyols or other polyfunctional alcohol-containing materials.

The present invention provides (a) the N-(polyoxyalkyl) of the present invention;
-N-(alkyl)amine alone or in some cases in combination with other polymers having active hydrogen atoms, and (b) an organic polyinsyanate, optionally (c) addition A method of making a polyurea foam is provided which includes reacting in the presence of a polyurea or polyurethane-urea product. When foams are being manufactured, these additives typically include catalysts, blowing agents, crosslinking agents, and foam stabilizers.

The reaction and foaming operations can be carried out in any suitable manner, preferably by a one-shot technique.

Organic polyisocyanates useful in preparing polyureas or polyurethane-urea distomers according to the present invention are organic compounds containing at least two isocyanate groups. Such compounds are well known in fraction mf. Suitable organic polyisocyanates include hydrocarbon diisocyanates (eg alkylene diisocyanates, arylene diisocyanates) as well as the known triisocyanates, polymethylene poly(phenylene isocyanates). Examples of suitable polyisocyanates are: 2.4-diisocyanatotoluene, 2.6-
diisocyanatoethane (TDI) methylene bis (4
-cyclohexyl isocyanate) t-isophorone diisocyanate, 1.2-diisocyanatoethane, 1.3-
Diisocyanatopropane, t2-diisocyanatopropane, 14-diisocyanatobuta/, 1.5-diisocyanatopentane, i,6-diisocyanatoethane/, bis(3-incyanatopropyl) ether, Bis(3-isocyanatopropyl) sulfide, 1,7-diynecyanatohebutane, t5-diisocyanato-2,2-dimethylpentane, t6-diisocyanato-3-methoxyhexane, t8-diisocyanato-octa/, t5-diisocyanato- 42,4-trimethylpentane, 1,9-diisocyanatononane, tlo-diisocyanatodecane, t
4-diisocyanatooclohekib/and their isomers, 1,10-diisocyanatopropyl)ether of t4-butylene glycol, tll-diisocyanatodendecano, 1,12-diisocyanatododeca/bis (incyanatohexyl)sulfide, 14-diisocyanatobenzene, 45-diisocyanato-0-silene, 4.6
-diisocyanato-m-xylene, 2.6-diisocyanato p-xylene/, tetramethylxin diisocyanate, 2.4-diisocyanato-1-chlorobenzene, 2.4-diisocyanato-1-nitrobenzene, 2
．． 5-diisocyanato-1-nitrobenzene, 2.4'
and 4.4'-cyphenylmethane diisocyaner) (M
L) I) and their derivatives, 5,5-diphenyl-methylene diisocyanate, polymethylene poly(phenylene isocyanate) and mixtures thereof. These references and numerous patents, such as U.S. Patent No. 2.685.73EJ
No. 2,950,265, No. 3,012. It is described in Rollo No. 8, No. 3.544.162 and No. 1562.979.

Additional aromatic polyinsyanates include = p-7
22 diisocyanate, polymethylene polyphenylisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene/-14-diisocyanate, bis(3-methyl-3-ynecyanatophenyl)methane, bis(3-methyl-4-ynecyanatophenyl)methane, anatophenyl)methane, 4,4-diphenylpropane diisocyanate.

Any known catalyst useful in the production of polyurea or polycrethane/urinary foams may be used. Typical catalysts include (a) tertiary amines such as bis(2,
2'-dimethylamine) ethyl ether, trimethylamine, triethylamine, N-methylmorpholif, N-
Ethylmorpholine, N,N-dimethylbenzylamine,
N, N-dimethylethanolamine, N, N, N,
N-tetramethyl-1,5-butanediamine, triethanolamine, t4-diazabicyclo-(2,2,2
) Octane, hexamethylenetetramine, pyridine oxide, etc.; Q11) Tertiary phosphines, such as trialkylphosphines, dialkylbe/dylphosphines, etc.: (
(d) Acidic metal salts of strong acids, such as ferric chloride, stannic chloride, stannous chloride, Antimono trichloride, bismuth nitrate, bismuth chloride, etc.: (e) Chelates of various metals, such as acetylaceto/, hendiylacetone, trifluoroacetylacetone, ethylacetoacetate, turitylaldehyde, cyclopentanone-2-carboxylate,
Acetylacetone imine, bis-acetylacetone-alkylene diimine, salicylaldehyde imine, etc. and associated metals, such as It'r Be.

