CA1179098A

CA1179098A - Synthetic polymers by polyisocyanate polyaddition process

Info

Publication number: CA1179098A
Application number: CA000365946A
Authority: CA
Inventors: Richard C. Baron
Original assignee: Polaroid Corp
Current assignee: Polaroid Corp
Priority date: 1979-12-03
Filing date: 1980-12-02
Publication date: 1984-12-04
Also published as: DE3070132D1; KR840000523B1; EP0032547B1; EP0032547A3; AU538880B2; US4328322A; KR830004349A; EP0032547B2; AU6502680A; EP0032547A2

Abstract

ABSTRACT
Synthetic polymers and a process for their prepara-tion by a polyisocyanate polyaddition reaction are described.
Synthetic polymers are provided by the reaction of a polyiso-cyanate with substantially an equivalent amount of an oligomeric para-, meta- or di-meta-aminobenozic acid ester or amide having the formula wherein n is an integer of from 2 to 4; each x is one or two;
each benzoyl nucleus is para-, meta- or di-meta- amino-substi-tuted; each Z is -O- or -?-; and G is an n-valent radical which may be obtained by the removal of hydroxyl or amino groups from an n-valent oligomeric polyol or polyamine having a molecular weight of from about 400 to about 6,000. Useful synthetic polymeric products can be simply and effectively provided by reaction of the polyisocyanate and the oligomeric aminobenzoic acid ester or amide reactants without the requirement of additional curative or chain-extending agents.

Description

~30''~

Title: Synthetic Polymers By Polyisocyanate Polyaddition Process BACKGRO~ND OF T~IE INVENTION
This invention relates to synthetic polymers and to methods for their preparation by an isocyanate polyaddition pro-cess. More particularly, it relates to the production of such syn-thetic polymeric products by the reaction of an oligomeric para-, meta- or di-meta-aminobenzoic acid ester or amide and a polyiso-cyanate.
The production of polymeric products such as poly-urethane elastomers by the diisocyanate polyaddition process has found widespread commercial applica~ion and is described in numer-ous patents and other literature. Typically, the production of an elastomer by the diisocyanate polyaddition process will involve the formulation and curing of a composition comprising a polyol, a diisocyanate and a chain-extending or curing agent. Frequently, the polyol, such as a polyester or polyether polyol having term-inal hydroxyl groups and a molecular weight, for example, in the range of 750 to 2000, will be pre-reacted with a diisocyanate to provide an isocyanate-terminated pTepolymer which may then be ~0 reacted with a chain-extending or curing agent for the production of a polyurethane elastomer.
Various systems have been utilized for the production of polyurethanes from a liquid or semi-liquid state. Notably, the commercial manufacture of polyurethane elastomers has been accom-plished by the reaction of a polyol and a toluene diisocyanate (TDI), either in admixture or pre-reacted, and a chain-extending or curing agent such --1-- , ~7~918 as ~OCA, i.e., 4,4'-methylene bis~o-chloroaniline). Similarly, a system based upon a polyol and 4,4'-diphenylmethane diisocyanate (MDI) and a l,~-bu~anediol curative has achieved commercial application as ar~ alternative to TDI-MOCA systems for the production of polyurcthane elastorners.
The variou~ systems utilized ~or the production of synthetic polymexs may have certain disadvantages with regard to the handling and working of the systems and the properties of ~he resulting polymeric materials. Thus, for example, the utilization of a MOCA or other diamine curative may necessitate the heating of the reaction com-ponents to assure adeguate mixing of the curative and to pr~vcnt crystalliz~tion thereof from the reaction system.
The employment of eleva~ed temperatures may, however, increase reactivity and cause premature curing thereby limiting the time available for mixing and handling the desirod mixture. Similarly, certain problems are associated with the utilization of 1,4-bu~anediol curative in, for example, a 1,4-butanediol~MDI system. The curative tends to pick up moisture as the result of exposure to the atmosphere and frequently results in the appearance of bubbles or foaming in the cur~d pol~mer. In addition, the re~ulting polymeric material often exhibits a "cheesy" character, thus, hampering demolding of fabricated pieces. Neither the employment of a 25~. TDI/MOCA system nor a 1,4-butanediol/MDI system is especially suited to a hand-mixing operation from the standpoint of pot life, and where the manufacture of cured parts by ~abricators utiliziny such operations is an Lmportant considera~ion, the employment of such systems may be decidedly disadvantageous.

~ ~7~30~

The polyurethane materials of commerce, in addition to the presence of repeating ureth~ne ~roups, may contain other groups such as urea, ester, ether, aromatic, amine, biuret or allophanate groups. The number, variation and repeatability of these groups along with the urethane groups will depend upon the active hydrogen-bearin~ materials reacted with a diisocyanate for production of a polymer. The manner in which these groups are combined will determine to a large extent the major physical properties o~ the finished polymer.
While the utilization of a particular reaction sys~em involving particular reactants will b~ determined in part by the dictates of major physical prope~ties required in a finished polymer, the convenience and ease of handling ~nd fabrication will likewise be important considerations in the utilization of a 1~ particular system for the production of a polymeric material.
Accordingly, a system for the production, by a simple and eff~ctive isocyanate polyaddition proce~s, of synthetic polymers exhibi~ing useful physical properties will be especially advantag~ous.
SUMMARY OF THE INVEN~ION
The present invention provides synthetic pol~mers by an isocyanate polyaddition process whereby a polyisocyanate is reacted with substantially an equivalent amount of an oligomeric para-, meta- or di-meta-aminobenzoic acid ester or amide having the formula . O ~
C-Z- ~G
(H2NrX ~

wherein n is an integer of from 2 to 4; each x i~ one or two;
each benzoyl nucleus is para-, meta- or di-meta- amino-H

