JPS60179422A - Production of ionomer and polyurethane elastomer from adduct of monoether polyol and polyether polyol having carboxylic acid group - Google Patents

Abstract

PURPOSE:To form an ionomer suitable for use in the production of a polyurethane elastomer, by reacting a mono- (or poly-) ether polyol with a specified dicarboxylic acid and neutralizing the reaction product with monovalent - tetravalent metal ions. CONSTITUTION:A mono- (or poly-) ether polyol (e.g., diethylene glycol or polyoxyethylene triol) is reacted with at least one ethylenically unsaturated dicarboxylic acid selected from among maleic, fumaric and itaconic acids in a weight ratio of about 99:1-70:30 in the presence of a peroxy free radical initiator (e.g., hydrogen peroxide or benzoyl peroxide). The formed adduct is neutralized with monovalent - trivalent metal ions of Group I a, IIa, VIII, I b or IIb (e.g., Na<+>, K<+>, Ca<+2>, or Mg<+2>) to convert about 10% or above carboxyl groups into a salt. In this way, a metal salt (ionomer) of mono- (or poly-) ether polyol adduct having a carboxylic acid group can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to the use of metal salts selected from monoether and polyether polyol adducts containing carboxylic acids (
ionomer). The invention also relates to these ionomers as compositions. The invention also relates to polyurethane elastomers made from ionomers in conjunction with methods for making these ionomers.

[Conventional technology]

The reaction of carboxylic acids with polyols is well known. The best known reaction between these compounds is the reaction where the acid groups react with the OH groups in the polyol to form the polyester polymer, although other reactions are also known. US Patent No. 4
, No. 250.077 'El (by Bonin %) mixes a monoolefinically unsaturated carboxylic acid with many types of polyols and then polymerizes the mixture with a free radical generator to produce a graft polymer. It shows. The preferred carboxylic acid (and the only acid used in the examples) is acrylic acid, which is homopolymerized by itself. It must be noted that this document does not teach the exact mechanism by which the "polymerization" reaction takes place.

U.S. Patent No. 4.365.024 (Frentzel)
is suitable for incorporation into polyurethane foams by reacting a polyoxyalkylene adduct with an esterified unsaturated dibasic acid containing 4 or 5 carbon atoms under free radical polymerization conditions. Indicates the production of surfactants.

The mechanism of this reaction is called grafting. That is, the ψ reaction product consists of a polyoxyalkylene adduct backbone to which "grafts" of dissonant diesters are attached at intervals. See lines 46-51 of Volume 4 of this patent specification. This patent further states that [given that, as is well known, the unsaturated diesters of the present invention cannot be homopolymerized, this reactor'r:
'j is believed to involve the addition of a single diester unit to a polyoxyalkylene adduct backbone.'' It teaches that these surfactants can be used in phenolic foams, polyincyanurate foams, and polyurethane foams.

U.S. Patent Application No. 5N475,785 (Fren
tze 1) and 5N475,786 (Fren
tzel % ) was released on March 16, 1986! 11 is prepared by adding a small amount of maleic acid, fumaric acid, itaconic acid or mixtures thereof in the presence of a peroxy free radical initiator to a polyhydroxy-containing monomer.
or the preparation of carboxylic acid-containing mono- and polyether polyol adducts by reaction with polyether compounds (eg polyether diols or triols). These patent applications also disclose the preparation of polyurethane prepolymers and aqueous polyurethane dispersions from the carboxylic acid-containing mono- and polyether polyol addition products described above.

[Problem that the invention seeks to solve]

These selected carboxylic acid-containing mono- and polyether addition products have been found to be particularly advantageous for the production of ionomers and polyurethane elastomers. A single acid unit on the backbone provides sufficient sites to react with metal ions to form an ionomer, which in turn can be converted into a polyurethane elastomer.