Ml, Zn, act, pb, Tt, Zr+S
ne Ass BL Cr, NolMnt FeeCo
, Ni, which can be obtained from ionic compounds such as MoO□→, UO2++; (f) alcoholades and phenolates of various metals, such as Ti(OR)4t
5n (OR) 48n (OR) @ Al (OR)
s (wherein R is alkyl or allyl),
and reaction products of alcoholades with carboxylic acids, beta-diketones and 2(N,N-dialkylamino)alkanols, such as the well-known compounds obtained by the above or equivalent procedures: (g) organic acids; Various metals, such as alkali metals, alkaline earth metals, A I + Sn
e Pb+ Mrle Co t B and its salts with copper, including, for example: sodium acetate, potassium laurate, calcium hexanoate, stannous acetate, stannous octoate, stannous oleate, octane. acid lead,
Gold dust desiccants, such as manganese and cobalt naphthinate, etc.) Tetravalent tin, tetravalent and monovalent Age Sb and B
organometallic derivatives of i and metal carbonyls of iron and cobalt.

Among the organotin compounds worthy of particular mention are the following dicarbo/i! i! Dialkyltin salts of, e.g. evadibutyltin diacetate, dibutyltin silacrate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate), dibutyltin-bis(6-
Similarly, rutin hydroxide in trial, cyto in dialkyltin, dialkyltin dialkoxy, cyto or dialkyltin dichloride may be used. Examples of these compounds include nitrimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis(impropoxide), dibutyltin-bis (2-dimethylaminopentylate) t-dibutyltin dichloride, dioctyltin dichloride, etc.

Tertiary amines may be used as the first catalyst to promote the reactive hydrogen/isocyanate reaction or as the second catalyst in combination with one or more of the metal catalysts mentioned above.

Metal catalysts, or combinations of metal catalysts, may also be used as promoters without the use of amines. Catalysts are used in small amounts, such as from about 0.001 to about 5%, based on the weight of the reaction mixture.

Examples of representative crosslinking agents include, but are not limited to, nigericolamine, diethanolamine, triethanolamine, monoethanolamine, methyljetanolamine, impropanolamine, 2-hydroxyethylpiperazine. , aminoethylethanolamine, 2
-Aminoethanol, diisopropanolamine, Quadrol (registered trademark) tA-S
11-aminoethylpiperazine, p-phenylenediamine, m-phenylenediamine, glycol; nlubitol, ethylene glycol, chrycerin.

When forming polyurea or polyurethane foam,
A blowing agent is used in the reaction mixture. A suitable blowing agent is
For example, the total weight of N-(polyoxyalkyl)-N-(aluminum)amine and polyol or other suitable blowing agent that is vaporized by the exotherm of the reaction, or a combination of water and other blowing agents. About 0.1 to about 10fE amount% based on
It usually contains 50% of water. Specific examples of polyurea and polyurethane blowing agents include: halogenated hydrocarbons,
For example, trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane, tl-dichloro-1-fluoroethane, 1,1,2-1J/RORO1.2.2-trifluoroethane, hexa2 “Rheolocyclobutane, octafluorocyclobutane, etc.

Another group of blowing agents includes thermal nonnitrosoterephthalamides, amine formates, formic acids, etc., which liberate gas when heated. A normally preferred blowing method for producing flexible foams uses a combination of water or water plus a fluorocarbon blowing agent, such as trichloromonofluoromethane. The amount of blowing agent used will vary depending on factors such as the desired density, hardness, etc. of the foamed product.

Where applicable, it is also within the scope of the invention to use small amounts of 7 ohm stabilizers or other nucleating agents, such as from about 0.001 to 5.0 weight percent based on the total reaction mixture. The foam stabilizers or surfactants used are known and may vary depending on the particular application.

Suitable stabilizers for slabstocks include "hydrolyzable" polysilicone-polyoxyalne block copolymers, such as U.S. Pat. No. 2,854,748 and U.S. Pat.
The block copolymers described in No. 0 are included. Another useful group of foam stabilizers are "non-hydrolyzable" polysiloxane-polyoxyalkylene block copolymers, such as U.S. Pat.
The latter group of copolymers are the block copolymers described in the above-mentioned polysiloxane-polyoxyalkylene block copolymers in which the polysiloxane component is formed by carbon-to-oxygen-to-silicon bonds, or rather by direct carbon-to-silicon bonds. It differs in that it is bonded to a polyoxyalkaline phosphor component. These various polysiloxane-polyoxyalkylene block copolymers preferably contain from 5 to 50% by weight polysiloxane polymer, with the remainder being polyoxyalkylene polymer. Yet another useful group of foam stabilizers is disclosed in U.S. Pat. No. 3,905.92.
It consists of polysiloxane in cyanoal as described in No. 4. Also useful are the siloxanes described in US Pat. No. 4,194.735.

Nidistomers can also be made from the N-(polyoxyalkyl)-N-(furkyl)amines of this invention. Chain extenders and polyisocyanates are also used when forming such didistomers.