substituted; each Z is -O- or _l_ ; and G i~ an n-valent radical ~9C198 which may be obtained by the removal of hydroxyl or amino groups, respectively, from an n-valent oligomeric polyol or polyamine having a molecular weight of from about 400 to about 6,ooo.
Thus, synthetic polymers having useful and desirable physical properties can be simply and effectively provided from a reaction system based upon substantially equivalent amounts of a polyisocyanate and an oligomeric para-, meta- or di-meta-aminobenzoic acid or amide of the afore-described formula. The present invention is based in part upon the incorporation of the backbone of an oligomeric polyol or polyamine, in the form of an n-valent radical G, into an aminobenzoic acid ester or amide having the hereinbefore described formula and the utilization of the resulting oligomeric aminobenzoic acid ester or amide in a polyisocyanate addition process, without the required employment of a curative or chain-extending agent, in the production of useful synthetic polymeric products. In its process aspect, the present invention, thus, provides a method whereby such synthetic polymeric products can be simply and effectively provided by the reaction of a polyisocyanate and the oligomeric aminobenzoic acid ester or amide. This method, thus, represents a departure from the conventional isocyanate polyaddition process involving the reaction of a curative or chain-extending agent with an admixture or pre-reacted product of a polyol and a polyisocyanate. Various objects, details, operations, uses, advantages and modifications of the invention will be apparent from the following more detailed description.
Thus in a first aspect this invention provides a synthetic polymer substantially free of the reaction product of an isocyanate and a polyalkylene ether glycol or polyol and substantially free of salts formed during production of the polymer by reaction of a basic material and an amine salt and ~Bl 909~
comprising the reaction product of a polyisocyanate and substantially an equivalent amount of an oligomeric aminobenzoic acid ester or amide having the formula ¦ ~ C - Z ¦ G

H2N)X n wherein n is an integer from 2 to 4; each x is one or two; each benzoyl nucleus is para-, meta- or di-meta-amino-substituted;

H

each Z is -0- or -N-; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,ooo.
In a second aspect this invention provides a process for preparing a synthetic polymer from a reaction mixture substantially free of polyalkylene ether glycols or polyols and acidic reaction rate-controlling amine salt-forming agents, said process comprising reacting a polyisocyanate with substantially an equivalent amount o~ an oligomeric p-aminobenzoic acid or amide having the formula O
~ C - Z - -G

(H2N)x _ n wherein n is an integer 2 to 4; each x is one or two; each benzoyl nucleus is para-, meta- or di-meta-amino-substituted;

each Z is -0- or -~-; and G is an n-valent radical obtained by removal of hydroxyl groups or amino groups from an n-valent -4a-~79098 polyol or polyamine having a molecular weigh'c of frorrl about 400 to about 6,300.
In a third aspect this invention provides a synthetic polymer which consists essentially of' the reaction product of a polyisocyanate and substantially an equivalent amount of an oligomeric aminobenzoic acid ester or arnide having the f'ormula O
~ C - Z - -G

(H2N)x _ n wherein n is an integer from 2 to 4; each x is one or two; each benzoyl nucleus is para-~ meta- or di-meta-amino-substituted;

each Z is -0- or -N-; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6~ooo .
In a fourth a.spect this invention provides a process for preparing a synthetic polymer which comprises reacting a mixture which consists essentially of a polyisocyanate and substantially an equivalent amount of an oligomeric aminobenzoic acid or amide having the formula ~3_ 1l H2 x ~n wherein n is an integer from 2 to 4; each x is one or two; each benzoyl nucleus is para , meta- or di~meta-amino-substituted;

each Z is -0- or -N-; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol -4b-P ~i ~1~79C~8 or polyamine having a molecular weight of from about Llo0 to about 6,ooo.
DETAILED DESCRIPTION OF THE IN~ENTION
. _ . .
As described hereinbefore, the synthetic polymers of the present invention are prepared by a polyaddition process whereby a polyisocyanate is reacted with a substantially equivalent amount of an oligomeric aminobenzoic acid ester -Llc-~1~

~L17~0~!3 or amide having the following formula:
r . O -~ C-Z- ~G
(H2N~ ~

wherein n is an integer of from 2 to 4; each x is one or two;
each benzoyl nucleus is para-, meta- or di-me~a- amino-substituted; each Z is -C- or ~N- ; and G is an n-valent radical which may be obtained by the removal of hydroxyl groups or amino groups t respectively, fro~ an n-valPnt polyol or poly-amine having a molecular weight o~ from about ~00 to about 6,000. It will be appreciated that the characteriz~tion o~
radical G (as an n-v~lent radical which may be obtai~ed by the removal oF hydroxyl groups or amino gxoups, respectively, ~rom an n-valent polyol or polyamine) is set forth for con-venience in defining the nature o~ radical G pe~ se, notwith-standing that abstraction or removal o~ hydroxyl or amino groups ~rom such polyol or polyamine is not mechanisti-cally involved in the syn~hesis or productio~ of the oligomeric aminobenzoic acid esters a~d amides hereof.
It will be seen from inspection of the formula set for~h hereinbe~ore that the oligomeric aminobenzoic acid esters utilized in the present invention co~prise di-, tri- and tetra-~aminobenzoate) esters of oligomeric polyol materials where n is, respectively, 2, 3 or 4. Correspondingly, the oligomeric aminobenzoic acid amides comprise di-, tri- and tetra- (aminobenzoic acid) a~ides o~ oligomeric polyamine materials where n is, respectively, 2, 3 or 4. Inasmuch as the aromatic rings of the benzoyl moieties o~ th~ esters and amides each contain one or two amino groups, the oligomeric amino benzoic acid esters a~d amid~s may ~e tenmed oligomeric poly-amines. Accordingly, the term"oligomeric polyamineU can be utilized in reference to the essential aminobenzoic acid ester or amide components o~ the polyaddition product and process of the present invention.
The oligomeric aminobenzoic acid esters utiliæed in the practice of the polyaddition process of the present invention are aminobenzoate esters of oligomeric polyol materials and can be conveniently provided by reaction of a nitro-substituted benzoyl halide, or a nitro-substituted benzoic acid, wi~h a suitable polyol, such as a polyalkylene ether or ester polyol, followed by reduction o~ th~ nitro groups of the resulting product to the corresponding amino groups. Thus, for examplet an oligomeric diotp-aminobenzoate) ester useful herein can be prepared by reaction of ~wo moles of p-nitrobenzoyl chloride with one mole of a dihydric alcohol such as poly(ethylene glycol) having a molecular weight in the range of from about 400 to about 6,000 and by reduction of the resultin~ poly~ethylene glycol) di-(p-nitro-ben..oate) ester. This reaction is illustrated by the following :-20 reaction scheme wherein the value o~ integer a is such as to provide a molccular weight withill the aoredescribcd ranye:

2 ~ C-Cl ~ HO~CH2-CH2-o~a H
Mol.Wt. 400-6,000 Ol o 02N~C~ 2~C~ aC ~NO [H~

Il 1!
~I~N ~ 2 ~ -~aC ~ 2 In like man~er, oligomeric aminobenzoic acid amides useful herein can be provided by reaction o~ a nitro-s~stituted b~nzoyl halide, or a nitro-substituted benzoic Lt;~

acid, wi~h a suitable polyamine, followed by a reduction of ~he benzoyl halide or benzoic acid nitro-substituent~ to corresponding amino groups. For example, an oligomeric di~
(p-aminobenzoic acid) amide useful herein can be prepared bY
reaction of two moles of p-nitrobenzoic acid with one molc o~ an oligomeric diamine such as a propoxylated propylene diamine having a molecular weigh~ in the range of from about 400 ~o about 6,000 and by reduction o~ the nitro groups to ami~o groups. This reaction is illustrated by the following reaction scheme wherein the value of integér c is such as to provide a molecular weight within the afore-described range:
7~1 3 l H3 2N ~ C-OH ~ H2N~CH2-CH~O ~ C~2-CH ~ NH2' --~~

02N ~ -N ( ~ -CH-O ~ CH2-CH~- N-C ~ N0 HzN ~ C-N~CH -CH-O~ ~ 2 The nature of radical G of the aminobenzoic acid esters and amides can v~ry and will depend upon the nature of the oligomeric polyol an~ polyamine materials utilized in the preparation thereoS. As indicated previously, the radical G
will be derived from a polyol or polyamine material having a molecular weight of from about 400 to about 6,000. Preferably, the polyol or polyamine will have a molecular weight in the range o~ about 650 to 2, 000 . The radical G can comprise an n-valent saturated or unsaturated, straight chain or branched chain hydrocarbon radical which can be interrupted by oxygen ether atoms. For example, wh~re a polyether polyol or a poly-ether polyamine is utilized in the preparation of an oligomeric aminobenzoic acid or amide, the corresponding G radical will comprise repeating oxygen ether atoms. Preferably, radical G
will include such oxygen ether atoms.
It will be appreciated from inspection of the herein-before described representative formula that the nature of n-valent radical G will vary with the value of integer n.
Thus, where n is two, radical G will be a divalent radical -G- obtained by removal or abstraction of two hydroxyl or amino groups, respectively, from an oligomeric polyol or poly-amine having a molecular weight of from about 400 to about 6,000. In the case where n is three, G will represent a tri-valent radical -?-, obtained by removal of three hydroxy or amino groups from a polyol or polyamine having a molecular weight in the same range. Similarly, when n is four, radical G will represent a tetravalent radical -?-, obtained by removal of four hydroxyl or amino groups from a polyol or polyamine having a molecular weight in the same range.
The Z moieties of the oligomeric aminobenzoic acid ester and amide compounds hereof can independently be oxygen or imino groups and, accordingly, each Z is defined as being -O- or -?-. While the utilization of, for example, an ologomeric polyol or polyamine having, respec-tively, only hydroxyl or amino groups will be preferred from the standpoint of convenience and ease of preparation, compounds having both hydroxyl and amino groups can be utilized for the preparation of mixed aminobenzoic acid ester/amide compounds hereof. The preparation of such compounds can be illustrated by the following reaction scheme:

1 Li79~)9~ , 02N~C-Cl ~ HO-G-NH2 ~
Mol, Wt. 400-6,000 O?N~C-O G-N-C~NO ' ~

H,N ~ C-O-G-N-C ~ NH~

A numbe~ o~ polyol materials can be suitably smployed S ~or the preparation of the oligomeric aminobenzoic acid asters utili2ed herein. Examples of such polyols, which pro-vide divalent, trivalent or ~etravals~ G radicals include oligomeric diols, such as polyalkyleneether glycols and poly-alkylene-arylene-e~her glycols; oligomeric triols, such as the polyalkyleneether glycerols or mixed polyalkylene-arylene-ether glycerols; and oligomeric tetrols, such as the polyalkyleneether pentaerythritols or mixed polyalkylene-arylene-ether pentaerythritols.
A pre~erred class of polyol materials use~ul in the preparation of the aminobenzoic acid esters herein comprises the polyalkyleneether glycols which provide a divalent G
radical and which may be represen~ed by the formula HO-~ROt-aH
wherein R is an alkylene radical containing up to ten carbon atoms and a is an integer sufficient to provide a molecul~r weight within the range of ~rom about 400 to 6,000, and pre-ferably, from about 65~ to about 2,000. Preferably, R is ~n alkylene radical of from 2 to 4 carbon atoms~ Examples o~
polyalkyleneether glycols use~ul herein include polyethylene-ether glycol, polypropyleneether glycol, polyhexyleneether glycol, polytetramethyleneether glycol, polydecamethylene-ether glycol, poly-1,2-dimet~yl ethyleneethex glycol and the g_ copolymer of ~Ptrahydrofuran and l-allyloxy-2,3-epoxypropane.
The polyalkyleneether glycols herein can be readily obtained, for example, by polymerization to suitable molecular weight of an alkylene ether, e~g., e~hylene oxide, tetrahydrofuran, pro-S pylene oxide, or, an admixture thereof~ in ~he presence of water or other low molecular weight alcohol or hydrogen-donor compound.
The polyalkylene-arylene-ether glycols can also be employed for the preparation of oligomeric p-amlnobenzoic acid esters utilized herein~ These ~lycols, similar in structure to the polyalkyleneether glycols, additionally contain arylene radicals. Thus, arylene groups such as phenylene, naphthyiene and anthracene radicals can be presen~ in the polyalkylene-arylene-e~her glycols. In general, the a~ylene groups will be ~resent in minor proportion rela~ive to the alkylene groups.
Normally, the glycol will contain at least one polyalkylene-ether radical of molecular weight of about 500 for each ar~lene radical.
Another class of polyol materials suited to ~he pre-paration of oligomeri~ aminobenzoic acid esters useful he~ein comprises the class o~ hydroxy-containing hydrocarbon polymer materials having a molecular weight in ~he ran~e of from about 400 to 6,000. Accordingly, the radical G derived therefrom will comprise an n-valent saturated or unsaturated, straicht or branched chain hydrocarbon radical which may be obtain~.d by removal of hydroxyl groups from a saturated or unsaturated straight or branched chain hydrocarbon polymer having a molecular weight within the previously set forth range.
Preferably, the n-valent G radical will be an aliphatic hydrocarbon radical derived from an aliphatic hydro-c.lrbol~ ~olyol. Examples of ~uitablc hydrocarbon polyol ~ 10--~'7~