[Failure to solve the problem]

Accordingly, the present invention is directed to a method for preparing the gold nine salt (ionomer) of a carboxylic acid-containing mono- or polyether polyol addition product, which method comprises: (a) maleic acid, fumaric acid, itaconic acid and mixtures thereof; An ethylenically unsaturated dicarboxylic acid selected from the group consisting of The weight ratio of the mono- or polyether compound contained is approximately 9.
9:1 to 70:30, and (b) a sufficient amount of the addition product formed in Periodic Table 1a, 2a, 8
, neutralizing with a metal ion selected from the group of monovalent, divalent or trivalent metal ions of Groups 1b and 2b to convert at least about 10X of the carboxylic groups in the addition product to salt groups. It consists of things.

These ionomer compounds can be used in additional step (C) below.
can be used in the production of polyurethane elastomers. That is, step (c) is carvone? '; 34-containing monoether or polyether polyols by reacting at least one of these B4K products with polyisocyanates to produce polyurethane distomers containing carbon-limiting salts. Become.

Additionally, these polyurethane elastomers can be used as plastic products and other useful products.

Furthermore, the present invention is directed to the above metal salts of these carboxylic acid-containing monoether and polyether polyols and the resulting polyurethane elastomers as novel compositions. The group-initiated addition reaction is thought to occur through a three-step mechanism. That is, it is the following equation (1
) to (X). Here, the monoether polyol or polyether polyol used is A, one of the selected molecules is B, and the free radical initiator of the peroxy type is represented by RQQR: Initiation: ROOR--2RO (1) Propagation: A + RO・−→A・+ROH(n)A・10B −
→ A-B・θ11) A-B-+ A −-A-B + A-+IV) A-B
・+ROOR-→A-p-OR+ RO(V)A-B・
10 RO) I -1 → A-B + RO- (to) stop: 2po-=-----→ROOR (VIOA・+A・−-
-1-A-A Busy hB・+A・--1→A-B-A (IX)AB・+
AB--11-ABBA (X) Tripropylene glycol (TPO) is M4 (polyether polyol (A)
and maleic acid [cis-HooccH=cncoo
H] or fumaric acid [trans-HooCCH-CHC00
When using any of the above equations (n), Cll0 and (Ill0) as the following equations (Ila), (Ill&) and CPJ8. )
It is expressed as: HHH (TPO) HH ) (H Hc-aH' Q=O0=0 0H0H OHOH As shown in the above equation (Ill&), the carboxylic acid is the oxygen in the ether bond (c-Q-0) Substitute a hydrogen atom on a carbon adjacent to an atom.For TPG as a polyether polyol, there are three other positions where the acid group could substitute a hydrogen. In theory, each carboxylic acid group can cover all 4 carbon atoms on TPG.
It is possible to combine in two positions. In fact, steric effects prevent the binding of many acid groups on such short polyether polyols.

On longer polyether polyols, many carboxylic acid groups can be attached.

Malenic acid, fumaric acid and itaconic acid [HOOOOH
, O(=OH,) C0OH':l is a slightly ethylenically unsaturated dicarboxylic acid that can be used in the present invention because it does not homopolymerize. Free radical addition reactions with these remove hydrogen from other polyols [equations above (
mV)] or other hydrogen atom source. Maleic acid and fumaric acid or a mixture of both are preferred from cost considerations.

Polyhydroxy-containing monoethers and polysaccharides suitable for the present invention. Ether compounds contain two or more hydroxyl groups and one or more ether bonds (C
-0-C) and having a molecular weight from 106 to about 20,000. The compounds are commonly referred to as monoether polyols or polyether polyols. Two or more hydroxyl groups are required to react with the polyisocyanate to form the polyurecne prepolymer. Ether bonds are necessary for the generation of free radicals on adjacent carbon atoms. J, Org, by VoMalatesta and J, O,5caiano (
! hem, , 19 B 2 , 47 , 1455-
See "Absolute rate constants for the reaction of tert-butoxyl with ethers: the importance of stereoelectronic effects" on page 1459. Polyester polyols and other types of polyols that do not contain ether linkages could not be used in this reaction, but the reaction with polyisocyanates was similar to 1. It could be used as an auxiliary polyol and its analogues.

In particular, suitable monoether polyols include diethylene glycol and dipropylene glycol. Because of their relatively short length, Ig-, mo/, x-del polyols are usually not used alone, but in combination with polyether polyols.