Useful chain extenders include low molecular weight (ie, less than about 400) polyfunctional compounds that can react with the isocyanate. Typical examples include near-amino alcohols such as methylgetanolamine, ethanolamine, jetanolamine, glycols;
4-butanediol, ethylene glycol; aliphatic diamines; aromatic diamines: e.g. 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-45-diethyl-2,6-diaminobenzene (both of these The substance is also called diethyltoluenediamino or DETDA) tt-butyltoluenediamine 1.3
．． 5-Triethyl-2,6-diaminobenzene! 1.
5. 5'-tetraethyl-4,4'-diaminodiphenylmethane, etc.

A particularly preferred aromatic diamine chain extender is 1-methyl-
45-diethyl-2,4 diaminobenzene or a mixture of this compound and 1-methyl-3,5-diethyl-2,6 diaminobenzene. Also, U.S. Patent No. 4,246,
565 and 4,269,945 can be included.

When making polyurea elastomers, the polyisocyanates described in the discussion of polyurea and polyurethane-urea foams are considered suitable. especially,
The most preferred aromatic polyinsyanate for use in polyurea elastomers is MDI (4,4' diphenyl-methane diisocyanate) or derivatives thereof, including prepolymers. Such derivatives include conventional liquid forms as described in US Pat. No. 3,594,164 and so-called modified forms as described in US Pat. No. 3,152,162. MDI in liquid form is preferred, as pure MI)I can be solid and difficult to use.

The use of incyanate '1 is preferably in stoichiometric or greater than stoichiometric amounts based on all ingredients in the formulation, where the stoichiometric amount of incyanate is Equal to the sum of the number of equivalents of chain extender and N-(polyoxyalkyl)-N-(alkyl)amine.

As mentioned above, additional catalysts are not required in the production of nidistomers, but may be used. In a preferred embodiment, no additional catalyst is used.

Other conventional formulation ingredients, such as stabilizers or emulsifiers, also known as silicone oils, may be used in the formulation required. The stabilizer may be an organosilane or siloxane.

If desired, reinforcement materials known to those skilled in the art may also be used. For example, chopped or milled glass fibers, chopped or milled carbon fibers, and/or other inorganic fibers are useful.

Post-curing of the nidistomer is optional, but post-curing improves some properties such as heat sag. The employment of post-curing depends on the desired properties of the final product.

The precise scope of the invention is set forth in the claims, and the following specific examples illustrate certain aspects of the invention and, in particular, point out ways of evaluating the invention. However, the examples are set forth for illustrative purposes only;
Others should not be considered limitations on the invention. All parts and percentages are by weight unless otherwise specified.

Example Definition Polyol≠1=propylene oxide and polyoxyalkylene oxide triol made by Glycerigata et al. The product has a hydroxyl value of 64 KOH/.

has.

Polyol ≠ 2 = cytodiol in polyol made from pylene oxide and propylene glycol. The product has a hydroxyl number of 264! IvK0H/l
has.

Polyol 3 = polyoxyalkylene oxide triol (1
(polymerized at 05°C). The product has a hydroxyl value of 28■
It has KOH/.

Polyol number 4 = hydroxyl value 35.5wgKOH/made from propylene oxide and ethylene oxide,
A polyoxyalkylene oxide triol having Ethylene oxide inclusion is present as a cap at 16.5%.

Polyol Bin 5: polytetramethylene glycol diol with a molecular weight of about 2000.

Polyol-#6=Sialkylene ocytodiol in polyolefin having a molecular weight of 400 made from ethylene oxide.

Polyol *7 = Polyoxyal/oxide hexol made from propylene oxide, ethylene oxide, and sorbitol. The final product has a hydroxyl number of 2
It has 8qKOH/f. Ethylene oxide content is 10
weight - and exists as an internal block.

Voriolki 8 = Polyoxyalkylene oxide triol made from propylene oxide and glycerin. The final product has a hydroxyl number of 650 KOH/.

T-5000 triol was aminated with ammonia to arrive at all primary triamines similar to those taught in US Pat. No. 654,370.

triamine. The product was purchased from Texaco Chemical Company as Jeffamine (Registered Trademark a).
) I purchased it with the display of T-5000.

Catalyst +1 = Nickel catalyst, commercially available as "Nickel 5156PJ" by the Versior/Filtrol partnership.

Catalyst + 2-7 Raney Nickel commercially available by Activated Metals.

Catalyst 4++3=70% bis(dimethylaminoethyl)ether in dipropylene glycol.

Catalyst-44 = 55% in dipropylene glycol (D-triethylene diamine.

Catalyst ≠ 5-Kalushi Senyat! Copper catalyst commercially available as DE-508TN. Copper oxide 8 to aluminum oxide
2% is attached.