materials include the polyols obtained ~rom the pol~nerization of polymexizable e~hylenically unsaturated monomers, such as 1,4-butadiene, and by the introduction of hydroxyl groups in known manner. Such polyol materials are known and can be preparad, for example, by free-radical initiated polymeriza-tion of a polymerizable ethylenically-unsatuxated monomer to provide a dicarboxylate-substitu~ed hydrocar~on polymer, for example, a dicarboxyla~e-~erminated polymer. Reduction in known manner provides an aliphatic hydrocarbon polyol, for example t an aliphatic hydrocarbon diol. A suitable me~hjod ~or the production of such polyol materials is described in greater detail in U.S. Patent 2,888,439 (issued May .^6, 1959 to D . M. Simons).
As indicated previously, the polyol materials useful for the preparation of the oligomeric aminobenæoic acid esters utilized herein also include polyols capable, by abstrac-:ion, respectively, of three or ~our hydroxyl groups, of pro-~riding a trivalent or tetravalent radical G. Thus, polyalkylene-ether polyols and mixed polyalkylene-arylene-ether polyols derived from such polyhydric alcohols as glycerol, trimethylol-propane, pentaerythritol and the like can be employed. Such materials can be obtained by oxyalkylation as, for example, by reaction of glycerol or pentaerythritol with ethylene oxide, propylene oxide or a mixture thereo~. The resulting tri-functional and tetra~unctional ethers may be advantageously employed for the preparation o~ oligomeric tri- a~d tetra-(aminobenzoate) esters which can be sui~ably employed ~or the production of polymers having increased cross-linXing.
A variety o~ polyamines can be utilized for the preparation of oligomeric aminobenzoic acid amides useful v~
herein. Examples of such polyamines, which provide divalent, ~rivalent or tetravalent G radicals include oligomeric diamines, txiamines and tetramines. For example, oligom~ric diamines ~seful ~or the provision of oligomeric aminobenzoic acid amides include polyamines of the formula 2 ~ ~ ~d 2 wherein each of Rl and R2 is a divalent saturat~d or unsaturated, straight chain or branched chain hydrocarbon radical; c i5 zero or an integer; d is an integer; and the combined value of c and d is such as ~o provide a molecular weight for ~he polyamine of ~rom about 400 to about 6,000. Preferably, each of ~1 and R2 is an aliphatic, straight or branched chain divalent hydrocarbon radical, e.g., an alXylene radical of from 2 to 10 carbon atoms, and more preferably from 2 to 4 carbon atoms. Suitable polyamines are known and commercially available and can b~ obtained, ~or example, by polymeriz~-tion of ~n alkylene oxide and conversion of terminal hydroxyl groups to amino gxoups by known amination technique.
The polyol and polyamine materials from which tlle n-valent G radical is derived can contain substituent moieties where such substituents do not interfere with the desired re-action o~ the aminobenzoic acid ester or amide with an iso-cyanate. Alkyl or halo substituents, for example, can be suit-ably present. The n-valent G radical can also ccntair. repeati~g 2S oxygen ether atoms as will be the case where the polyol or polyamine from wh_ch radical G is derived comprises, for example, a polyalkyleneether glycol, a polyalXyleneether glycerol, a polyalkyleneether pentaerythritol, a mixcd polyalkylene-arylene-ether polyol or an amine-terminated polyalkyleether. The polyol and polyamine materials c~n additionally contain ester linkages. Thus, polyol materials of suitable molecular weight, i.e., in the range o~ from about 400 to 6,000, having est0r linkages as may be obtainedt for example, by reaction of a polycarboxylic acid and a polyhydric S ma~erial can be suitably employed. Examples of such polyols having ester groups include the oligomeric polyester polyols such as may be ob~ained by the condensation o~ adipic acid and ethylene glycol.
~he oligomeric aminobenzoic acid esters utilized herein ~or the production o~ polymeric products include the di-(aminobenzoate) esters (obtai~ed, for example, by reaction o~ two moles of a nitro-substituted benzoyl chloride with one mole of an oligomeric glycol having a molecular weight of about 400 to about 6,000, ~ollowed by reduction of nitro-to-amino- groups); and the tri- (aminobenzoate) esters (from three moles o~ a nitro-substituted benzoyl chloride and one mole of an oligomeric triol oÆ moleoular weight of about 400 to about 6,000, ~ollowed by reduction of nitro-l.to amino- groups).
Similarly, the oligomeric aminobenzoic acid esters include the tetra-(aminobenzoate) e~ters derived from four moles of a ^nitro-substitut~d benzoyl chloride per mole of an oligomeric te~rol o~ molecular weight of about 400 to about 6,000, followed by a suitable nitro- to ami~o group reduction. These oligomeric aminobenzoat~ esters can conveniently be repre-sented by the following foxmulae;

o o C - O - G - O - C ~
~N) (NH ) x Formula I 2 x c~

( H 2N >~X~
~J
c = o 1l ; und ( 2 M~2)x Formula II

(H2N~ ~

C = O

~ _ o ~ o~
(H2N O NF12 )x C = O

( H2N
Pormula III

Similarly, the oligomeric aminobenzoic acid amides utilized herein for the production o~ polymeric S products include the di~aminobenzoic acid) amides, ~he tri-(aminobenzoic acid) amides and the tetra- (aminobenzoic acid) amidesO These oligomeric aminobenzoic acid amides can convenie~tly be represe~ted by the following formulae:

~ C - N - G - N - C ~
(H2N)x Pormula IV N~2)x 9~

( H2Nt;~

c - o C - N - G - N - C ~
(~ N ~ NH2)x Yormula V

2 ~
I! ,J
C = O

(H2N ~ C - N _ I _ N - C ~ NH2)x C = O
~ .
( H2N~X
Formula VI

In the formulae sh~wn ~or ths oligomeric amino-benzoate esters hexPo~ (Formulae I, II, and III) and the oligomeric aminobenzoic acid amides (Formulae IV, V, and VI), G w~ll represent, respectively, a divalent, trivalent or tetra-valent radical derived from a polyol or polyamine having a molecular weight in the range of about 400 to about 6,000, and preferably, in ~he range of from about 6S0 to about 2,000.
AS will be apparent from inspection of each of the formulae set forth hereinbefore, the phenyl group of each benzoyl moiety

3~

. . , contains one or two amino groups depending upon the value of each x as one or two. The amino groups are posikioned such that each benzoyl nucleuY is para- amino-~ubstituted, meta-amlno-substituted or di-m~a- amlno-substituted. Accordingly, the oligomeric aminobenzoic acid esters and eaters hereof are inclusive of para-aminobenzoic acid esters and amides; meta-aminobenzoic acld esters and amides; and di-m~ta-aminobenzoic acid esters. It will be appreciated that each benzoyl moiety of an oligomeric aminobenzoic acid ester or amide hereof, while para-, me~a- or di-me~a- amino-substituted, need no~ be indenti-cally substituted. Prefexred oligomeric aminobenzoic acid esters and ~mides herein are those wherein the benzoyl ~oieties are each para- amino-3ub~tituted. In addition to the amino-group substitution of the benzoyl moieties, the benzoyl groups can be substituted with non-interfering groups. Accordingly, the benzoyl moiPties of the amlnobenzoic acid e~ter and amide compounds hereof ca~ be substituted with halogen, alkyl ox other substituents which do not interfere with the desired polyiso-cyanate addition proce~.
Examples of oligomeric aminobenzoic acid esters useful herein and represented by Formula I include the following wherein a and b are integers having values corre~ponding to molecular weights for the polyols from which they are derived of from about 400 to about 6,000.
O O
A.2N ~ C-O ~ ~2-C~2-O ~ C ~ NH2 B.H2N ~ C~O ~-CH2-CH2-C~2~CH20~ C ~ ~H2 C.H2 ~ C-O ~CH2-C~2-~2 CH2~~a~ ~ NH2 7~30951 D H2NK~C-O ~CH2-C~2-CH2 ~H20~ ~NNH2 o c~3 o E . H2N ~ ~ _O ~ CH2 -CH - O -~- C ~-NH2 ; and Ol C~3 O
F EI2N~3C-O ~ CH2-CH2- ~C~2-CH-O~ ~NH2 Examples of oligomeric ami~obenzoate esters useful herein and represented by Formula II include the S ~ollowing wherein a and b are integers havir~g values corres-ponding to the molecular weights for the polyols from wh~ch they are derived of ~rom a~out 400 to about 6,0û0.

G. CIH3 H2 C~ - O ~ C~2-C~ ~ ~i C~3N~2 ; and IH2 O ~ CH2--CH 0~ C ~NH2 H CH2 O ~ CH2-CH O ~ CH2-CH-O ~C~N~2 CH O~ C}I -C~l O ~ CH2-C~ ;3N~2 112 0 ~ C~2~CI -O ~CH2-C~ -O -~C~;3NH;2 ~ 9 ~ ~

An example of an oligomeric aminobenzoate ester represented by Formula III includes the following wherein each a is an integer having a value corresponding to a molecular weight for the polyalkyleneether pentaerythritol fxom which the aminobenzoate ester is derived of from about 400 ~o about 6,000.

I. ~ ~ ~t-a C ~ NH2 ~2N ~ ~ a ~ ~ ~ -C~-Ota-C ~ NH2 ~ CH ~ ~ NH2 Examples o~ oligomeric aminobenzoic acid amides use~ul herein a~d represented ~y Formula IV include the followi~g wherein each c is an integ~r having values corres-ponding to molecular weigh~s for the polyamines from which they are deri~ed o~ from about 400 to about 6,000.

J- H2N ~ 2-CH2- ~ CH2-CH2~-N-C ~ ;and K. ~2N ~ C!N~C~-CH - O ~ C~ ~ ~ N-C ~ .

An example of an oligomeric aminobenzoic amide ~seful her~in and ~epresent~d by Formula V is the following wherein each c has a value corr~sponding to the molecular weight for the polyamine from which ~he amide is derived of from about 400 to ~bout 6,000.

~9~913 2 2 CH O ~ CH2-CH2 ~ N-C ~NH2 L IH O ~CH2 CH ~CH2-CH2 ~ N-C ~NH2 C}I~ - O ~ CH2-CH - 0 ~ CH2-CH2 ~ N-C ~ NH2 . An example of an oligomeric aminobenzoic acid amide represented by Formula VI includes the following wherein each c is an integer having a value corresponding to a molecu~ar Sweight ~or the polyamine from which the amide is derived of ~rom about 400 to about 6,000. ~3 HlOI
~a2-o~2-~ ~ 2dc~ c~ 2 M, l ~ C113 ~--C52~N~-C 43N~2 CH3 t) {)(CH2~CH2-CH2)N-C ~3 NH2 The synthetic polymers prepared ~y the proc~ss o~
the prese~t inven~ion ~re prepared by a polyaddition process involving the reaction of an oligomeric aminobenzoic acid ester or amide as defined hereinbe~ore with substantially an equivalent amo~t of a polyisocyanate. In accordance with such a process, an oligomeric aminobenzoic acid e~ter or amide havi~g, ~or example, the structure xepresented by Formula B or ~ will be reacted with substantially an equimolar amount of a diisocya~ate, ~or example, a diisocyanate such as

4,4'-diphenylmethane diisocyanate.