Suitable polyether polyols have 2 to 8 water r'l:
It includes various polyoxyalkylene polyols having 2 groups and mixtures thereof. These can be prepared by condensing an alkylene oxide or a mixture of alkylene oxides with a polyvalent initiator or a mixture of polyvalent initiators using random or stepwise addition according to well-known methods. Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, amylene oxide; aralkylene oxides such as styrene oxide and halogenated alkylene oxides such as trichlorobutylene oxide; tetrahydrofuran, shrimp chlorohydrin and the like. Things can be mentioned. The most preferred alkylene oxides are ethylene oxide, propylene oxide or mixtures of these two oxides using random or stepwise oxyalkylation.

The polyvalent initiators used to prepare the polyether polyol reactants include compounds of manure and mixtures thereof = (a) ethylene glycol 1,3-propylene glycol, 1,2-propylene glycol, butylene glycol; (b) aliphatic diols such as fukundiol, bentanediol and the like; (b) aliphatic) diols such as glycerin, trimethylolpropane, trimethylolpropane, trimethylol, Hegisa/and their fA-IJJ versions; /c) (d) polyamines such as tetraethylenediamine and (θ) alkanolamines such as jetanolamine, triethanolamine and their λ10 and above. .

A clever group of multi-initiators used to convert polyether polyol reactants are aliphatic diols and triols such as ethylene glycol, propylene gellicol, chrycerin, trimethylolpropane and the like. Consisting of

The alkylene oxide-polyhydric initiator condensation reaction is preferably carried out in the presence of a catalyst such as KOH, which is well known in the art. This reaction is preferably carried out using a sufficient proportion of alkylene oxide to provide a final polyol product having an average molecular weight of about 200 to 10,000, more preferably about 300 to 6,500. . Thereafter, the catalyst is removed and the hydroxyl-
Preferably, the polyether polyol remains which can be used to prepare the mother-in-law prepolymer.

Preferred polyether polyols are from diols, triols and mixtures thereof? J'r 4.

The most preferred polyether polyols for this invention are about 3
Polyoxyethylene diols and triols, polyoxypropylene diols and triols, block and random polyoxyethylene-polyoxybropylene diols and triols and mixtures thereof, with an average molecular weight of 00 to 6.500.

The monoether and polyether polyol reactants of the present invention may be reacted with a diacid or anhydride to form a polyester polyether polyol prior to the addition reaction of the present invention [step (a) above]. You can also do it. Therefore, polyester polyether polyols are produced which have carvone light distributions spaced apart in the molecule.

Any peroxy type free radical initiator can be used in the present invention. Other types of initiators are not suitable for the present invention.

Typical peroxy-type free radical initiators are peroxidized aqueous systems, and peroxidized dibendiyl, acetyl peroxide, penzoyl hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, per! lJ:・□・? Uroyl peroxide, butyryl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, diacetyl peroxide, dialphacumyl peroxide, dipropyl peroxide, diimpropino peroxide, isopropyl-t peroxide -butyl, butyl-t-butyl peroxide, dilauroyl peroxide, sifuroyl peroxide, ditriphenylmethyl peroxide, bis(P-methoxy-benzoyl) peroxide, P-monomethoxybenzoyl peroxide, superpositioned rubrene, ascari doll, t
-butyl peroxybenzoate, diethyl peroxy terephthalate, propyl hydroperoxide, isopropyl hydroperoxide, n-7' f hydroperoxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide, trans-decalin hydroperoxide, α-methylbenzyl hydroperoxide, α -Methyl-α-ethylbenzyl hydroperoxide, tetralin hydroperoxide, triphenylmethyl hydroperoxide, diphenylmethyl hydroperoxide, 2,5-di-methyl-2,5-bis(2-ethylhexanoylheloxy)hexane, 1 .1-bis(1
-butyl-peroxy)cyclohexane and t-butyl perbenzoate and hydroperoxides.