Catalyst ◆6 = Ni- due to Barshaw/Filtroll partnership! Nickel catalyst commercially available as 1288, 1/16 inch (16 m) extrudates O Surfactant ≠ 1 = Union Carbide L-554
Polysiloxane polyether block copolymer sold as 0.

Surfactant≠2=L-542 by union carbide
Polysiloxane polyether block copolymer sold as 1 0 Surfactant #3=Ninio/Carbide Y-10,
Polysiloxane polyether block copolymer sold as 184.

Incyanate A = Iaonate (registered trademark) 143 sold by Dak Chemical Co., Ltd.
MDI variant known as L.

Isocyanate B = toluene diisocyanate (2,4
80%: 2,620%) 0 incyane) C = meta-tetramethylxylylene diisocyanate sold by Cyanamide.

D = Cod by Dow Chemical
e) MDI preformer isocyanate sold as 205.

Chain extender A = Diethyltoluene diamino 0 sold by Lonza) Form modifier A = E published on May 6, 1987
PC Application Publication No. 220,297 (also October 1985)
U.S. Patent Application No. 791°5145 filed on May 25th
Form modifier prepared according to Example 7 of No.

Example 1 Preparation of N-(polyoxyalkyl)-N-(alkyl)amine with MW 500. Polyol number 1 (999,1
? .

0.605 equivalents) and isopropylamide 7 (51B, 9
f.

5.39 mol) and catalyst≠1 (25?) were charged into an autoclave (2 liters). The system was pressurized with hydrogen, 5 times pI, and then pressurized to 500 pI.
I changed it to Iif (55K?AG). reaction kk to 240
℃ for 12 hours. After cooling, the catalyst was removed by filtration and excess amine was removed by vacuum stripping. The isolated amine-terminated polyol has an amine value of 0.515 meq/? , had a conversion rate of 95% and contained 5.0% Kabli/G product. The tertiary amine content of this unique product was not determined. The following analysis of another patch, performed under the same conditions, showed that the primary amine content was 50% and the secondary amine content was 50% (both total reactive amines, total amines - secondary). (measured as a percentage of triamine) tertiary level is 0.05
7 ””/f.

Example 2 Method for manufacturing diol with MW 10,000.

Polyol dl121600f, which was dehydrated to 0.011% water in a 5 gallon autoclave, and Hepta 716
00r and 10f of medium sacyanocobaltate were charged to the zinc. The reactor was purged with nitrogen and evacuated at room temperature for 2
psia (0,14'/CIl!A) PC. The catalyst was activated at 80°C for 2.5 hours and propylene oxide 380F [partial pressure 20 psi (t 4 '/c
d) 3 was supplied.

The lag phase is hardly observed and tuckout (coo
The pressure dropped as soon as the onset of kout) occurred. Propoxylation continued at 80°C. The reaction was fast and the addition rate was controlled by the system's ability to remove heat.

A total of 21,242 f of propylene oxide was fed.

All volatiles were removed by polyol stripping.

Analysis shows that the polyol has a hydroxyl value of 21.011P)
H/f unsaturated 0.009''/f, moisture 0.014
% and viscosity &2566cks.

Example 5 N-(polyoxyalkyl)-N- with MW 1α000
Method for producing (alkyl)amines (difunctional).

The procedure used was that of Example 1. Polyol 800F (0,1697 equivalents) from Example 2, Isopropylagun 225.9F (3,82 equivalents), and Catalyst No. 128
2 (3.5% based on polyol) and hydrogen [200
p! 1i (14'/i)] was heated to 220°C for 66 hours. Amine number 0.185” cIq/ and conversion rate 8
A product with 7.1% was obtained. Tertiary amine content is 59
The primary amine content was 41.

ψ: 14-10 The overall procedure used was that of Example 1. In some cases, autoclaves of different dimensions were used;
9. The reaction conditions were the same. In each of the experiments below, polyol ≠ 3 passed 10 times! It was reacted with a tertiary amine of the designation J for about 19 hours under the following conditions: Catalyst charge: 65-1 based on polyol initial hydrogen pressure 200 pat
(14'/cd)t reaction 1-degree 190°C 0 deceleration is shown below: 4-kfx tl, 418 85.5 65.5
53.7 0.00445 Outer n-7”0 pi & 0
．． 576 76.7 74.5 25.7
Q, 0196 Jiinhoru 0.5B6 7
8.7 96.0 4.0 0.0657 J-B'f+ 0.450 91.8 8
4A I5.5 0.0468 77b
O,47496,77102200,0074
9-') 7L-A10.464 95.0 95.6
6.4 0.01410〃Mashirase Sacrilege 0.412 87.
6 100.0 0.0 0.00! *meq/f
Example 11: Process for producing N-(polyoxyalkyl)-N-(alkyl)amine from polyol #3 using mixed amine raw materials.