Polyisocyanates useful in the production of synthetic polymers by the process of the present invention include a vaxiety o~ polyisocyanate ~aterials employe~ in the production of conventional ~olyurethanes. These include a variety of aliphatic polyisocyanates and aromatic poly-isocyanates Examples of sui~a~le polyisocyanates include the toluene diisocyanates (T3I) such as 2,4-toluene diisocyanate;
2, 6-toluene diisocyanat~; mixtures of TDI isomers such as a mixture (80/20 by weight) of 2,4-toluene diiso¢yanate and 2,6-toluene diisocyanate or a mixture ( 65/35 by weight) of 2,4-toluene diisocyana~ and 2,6-toluene diisocyanate;
tetramethylene dii~ocyanata; hexamethylene diisqcyanate;
xylene diisocyanate; 195-napththylono diisocyanate;
1,4-phenylene diisocyanate; 4,4'-diphenylmethane diiso-cyanate (MDIt;4,4'4"-triphenylmethane triisocyanate; and 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate. Aliphatic diisocyanates such as the C36 aliphatic diisocyanate derived from the dimer o~ ricinoleic acid can be suitably employed and are commercially available, for example, as DDI-1410 (Henkel Corporation, Resin Divlsion, Minneapolis, Minnesota).
The polyisocyanates hereof are known polyisocyanates in the field o~ polyurethane technology and can be employed singly or in admixture. Other examples of such polyisocyanates ean be found, for example, in Products, E.N.Doyle, Mc~raw-Hill Book Company, page 27 (1971).
Preferred polyisocyanates for employm~nt in the process of the present invention are polyi~ocyanate materials in a liquid form at ambient temperatures. ~hese materials ~ ~7909~
facilitate the production of polymeric products from normally liquid oligomeric aminobenzoic acid esters or amides and obviate the requirement of melting a solid polyisocyanate as a prerequis-ite to providing a suitable reaction mixture. Suitable liquid polyisocyanate materials are known and include, for example, polymeric MDI (4,4'-diphenylmethane diisocyanate) products obtained as by-products from the synthesis of MDI.
In the production of MDI by the condensation of aniline with formaldehyde and the conversion of amino to corresponding isocyanate groups, a content of the initially formed bis-adduct of aniline and formaldehyde reacts further with the reaction mixture to form polymeric aniline derivatives which are in turn converted to isocyanates. Typically, such polymeric derivatives will have a functionality of from about 4 to about 15, for example, about 10 isocyanate groups per molecule. Products containing such polymeric polyisocyanates in the form of a pot residue after removal of pure MDI by distillation can be utilized.
Similarly, polyisocyanate products comprising such polymeric polyisocyanate species in admixture with pure MDI, i.e. the undistilled reaction mixture, can also be employed. Polymeric MDI products can be employed herein to advantage and are commer-cially available under such trade designations as Rubinate M~
(available from Rubicon Chemicals Inc., Geisman, La.) and PaPI 27, PaPI 135, PaPI 580 and PaPI 901~ (available from the Upjohn Company, Kalamazoo, Michigan).
Another liquid polyisocyanate material which can be employed where cross-linking is desirably introduced into the polymeric products hereof comprises an admixture of MDI and a tri-functional cycloaddition product of MDI. An ~Trade Mark ~r~

3.~
admixtur~ of MDI and a ~ri-functional cycloadduct having the foll~wing structure, whexe R is ~ CH2 can be employed:
~N- R NCO
OCN-R-N C

0/~ NCO
Such an admixture is avai~.able under the de~ignation "Liquid MDI", Isonate 143L ~e Upjohn Company, Kal~mazoo, ~ichigan).
The process of the present invention can be u~ilized ~or the production of poly~eric products by reaction of an oli-gomeric aminoben20ic acid ester or amide and substantially an equivalent amount o~ the polyisocyanate under a variety of reaction conditions. The reaction can be suitably conducted under conditions of room temperature with the provision of polymeric products within ~uitable pot-life and demold-time parameters. Whexe desired, to facilitate polymerization, the reaction system can be heated. It has been found, however, that the process of the present invention permits the fabri-cation of polymeric pieces from reac~ion mix~ures having, in general, a pot life of at least ~ive minutes and that the polymeric pieces can be demolded within abou 15 minutes.
The oligomeric amlnobenzoic acid ester or amide and polyisocyanate components are reacted in sub~tantially equivalent proportions. As used herein, the term "substan-tially equivalent" refers to the utilization, in genexal, of an amount of polyisocyanate reactant of about 0.9 to 1.2 equivalents per equivalent of the oligomeric ami~lobenzoic ester or amide, based upon the isocyanate groups and amino groups, respectively of the polyisocyanate and oligomeric -2~-~ 7 9 anunobenzoic acid ester or amide reactant~. Pr~ferably, fro~
about 1.0 to about 1.15 equivalent of polyisocyanate material per equivalent of sligomeric ~minobenzoic acid ester or amide is employed.
The particular oligomeric aminobenzoic acid ester or amide and polyisocyanate reactants utilized in the conduct of the process of the inventio~ can be varied for desired con-trol of elastomer properties in finished pieces, for control of handling characteristics or to otherwise permit latitude in reaction conditions. The aminobenzoic acid esters and amides utilized herein can be employed in a polyisocyanate polyaddi-tion process in admixture. For example, a mixture of a para-aminobenzoic acid e~ter or amide can be utilized in combination with a meta-aminobenzoic acia ester or amide. Where a mixture of the p-amunobenzoic acid ester or amide and meta- aminobenzoic ~cid ester or amide is employed, the polyisocyanate will be utilized in an amount sub~tantially equivalent, a~ defined herein, to ~he amine functionality of the mixture of aminobenzoic acid ester or amide. A mixture, for example, o~ oligomeric amino-benzoate esters having para- and meta- amino subs~itution can be employed for de~irable control of rate of reac~ion. Such mixtures include a mixture of a di(4-aminobenzoate)ester having the formula Ol O
~2N ~ C - O - G - O - C ~ NH2 wherein G represents a divalent radical obtained by the removal o~ two hydroxyl groups from an oligomeric polyol having a molecular weiyht in the range oS about 400 to about 6,000; and ~rom about 1~ to abou~ 50% by weigh~ of said di-(4-aminobenzoate) ester, of a di-(3-aminobenæoate) ester having the formula ~7~V98 ~ C-O-G-O-C ~ ~2 wherein G represents a divalent radical obtained by the removal o~ two hydroxyl groups from an oligomeric polyol having a molecu-lar weight in the range of from about 400 to about 6,000.
A preferred polyaddition reaction system utilizingsuch an admixture involves the reaction o~ a polyisocyanate with a mixture of isomeric aminobe~zoate esters having the formulae O O