As mentioned above, the weight ratio of all monoether polyether(s) and polyether polyols (furnace) used for the non-dicarbonate fermentation is from about 99=1 to about 7.
It should be 0:30. If less than about 1 jL W parts of nucleic acid are used per about 99 parts by weight of the polyol, the properties of the polyol will hardly change and the reaction will be meaningless for many applications. About 30 parts per about 701 parts of the polyol
When more than 1 part by weight of the catalyst is used, a significant portion of the nucleic acid often does not react with the polyol because sufficient active sites are not present. This weight ratio is approximately 95:5 to 80:2
It is preferable to set it to 0.

Besides the selected reactants, peroxy-type initiator and weight ratios as described above, the other reaction conditions at this stage are also not specific to the invention, and the process of the invention is not amenable to any particular conditions. Should not be limited. This reaction takes place at approximately 25°C.
Preferably it is carried out at a temperature of -150°C, more preferably the reaction temperature is in the range of about 80°C to 160°C. The reaction temperature should be high enough to activate the peroxy-type free radical initiator for this reaction. In some cases, it is desirable to add a free 11f group promoter, such as a redox catalyst, to accelerate the reaction. The reaction time depends primarily on the reaction temperature employed; suitable reaction times are about 30 to 600 minutes. The reaction is monitored by following and detecting the disappearance of mylene alpha, fumaric acid or itaconic acid in the reaction mixture by conventional analytical methods.

Generally, this reaction can be carried out without a solvent. However, in some cases, when using solid polyether polyols, it is desirable to dilute the reaction mixture with water or other solvent to facilitate the reaction.

Furthermore, the present invention does not particularly require a reaction pressure above or below atmospheric pressure. Atmospheric pressure is preferred to avoid the expense of special reaction vessels. The free radical initiated reactions of this invention can be carried out under conditions well known as suitable for free radical polymerization. The reaction consists of the reactants, initiator(s) and optionally free radical promoter(s) until the reaction is complete.
and solvent at a temperature of about 25°C to 150°C in an inert atmosphere (
Advantageously, this is carried out by mixing with a solid material blanket).

The initiator(s) and optionally promoter(s) and solvent may be added at the beginning of the reaction or may be cooled in portions at intervals during the reaction.

Similarly, one unsaturated acid reactant(s), and monoether polyol(s) or polyether polyol(s).
The reactants may be mixed at the beginning of the reaction or brought together gradually as the reaction progresses. The adduct produced by this reaction is generally water-insoluble.

As mentioned above, the produced addition product can be converted into carbon M in the addition product according to the present invention.7. +H at least about 10
% to Kanabashi salt groups (eg cooNa). The presence of these salt groups increases certain physical properties of the polyurethane elastomers made therefrom, such as hardness, tensile strength and flexural elongation, but does not significantly reduce elongation. Therefore, the obtained polyurethane elastomer can be obtained without using an extender and a polyisocyanate.
7 physical properties.

Suitable metal cations for forming the ionomers of the invention are those of the Periodic Table of 1a, 2a, 8.1b and 2b.
() (anabook of Chemist
ry and Physics, Chemical R
u'bfer Pu'bliehlng Co, +6
5rdEd, see inside cover)
The metal ions of 1115 are Na+, K", Li",
Agj HBr and Ou+. Suitable divalent metal ions include Mg+2.Oa'', Ba+, cu+2.
Pd+", Pt+2. Cd + HBr-1θ,
C (compilated with %j, Nl+2 and zn+2)
Ru. 9 The incorrect pentavalent metal ion is Fe+3. Preferred metal ions are, in part, those of the alkali and alkaline earth metals, especially Na+, K+, 'C!
a'' and Mg+2 are preferred from the viewpoint of reaction rate.

Ionomers containing metal ions greater than 77!1i can still be used.

Kanahashi ions can be produced by adding a metal-containing chemical to a water bath solution and dissipating metal cations from anions. Suitable anions include hydrate, oxide, formate, acetate, nitrate, carbonate, and bicarbonate. Other metal-containing compounds that exhibit some degree of ionization in water can also be used. Hydrate and oxide anions are preferred because they do not produce impurities that require separation from the bath liquid.