The procedure used was that of Example 1. polio/L45
Bool, diimpropylamine 5089,
Inglobilamine 44F, catalyst +128F and 200 pat (14"/-) of hydrogen were added to 2 liters of autoclave. The mixture was heated at 190°C for 20.5 hours.
heated to. The catalyst was removed by filtration and excess amine was removed by vacuum stripping.

The isolated product had the following analysis: total amine f
lli O-457"q/f-conversion" 497.2 To
, m 90%, tertiary amine 710% and tertiary amine 70017ml! Iq/10 Example 12 Preparation of N-(polytetramethyleneoxy)-N-(alkyl)amines of molecular weight approximately 2 (JOO) using a tertiary amine with a catalyst≠1.

The procedure used was that of Example 1. Polyol 5 (515,9F) and diisopropylamine (523
, 8F) and t&≠1 (253F) were charged into a 2 liter reactor. The reactor was purged with hydrogen to remove air and pressurized with hydrogen to 200 Pa1 (to 14) K.
did. The yarn was heated to 190°C and held at that temperature for approximately 21.5 hours. The catalyst was separated and the excess extensible material was removed resulting in a product with the following analysis: Total amine CL 7
68 m”/f, conversion rate 80 cm, secondary amine 94 cm,
Primary amine 6ch.

Example 16 Approximately 400 using a secondary amine with a nickel catalyst
Method for producing 0 molecular weight N-(polyoxyethyl)-N-(alkyl)amine.

The procedure was the same as in Example 1. Polyol≠6 (558,
Of), diimproamine (1357,8F), and t#, 4-1 (42,69) in a 1 gallon reaction vessel R.
I charged K. The reactor was purged with hydrogen to remove air and pressurized with hydrogen to 200 psi (14'/cIi).
If I did it.

The yarn was heated to 190°C and held at that temperature for approximately 23.5 hours. The catalyst was separated and excess volatiles were removed resulting in a product with the following analysis: Total Amy 5.78ff.
leq/f, E '491%, Q27min 929k
, Daiichi Ami 78%.

Example 14 Molecular weight 6000ON using secondary amino/ with catalyst → 5
-(Polyoxyalkyl)-N-(alkyl)amine Preparation 0 The procedure used was that of Example 1. Polyol 4-5
(1620,!M) and diisopropylamine (640,!M)
, 4f) and catalyst ≠ 5 (42,6f - tablets ground into powder under inert atmosphere) in 1 gallon of reaction &
It was installed in the equipment. The reactor was purged with hydrogen to remove air and pressurized with hydrogen to 20 l pat (14'/ct
ll). The system was heated to 190°C and held at that temperature for approximately 25 hours. After removing the catalyst and removing excess extrusive material, the product has the following analysis: total 70.187"q/f, conversion 450%, seedlings 795%, secondary amine 71%.

Example 15 MW6000 with high secondary amine content by continuous process
A method for producing N-(polyoxyalkyl')-N-(alkyl)amine.

6 ft (18 m) long with adjustable heater and hydrogen inlet 1 inch (2.5 cm) outside diameter (OD)
Catalyst DH6284.5 in the vertical tube (high pressure tube material)
f was charged. The catalyst was activated with hydrogen at 150°C. A mixture of polyol 45 (ISA, 4%) and diisopropylamine (516%') was made and subsequently fed into a tubular reactor. Feed was started and the following conditions were established: pressure 1000 psi (70 sid); feed rate 6
2717 hours; temperature 210°C; hydrogen flow rate 22 standard cc/
Minutes. Materials were collected after conditions were equilibrated. After removing excess amine by vacuum stripping, the product had the following analysis: Total amines 0.404""
/l: conversion rate 82%; secondary amine content 73%; secondary amine content 27%.

A separate experiment was carried out as per Example 15 at 210° C. and 2937 hours resulting in the following product: Total Amine Q, 422
""/f: Conversion rate 86%; Niamine 58%: Niamine
Ami/42chi.

Example 17 Preparation of a 2000 equivalent (molecular weight approximately 12,000) hexafunctional N-(polyoxyalkyl')-N-(alkyl)amine containing a high secondary amine content.

Polyol-$7 (500(1), diisopropylamine (152B, 9f), and catalyst 1 (1 osr) were charged to a 2 gallon autoclave. The reactor was pressurized with hydrogen and vented to remove air. , then pressurized with hydrogen to 200 psi (14 KJ/e:d) and sealed. The mixture was then heated at 190° C. for 19 hours. After cooling, filtering, and vacuum stripping, the isolated product was With the following analysis: total amine yo, 4o6""/r; conversion (us (S %,: gniamine 75.1%: primary amine 24°) Example 18 Low amine containing high secondary amine content Molecular weight trifunctionality N
-Production method of (polyoxyalkyl)-N-(furkyl)amine.