H2 ~ C O ~ R ~ ~ a C ~ NH2 and 2N ~ C - O--~ R ~ ~a C ~ NH2 wherein each R is an alkylene of from two ~o ten, and preferably, two to four carbo~ atoms; and each a is an integer ~uch that the molecular weight o~ the polyalkyleneether glycols from which the aminobenzoate es~ers are derived is in the range of from about 400 to about 6,000, and pre~erably from about 650 to about 2,000. The utilization of an admixture of such isomers permits desired control o~ the rate of reaction of the polyisocyanate polyaddition process. The ~ontrolled addition of meta-substituted isomer thaving greater reactivity than the correspondin~ para-substituted isomer) to a reaction system comprising the para-substituted isomer permits pot life and demold times to be adjusted to more suitably ma~t the pot life/demold tim~ require-ments of particular applications.
2 n Another preferred polyaddition reaction system of tha present invention involves the reaction of a polyisocyanate with a mixture of an oligomeric di-(4-aminvbenzoate)ester and an oligomeric di-~3,5-diamino~enzoate)ester. Such mixtures include a mixture of a di-~4 aminobenzoate)e~ter h~ving the formula -24_ '790~
o o - 2N ~ C - O - G - O - C ~ N~2 wherein ~ represents a dival n~ r~dical obtained by the removal of two hydroxyl groups ~rom an oligomeric polyol having a molecular weight in the range of from about 400 to about 6,000; and ~rom about 1% to about 15% by weight of said di-(4-aminobenzoate) ester, of a di- (3,5-diaminobenzoate) ester having the formula H2~ Ol O NH
C - O - G - O - 1 ~ 2 ~ 2~ NH2 wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a mulecular weight i~ the range of from about 400 to about 6,000.
A prPferred polyaddition reaction system u~.ilizing ~uch an admixture i~volves the reaction of a polyisocyanate with a mixture of oli~omeric di-(amino~enzoate~ estexs having the formulae O O

~2N ~ C - O ~ R - O tr C ~ N~
and 2N ~ C - -~ ~ ~a ~ N~2 E~2N , NH2 wherei~ each R is an alXylene radical of f~om two to ten, and pre~erably, two to four carbon atoms; and each a i5 an integer such that the moleculax weight o~ the polyalkylene~ether glycols from which the aminobenzoate esters are derived is in the rango of from about 400 to abou~ 6,000, and prefer~bly from about 650 to about 2,000. The utilization of a content o~ the tetramine compound, i . e ., the di~ ( 3,5-diaminobenzoate) ester, in the polyaddition reaction ~ystQm permits cross-linking reactions to occur in ~he polyisocyanate reaction and, thus, provides a means for controlling cross~linki~g in accordance wi~h the dictates o~ physical properties r~quired in a particular elastomeric product.
The p-~minobenzoic acid esters and amides utilized herein can be reacted with a polyisocyanate, i~ desixed, in combination with, for example, a di(3-aminobenzoic)acid ester or amide and a di~3,5-diaminobenzoic)acid ester or amide. A
suitable reaction includes, ~or example, the reaction of a polyisocyanate with substan~ially an equivalent amount of a mixture of aminobenzoate esters comprising a di(4-aminobenzoate) ester having the ~ormula Ol O
H2N~3C - O - G - O - C ~ 2 and by weight of the di(4-aminobenzoate)ester, about 1% to about S0~, o~ a mixture o~ a di(3 -aminobenzoate)ester having the formula ~2N ~ C - O - G - O - C ~ NH2 and a di-(3,5-diaminobenzoate)ester having the formula 2N ~ C O - G - O - C ~

x2i~ N~2 wherein each G represents a divalent radical obtained by the removal o~ two hydroxyl groups ~rom an oligomeric polyol having a moiecular weight in ~he range o~ ~rom about 400 ~o about 6,000.
Where mixture~ of the oligomeric amlnobenzoic acid esters or amides, as described hereinbefore are desirably reacted with a polyi ocyanate, there ~7~3~

can be employed such mixtures as are obtained, ~or example, from the reaction of a mixture of nitro-subs~ikuted benzoic acids or halides with a polyol or polyamine, followed by reduction of nitro- to amino- groups. mus, two mole~ of a mixture of p nitrobenzoyl chloride and m-nitrobenzoyl chloride can be suitably reacted with a mole o~ polyol or polyamine for production of a statistical distribution of isomeric di[nitro-b~n20ic) acid esters or amides. Reduction of nitro- to amino-groups provides a corresponding mixture of isomeric di (amino-benzoic) acid esters or amides useful herein. Similarly, two moles of a mixture of p-nitrobenzoyl chlorid~ and 3,5-dinitro-benzoyl chloride can be suitably reacted with a mole of polyol or polyamine to provide a statistical distribution of nitro-substituted benzoic acid esters or amides, which upon hydro-genation, provides a mixture of amino-substituted oligomers use-ful ~or reaction with a polyisocyanate ac described herein.
A mixture o~ di-(aminobenzoate) e~ter and tri-(aminobenzoate~ ester oligomers, as represented by Formulas I
and II hereinbefore, can also be utili2ed, particul~r~y where increased cross-linking is desired. Sim~larly, mixtures of polyisocyanate reactants can be employed to advantage for con-trol of cross-linking in finished pieces. Accordingly, another reaction system of the present invention involves the reaction of a polyi~ocyanate with a mixture of oligomeric amino-benzoates comprising a di(a~inobenzoa~) ester as represented by the structure of Formula I, and hy weight of the di(amino-benzoate)ester, from about 1~ to about 20~, of a tri(amino-benzoate) ester having the structure of Formula II. Such reaction system permits the fabrication of liquid-cast elasto-meric pieces exhibiting desired physical properties while providing ef~icient pot life and demold time parameters.