The amount of metal ion should be sufficient to convert at least about 10 fii carboxylic acid groups to metal salts.

This is believed to be an approximate minimum of 151° of salt groups that in most applications will result in a significant change in the properties of the adduct. More preferably, at least a majority (i.e., about 50X or more) of the carboxylic acid groups are
It is better to convert it into a 4-salt group. For some applications, it may be advantageous to convert substantially all (ie, 95% or more) of the carboxylic acid groups.

This neutralization step is accomplished by simply adding the unneutralized adduct produced in step (a) to an aqueous solution containing the desired decomposed metal salt compound, allowing neutralization to occur in situ. You can also.

5. Polyurethane elastomer $'! The carboxylic acid-containing monoether and polyether polyol adducts produced as described above may be used to produce polyurethane elastomer products. These elastomers are made by reacting these metal salt compounds with at least one hairy polyisocyanate under conventional and well known reaction conditions.

Suitable polyisocyanates include free aromatic, cycloaliphatic, aliphatic diinocyanates and higher polyisocyanates. Diisocyanates are a preferred class of polyisocyanates. Ribbon group diisocyanates include hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-tetramethylene diisocyanate and 1,10-decamethylene diisocyanate.

A suitable aromatic diisocyanate is toluene-2,4-
or 2,6-diisocyanate (also known as a mixture or individually TDI), 1,5-naphthalene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate), 4-chloro-1,3-phenylene diisocyanate, 2,4'-diisocyanat diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 2,4-dimethyl-1,3-phenylene diisocyanate), 4,4'-diisocyanate diphenylneedle, penzidine diisocyanate), 4e4'
-diisocyanatodibenzyl, methylene-bis(4-phenyl-isocyanate) (also known as MDI) and 1,3-phenylene diisocyanate.

In addition to the presence of these two reactants, other reaction parameters for this polyurethane production process are also non-critical.
The invention should not be limited to any particular arrangement for carrying out this process.

For some applications, it may be desirable to add one or more chain extenders. These include any compound containing two active hydrogen-containing groups and having a molecular weight of 18-200. Specific examples include diols, diamines, hydrazines, dihydrazides and the like. A preferred diol is ethylene diol. Other suitable compounds include ethylenediamine, inphoronediamine, diethylene glycol and 1,4-butanediol.

The reaction rate between ionomer(s) and polyisocyanate(s) can be increased by using commonly known polyurethane biocatalysts. These include tertiary amine catalysts and organometallic compounds such as organoscissus and organosthmus compounds. However, the use of such catalysts is not critical to the invention.

Furthermore, VllJ agents, pigments and carbon black,
Halos such as silica and clay can also be incorporated into these urethanes.

incyane) (NCO) in the reactant Photoray hydroxyl (O
The ratio of H) groups preferably ranges from about 09=1 to about 1.2:1 dry weight, more preferably from about 1:1 to 1.05:1.

The preferred reaction temperature for producing elastomers is about 2
5°C to 150°C, with a well-built trench, about 25°C to 150°C.
It is in the range of 30°C.

In this polyurethane elastomer production step it is advantageous to add additional compounds which also react with incyanate groups. A combination of these for follow-up! It includes conventional compounds known to react with polyurethanes, polyether polyols, polyester polyols, and polyisocyanates to form polyurethanes.

The carboxylate-containing polyurethane elastomer of the present invention is white! 1II) jli 4. “It can be used as building parts, cane parts, and sports equipment.

〔Example〕

The following items are only for further explanation of the present invention, and parts and percentages are not specific. Depends on weight.

Example 1 Fumar Ijk (140 l) and polyether polyol (j) (3500 l) were placed in a three-necked flask. The mixture was heated to 105°C in a hot atmosphere with a pestle.
heated to. 1 [curtain initiator, 2,5-dimethyl-2,
3 g of 5-bis(2-ethylhexanoylperoxy)hexane was added every 1.5 hours. A total of 27 g of initiator was added within 13 hours to allow complete reaction of the fumar 11 stomach.