Polyol 4$=8 (60Of), diisoprobylamine/(3517,6F), and catalyst 1 (21f) were mixed into 2
A gallon autoclave was charged. The reaction was pressurized with hydrogen to remove air, then pressurized with hydrogen to 200 pat
(14'/cd) and sealed. The mixture was then heated at 190°C for 19 hours. Cool, filter,
One isolated product after IJ tubing had the following analysis: Total amines 5.62 meq 7y:
Conversion rate 714%: primary amine 95%; primary amine 15
tly.

reactivity studies Relative reactivity of the products from Example 1.

The slower rate of the product from Example 1 was confirmed in a series of gel formation studies with different incyanates. In all cases, a T-5000 control was run for comparison. In these experiments, the product from Example 1 and T-
5000 as an aromatic isocyanate (incyanate A,
(MDI variant) or an aliphatic incyanate (incyanate 0.m-tetramethylxylylene diincyanate 4-)
) to form the corresponding soft segment gel. Relative gel times were measured and are shown below.

'r-soo0 4 25 cases
1 5 approximately 400 amyl reacted rapidly with Incyanate A, and the product from Example 1 appeared slightly slower (note: gel times were adjusted to compare several experiments and to compare accurately). averaged). However, the product of Example 1 remained a higher quality gel of Isocyanate A (very stretchy, bulky, and not sticky). This means that the reaction with this MDI variant is more controlled. On the other hand,
T-5000tj consistently formed a gel containing a considerable amount of unreacted amine, and remained extremely sticky even when left undisturbed.

isocyanate) C, the product from Example 1 is T-50
It was considerably slower than 00.

RIM Processing/Physical Properties The product from Example 1 was evaluated in a standard polyurea formulation on a Mint-RIM machine against T-5000J'l.
The properties of polyurea elastomer blacks exceeding Nashi and 2O were determined.

Mixing studies in the processing mold filling, flow head profile and aftermixer areas showed that the reaction of the product from the Example 1 system was T-
I confirmed that it was slightly slower than 5000. Although the narrower mold and molding machine used in this trial did not allow for more rigorous evaluation of processing, the results suggest the potential for better mold filling with the product from Example 1.

Physical Properties The properties of the polyurea elastomer made in the trial were determined for materials that were post-cured (1 hour at 3757 (191°C)) and those that were not cured.Table ■, Example 19-2
In addition to the tensile properties of ○ similar to presented in 2, sag response (s
Ag response ) and flexural modulus were also evaluated. A polyurea based on the product from Example 1 is T-
It is clear that the properties are comparable to or slightly better than those containing 5000.

The dynamic mechanical properties of polyurea (see Table ■) were determined in the temperature range [-
Studied over 120-240°C.

The performance of the Nidistomers made from the amine of Example 1 was remarkable. Both Nidistomer systems showed the expected low temperature transition (Tf) at -53°C, and both systems had a significantly flatter temperature transition (Tm). ) was not shown at all. However, the nidistomer made from the amine of Example 1 had substantially better modulus multiples over a wide range of operating temperatures.

The amines evaluated in this study were made by the indicated amines of polyol Rin 1 with inglobil amine according to Example 1.

The resin component is amine polyether (+59.4%)! It consisted of chain extender A (30.5%).

No island medium was used. Incyanate is Inciane) Do, which is 1z5 rough free N based on MDI.
It was a CO soft block prepolymer.

4fL4 The ratio of fat to incyanate is 1. with an index of 105.
The slow wave used to make 0 black, which was 2/lO, was patented in U.S. Patent 4°189.
Mint -RIM s- as described in , No. 070
= It was. Heat the resin component to 55-60°C and heat the isocyanate to 60. ~65°C. The mold temperature was 120°C. The average shot time used to fill the mold was α5 seconds and most of the black was demolded after 1 minute (no attempt was made to study demold time). 22 blacks (8 based on T-5000 and 15 based on the product from Example 1) were made and properties were measured. Tensile and tear properties were determined using ASTM standard test stains. I asked about cutting materials.