The amber liquid product was cooled to room temperature and used without 31rta4 to prepare 4 medium gold JIA j', 4 (see Examples 2, 3 and 4 below!1). As a result of engineering R analysis of this carboxylic acid-containing polyether polyol,
There was no bond to 2j of fumaric acid at 1650 m-', indicating that the fumaric acid was completely reacted.

[Note] ■POLY-G■85-29-2'' (product name) manufactured by Olin Company of Stamford, Connecticut.

This polyether polyol is A triol with an average molecular weight of 6400, The glycerin initiator is first ethylene oxide, then ethylene oxide. Block reaction of oxide Yo#)! 1-゛! make silkworms

Example 2゜Calcium: Carboxylated polyol of Example 1 (2, OO'Og ), OaO (ts b, y 9
) and water (100, j7) were added. The mixture was heated to 90° C. with stirring. Conversion of the nucleic acids to calcium salts was complete after 3 hours, as determined by EMR analysis. Water was removed directly in air to obtain a liquid product.

Example 5 Preparation of Magnesium Salt Example 1. carboxylated polyol (2,000 Jil), MgO (24 g) and water (
100g) was added. After 3 hours at 90°C, engineering R analysis confirmed the completion of the conversion of the nucleic acid to ME salt. The water was removed under vacuum.

Example 4. Example 1. Carboxylated poly, t
-k (2,0009), ZnO (533 g) and water (
100g) was added. After 5 hours at 90° C., the reaction was confirmed to be complete by engineering analysis. The water was removed using a vacuum.

Example 5 Example of perforation of R-M molded product 1. Polyether polyol (172g) used in
Ethylene glycol description iQ IE, long-term agent (2B &),
Organo mercury catalyst ■ (11I), silicone deaerator ■ (
' 2 y + t4 ) and polymer incyanate ■ (
147, s 11) was weighed into its l1li() and placed in a large beaker. The contents were stirred for 1 minute, degassed in a true brush, poured into a 1/8" x 6# x 6# mold, and the 155 After curing for 24 hours at 135° C., the solid product was deposited from the mold and subjected to physical property testing.

The results are shown in Table 1.

[Note] ■NJ 07072. Karlstadt, 14
%SF-1080' (trade name), commercially available from GE Silicone Products Heartment, Waterford, NY 121BB. ) ■Polymer MDI 2% F3onate 143L is commercially available from Upjohn Co., Ltd., Polymer Chemical Division, Laporte, TX.
(Product name) Examples 6 to 9 The procedure of Example 5 was repeated except that the type of polyol, the weight of ethylene glycol, and the weight of isocyanate were changed. The results are shown in Table 1.

These results demonstrate that using the indicated ionomer, the hardness and flexural modulus of Example 5 were improved without the use of additional amounts of ethylene glycol and isocyanate. This shows an increase compared to . This means that by using fewer chain extenders and isocyanates, the cost of manufacturing products with these improved physical properties is reduced. Examples 8 and 9 differ from Example 5 in that the relative amounts of reagents were changed.
is different from Example 6. Examples 8 and 9 give moldings with relatively high hardness and strength.

Table I Example Polyol EG Mercury Catalyst Polymer Incyanate 5 85-29-2 1721128g, 1g,
147.5 fl.

6 Example 2 172 28 1 146.77 Example 3 1
72 28 1 146.78 85-29-2 12
9.5 3iS, 6 1 183.89 Example 2 129
．． 5 36.6 0.75 183.4 [Note] ■JFI measurement according to ASTM D 2240-75 ■AS
1111 standard by TM D 790-80 ASTM
By D 412-80? 1tll constant ■ Hardness IW without measurement ■ Flexural modulus ■ Elongation ■ Shore D -20'F 73°F 158°F 5X
46 3a511 19.7B3 14,196. 2
4055 42.472 22,331 16,203
20056 52.412 2a351 20,46
0 of 58 104.055 67.556 47,7
88 61.6772 143.520 92.183
65.856 4B35 Example 10 TDI) Polyether polyol (150 g) used in Preparation Example 1 of i'7 type, mercury catalyst ■ (1, I 11), silicone deaerator ■ (2 @
) and 2,4- and 2,6-) luenediamine diincyanate (TDI) (6,6y) were added in that order to a large beaker. Stir contents for 1 minute, degas
Pour into a 78' x 6' x 6'' mold. 24 min at 85°C.
After curing for a period of time, a solid sample was taken out 17 and subjected to physical property tests. The results are shown in Table ■.