Fence (“Wa Mo B Table ■ Atsuka ℃ + 25 64 78 + 70 55 62 +202 58 46 +240 25 56 Multiplu 20/+ 7o 2.4
2.1-20/-1-202532,8 -207+242 5.4
! L6 pieces Rheovibr
on) Mechanical Spectrometer, 2°C/min Form - N-(Polyoxyalkyl) - In this study, a standard foam formulation was used in the evaluation of all amine-terminated polyethers. The formulation was as follows: Polyether or amine 100 php water
4.0 catalyst 3
0.1 Catalyst 4 α4 surfactant 12
．． 0 Surfactant 22.0 7 Ohm Modifier 12.0 Isocyanate The ingredients were mixed to make 7 Ohm in a container on a drill press equipped with a 105 index turbine blade agitator. Stirring speed is 4000 rpm
Met. Polyether, water, excluding incyanate
The catalyst, surfactant and other additives were all added to the mixing vessel and stirred for 60 seconds. The mixture was allowed to stand for 15 seconds. Stirring was started again and incyanate was added and stirred for an additional 6 seconds. The mixture was then quickly poured into a 9X9X4 inch box and foamed. Each foam was then cured at 120°C for 5 minutes.

, a conventional polyol (polyol 4
+4) was used to make one control 7 ohm. This form combines surfactant 1 and surfactant 2 with surfactant 3.
It was made from the same ingredients except that it was used in place of . No problems were encountered when mixing or pouring the ingredients. The 7 ohm foamed to fill the container and showed a tendency to shrink when cooled after curing.

The polyurea foam was prepared from the regular N-(polyoxyalkyl-(alkyl)amine) prepared in Example 1 and from the T
I made it from -5000. When using T-5000,
It was not possible to create a form. Gel formation began immediately upon addition of isocyanate. The reaction was so fast that it was not possible to pour the ingredients out of the mixing container. No significant handling problems were encountered when the amine from Example 1 was used in the 7 ohm formulation above. Mixing was easily accomplished and the mixture was easily poured into foam containers. Although the overall reaction rate appeared to be slightly faster than that observed for polyol 4, it was certainly not close to that of T-5000. The 7 ohms produced completely filled the container and had no tendency to shrink after the foam was cured at 120° C. for 5 minutes. See Examples 25-26 in Table 1 for an overall summary.

Momo ratio heli Hand continuation supplementary book February 6, 1938

Claims (1)

[Claims] 1. N-(polyoxyalkyl)-N- having the following formula:
(Alkyl)amine: R[H]_(_h_z_)[(P)_p(S)_s(T
)_t]_z_-_(_h_z_) (wherein R is an initiator radical based on a compound containing a Zelewitinoff active hydrogen atom; H is a group represented by the following formula: ▲mathematical formula, chemical formula, There are tables, etc. ▼; P is a group represented by the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ S is a group represented by the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ; T is a group represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼; a is 0 to 175; b is 0 to 175; c is 0 to 30; n is from 1 to 3; when n is equal to 1, the sum of a+b+c must be equal to or greater than 2; R' is a carbon atom from 2 to
R″ is hydrogen or an alkyl group containing up to 18 carbon atoms; R″′ and R″″ independently contain from 2 to 12 carbon atoms is an alkyl group; h is 0 to 0.7; p is 0 to less than 0.5; s is 0.5 to 1.0; t is 0 to 0.15; z is an integer derived from the number of Zelewitinoff active hydrogens on the initiator, provided that when z is 2 and a and c are zero, b must be greater than 22). 2, R contains 2 to 6 carbon atoms, a is 0 to 50, b is 20 to 115, c is 0 to 15, R is an alkyl group containing 2 carbon atoms, N-(polyoxyalkyl)-N-(alkyl)amine according to claim 1, wherein R is an alkyl group containing 2 to 6 carbon atoms, and z is 2 to 6. 3, R contains 3 to 6 carbon atoms, a is 0 to 90, b is 25 to 98, c is 0 to 2, R″′ is isopropyl group, z is 3 to 6. N-(polyoxyalkyl)-N-(alkyl)amine according to claim 2, wherein 4 and R have a molecular weight of 18 to 400. oxyalkyl)-N-(alkyl)amine. 5. R is the following: ▲ Numerical formula, chemical formula, table, etc. ▼ ) amine. 6. N-(polyoxyalkyl)-N- having the following formula:
(Alkyl)amine: R[H]_(_h_z_)[(P)_p(S)_s(T
)_t]_z_-_(_h_z_) (wherein R is an initiator radical based on a compound containing a Zelewitinoff active hydrogen atom; H is a group represented by the following formula: ▲mathematical formula, chemical formula, There are tables, etc. ▼; P is a group represented by the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ S is a group represented by the following formula: ▲ Numerical formulas, chemical formulas, tables, etc. Yes▼; T is a group represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼; a is 0 to 175; b is 0 to 175; c is 0 to 30 ; n is from 1 to 3; when n is equal to 1, a+b+c must be equal to or greater than 2; R' is an alkyl group containing from 2 to 18 carbon atoms; R'' is hydrogen or an alkyl group containing up to 18 carbon atoms; R'''' and R'''' are independently an alkyl group containing 2 to 12 carbon atoms; h is 0 to 0. 3, p is 0 to 0.4, s is 0.7 to 1.0, t is 0 to 0.05, and z is 2 to 6, provided that z is 2 and and when a+c is zero, b must be greater than 22, and the equivalent weight of the amine is from 1,000 to 10,000)
. 7, R contains 2 to 6 carbon atoms, a is 0 to 150, b is 20 to 115, c is 0 to 15, and R' is an alkyl group containing 2 carbon atoms; , R″′
is an alkyl group containing 2 to 6 carbon atoms) z is 2 to 6, N-(polyoxyalkyl)-N-(alkyl)amine according to claim 6. 8, R contains 3-6 carbon atoms, a is 0-90, b is 25-98, c is 0-2, R″′ is isopropyl group, z is 3-90, N-(polyoxyalkyl)-N-(alkyl)amine according to claim 7, which is 6. oxyalkyl)-N-(alkyl)amine. 10. R is the following: ▲ Numerical formula, chemical formula, table, etc. ▼ ) Amine. 11, N-(polyoxyalkyl)-N having the following formula
-(Alkyl)amine: R[H]_(_h_z_)[(P)_p(S)_s(T
)_t]_z_-_(_h_z_) (wherein R is an initiator radical based on a compound containing a Zelewitinoff active hydrogen atom; H is a group represented by the following formula: ▲mathematical formula, chemical formula, There are tables, etc. ▼; P is a group represented by the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ S is a group represented by the following formula: ▲ Numerical formulas, chemical formulas, tables, etc. Yes▼; T is a group represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼; a is 0 to 175; b is 0 to 175; c is 0 to 30 n is 1 to 3; when n is equal to 1, a+b+c is equal to or greater than 2; R' is an alkyl group containing 2 to 18 carbon atoms; R'' is hydrogen; or an alkyl group containing up to 18 carbon atoms; R'' and R'' are independently an alkyl group containing 2 to 12 carbon atoms; h is 0 to 0.15; p is 0 to 0.4, s is 0.7 to 1.0, t is 0 to 0.05, and z is 3 to 6).12, R contains 2 to 6 carbon atoms and a is 0 to 150, b is 20 to 115, c is 0 to 15, R' is an alkyl group containing 2 carbon atoms, and R'''
N-(polyoxyalkyl)-N-(alkyl)amine according to claim 11, wherein is an alkyl group containing 2 to 6 carbon atoms. 13, R is 3 carbon atoms
-6, a is 0-90, b is 25-98, c is 0-2, and R″′ is an isopropyl group, N- according to claim 12 (Polyoxyalkyl)-N-(alkyl)amine. 14, R is molecular weight 18
N-(
Polyoxyalkyl)-N-(alkyl)amine. 15. The N-(polyoxyalkyl)-N-(alkyl)amine according to claim 14, wherein R is as follows: ▲Numerical formula, chemical formula, table, etc.▼. 16, N-(polyoxyalkyl)-N having the following formula
-(Alkyl)amine: R[H]_(_h_z_)[(P)_p(S)_s(T
)_t)_z_-_(_h_z_) (wherein R is an initiator radical based on a compound containing a Zelewitinoff active hydrogen atom; H is a group represented by the following formula: ▲mathematical formula, chemical formula, There are tables, etc. ▼; P is a group represented by the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ S is a group represented by the following formula: ▲ Numerical formulas, chemical formulas, tables, etc. Yes▼; T is a group represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼; a is 0 to 175; b is 0 to 175; c is 0 to 30 ; n is 1 to 3; when n is 1, a+b+c is equal to or greater than 2; R' is an alkyl group containing 2 to 18 carbon atoms; R'' is hydrogen; or an alkyl group containing up to 18 carbon atoms; R″′ is an alkyl or aryl group containing 2 to 12 carbon atoms; h is 0 to 0.15; p is 0 ~0.4, s is 0.7-1.0, t is 0-0.05, z is 3-6, and the equivalent weight of the amine is 1,000-10,000. be)
. 17, R contains 3 to 6 carbon atoms, a is 0 to 150, b is 20 to 115, c is 0 to 15, R' is an alkyl group containing 2 carbon atoms, R″′
N-(polyoxyalkyl)-N-(alkyl)amine according to claim 16, wherein is an alkyl group containing 2 to 6 carbon atoms. 18, a is 0 to 90, b is 25 to 98, c is 0 to 2, and R″′ is an isopropyl group, )-N-(alkyl)amine.19, R is molecular weight 18
N-(
Polyoxyalkyl)-N-(alkyl)amine. 20, R is the following: ▲ Numerical formula, chemical formula, table, etc. ▼ N-(polyoxyalkyl)-N-(alkyl)amine according to claim 19.