[Note] ■NJ 07072, Karlstadt, 14
10ocure 44" commercially available from Kosan Chemical Co., 400 Ban Street, NY 12188. Kame 5F-1080" commercially available from GE Silicone Products Department, Waterford, NY 12188. 11-13 Repeat the procedure of Example 10, but change the type of polyol and the weight of each component. The results are shown in Table H.

These results show that using the indicated ionomer, hardness and tensile strength are increased compared to Example 10 without chain extender and additional incyanate, with little change in elongation. .

/

Claims (9)

[Claims] (1) (a) at least one polyhydroxy-containing monoether or polyether compound with an ethylenically unsaturated dicarboxylic acid selected from the group consisting of maleic acid, fumaric acid, itaconic acid and mixtures thereof;
reacting in the presence of a peroxy-type free radical initiator and at a ratio of the amount of the polyhydroxy-containing monoether module to nucleic acid of about 99:1 to 70:50, and (b) the produced the addition product,
Sufficient amount of Periodic Table 1 a p Za p 8 g
Neutralization with a metal ion selected from the group of monovalent, divalent or hexavalent metal ions of groups lb and 2b, converting at least about 10% of the carboxylic acid groups in the addition product to salt groups. A method for producing a metal salt of a carboxylic acid-containing monoether and polyether polyol addition product. (2) The polyhydroxy-containing monoether or polyether compound can be used as polyoxyethylene diol, polyoxyethylene triol, polyoxypropylene diol, polyoxypropylene triol, block and random polyoxyethylene 7 polyoxypropylene diol and triol. , and mixtures thereof, having an average molecular weight of about 300 to 6500(7), and reacting with an acid selected from the group consisting of maleic acid and fumaric acid at a temperature of about 80°C to 130°C. The method according to claim 1. (3) Metal ion N a”* K+e Ll” T
Ag” * Hg+, “u+. Mg+l, Ca", Ba+1, cu+t
, cd+*, Hg+! , FB+2゜0(,+
t, H1+2, Zn", pd+t, p
The method according to claim 1, wherein the method is selected from the group consisting of t+t and a θ+3. (4) The method of claim 3, wherein said addition product is neutralized with a sufficient amount of a neutralizing agent to convert substantially all of said carboxyl-11 groups to salt groups. (5) A metal salt of a carboxylic acid-containing monoether or polyether polyol addition product produced by the method described in claim 1. (6) A metal salt of a carbon i'I=-containing monoether or polyether polyol addition product produced by the method described in claim 4. (7) (a) At least one polyhydroxy-containing monoether or polyether compound is
7. The weight of the monoether or polyether compound relative to the nucleic acid in the presence of an ethylenically unsaturated dicarboxylic acid selected from the group consisting of fumaric acid, itaconic acid and mixtures thereof and a free radical initiator of the peroxy type. reacting at a ratio of about 99:1 to 70:30 to form a carboxyl group-containing monoether module or polyether polyol adduct; (b) the formed adduct;
Neutralization with a sufficient amount of metal ions selected from the group of monovalent, divalent or trivalent metal ions of Groups 1a, 2a, 8.1b and 2b of the Periodic Table, converting at least about 10% of the carboxylic acid groups to salt groups; and (C) reacting the neutralized carboxylic acid-containing monoether or polyether polyol with an organic polyisocyanate to form a carboxylate-containing polyurethane elastomer. A method for producing a polyurethane elastomer containing a carboxylate salt. (8) The method according to claim 7, wherein the organic polyisocyanate is at least one aromatic, cycloaliphatic and aliphatic diincyanate. (9) N (1! The molar ratio of Q to OH groups is about 09:1 to 1
．． 8. The method of claim 7, wherein the ratio is 2:1. OQ A carboxylate-containing polyurethane distomer produced by the method according to claim 7.