:~17~0~

The synthetic polymers prepared by the process of the pxesent invention include cast polymeric materials which can, for example, be rormed by the casting of a mixture of an aminobenzoic acid ester or amide and a polyisocyandte and the curing thereo~ to a polymeric material. The polymeric materials can be ~ormula~ed to ~he charac~eristics oE thermo-setting or thermoplasti~ polymers. As used herein, ~he term "cast polymeric materials" refers to solid non-cellular synthetic polymers which are formed by the casting of the reaction mixture of the polyaddition process hereof and the curing thereo~ to a polymeric product. These cast polymers can be distinguished rom the cellular polymers ~ormed by action o~ a blowing agent and commonly referred to as polymeric ~oams.
The synthetic poly~ers of the invention also include, however, such polymeric foams which can be prepared by including any of a variety o~ blowing agents in the r~action mixtures from which the polymers o~ the in~ention are prepared.
Synthetia cast polymers prepared by the process of the present invention can be suitably formed by casting a reaction mixture of an aminobenzoic acid ester or amide and polyisocyanate, ~or example, into a mold and aLlowing the curing o~ the reaction mixture to a thermosetting or thermoplastic polymeric material. The reaction components ca~ be admixed in a container and the contents thereof can be discharged or other-wise in~ro~uced into a mold for desired curlng. A suitable technique for forming the cast polymers hereo~, pa~ticularly in high -production mod~s, involves the mîxing, as by in-line mixing, of the reaction components immediately prior to the casting of the reaction mixture into a suitable mold for curing.
The reaction components can be utilized in connection with con ventional casting and molding operations including extrusion, rotation molding an~ like operations where ~he reac~ion components are propor~ioned and mixed for curing to a solid non cellular polymeric material. While the reaction mixtures and process S hereof can be employed in the production of cast pieces or fabrications formulated to suit the requirements of haxd, abrasion-resistant, flexible pieces of thermose~ting or thermo-plastic character as desired, the process hereo~ can also be utilized in the production of solid cellular or non-cellular polymeric coatings or films. These coatings or films can be pro-vided by coating the reac~ion components, in neat form or in admixture with an organic solvent, onto a coatable substrate and allowing the coating to cure to the desired pslyme~ic film or coating.
lS The process of the present invention permits the realization of certain advantages in the manufacture of poly-meric materials, particularly cast elastomeric pieces or fabri-cations prspared by a Ya~iety o~ casting a~d molding operations.
As indicated hereinbe~oxe, the polymeric materials h~reof can be conveniently prepared without resort to the utilization of chain-extending or c~r1ng agents conventionally employed in the polyurethane art. The provision o~ an oligomeric moiety in anaminoben30ic acid ester or amLde, thus, permits the production of polymeric ~aterials having useful physical characteristics by the simple and direc~ reaction of an oligomeric aminobenzoic acid ester or amide as described herein with a polyisocyanate reactant. The requirement of diss~lving a solid curative in a reaction system as a prerequisite to the casting and production of polymeric products is, thus, also obviated.
It may be noted from the disclosure in U. S. Patent 3,256,213 ~issued ~une 14, 1966 to G. T. Gmitter et al.) that ~ ~7~

it has been proposed that a long chain polyamuno compound he substituted for all or part of the polyether glycol and polyol reactants theretofore employed in the production of cellular polyether-polyurethanes. Included among the polyamino organic compounds described as suitable for reaction with tha isocyanato groups of an isocyanate are the polyalkylene ethers terminated with primary or secondary amino groups, the aminoesters of hydroxy terminated polyalkylene ethers, the di(amino esters) of hydroxy terminated long chai~ aliphatic hydrocarbons derived from polydienes such as polybutadiene, polyisoprene and the li~e, and the polydiene diamines having substantially terminal amino groups and hydrogenated polydiene diamines which may or may not con~ain residual ethyle~lic double bonds in the molecules.
It is disclosed in the patent that a comple e replacement of t:he polyalkylene e~her glycols or polyol-~ by a long chain di- or polyamino o~ganic compound effects an al~ost instant-æneous reaction and that the good mixing necessary to produce a cellular product is obtai~ed only with difficulty. This diffi-culty is eliminated by forming a salt of the polyamino compound ~hich can then be thoroughly admixed with the isocyanate reactants, catalysts, surface active agents and the like without prematuxe reaction of the polyamino compound and isocyanate. The addition to this mixture o~ a basic material such as calcium oxide, tertiary amines or the like which reacts 2S with the ~mine salt to yield the free amine i~ described as per-mitting the reaction of the amine with ~he isocyanate such thatthe c~llular polyurethane is produced.
The process of the present invention represents a departure from the disclosure o~ U.S. Patent 3,256,~13 in that the process of the invention permits the production of poly-9~gl3 meric products ~y a sirlple an~ direc~ reaction o~ a polyiso-cyanate and an oligomeric aminobenzoic acid ester or amide as described hereinbefore without the presenae in the reaction mix~ure of polyalkylene ether glycols or polyols. The u~iliza-tion o~ such oligomeric aminobenzoic acid ester or amide ma~eri~ls as components for reaction with a polyisocyanate in accordance wi~h the present invention permits desired pro-duction of polymeric materials without inst~ntaneous or near-instantaneous reactivity. As indicated hereinbe~ore, the process of the present invention permits the ~abrica~ion of polymeric materials ~rom reaction mixtures having suitable pot~ e, in general, of at least ~ive minutes. ~his desirable reaction system parameter is realized without need of polyalkylene ether glycols or polyols or acidic agents utilized for reaction rate control by ~ormation of a polyamine salt. Inasmuch as the polyalkylene e~her glycols and polyols described in U.S. Patent NoO 3,256,213 are not incl~ded as reactants in the process of the present invention, the resulting polymers do not contain the reactlon products of an isocyanate and such polyalkylene ether glycols or polyols.
Similarly, the acidic, amine salt-forming agents described in U. S. Patent No. 3,256,213 are not employed in the process hereof. Accordingly, the production of such other salts as are formed by the reaction of an amine salt and a subsequently added basic material, as described in the patent~ i~ avoided.
It is, thus, a significant aspect o~ the pr~sent invention that the reaction mixture utilized in the production of the polymers in accordance with the process of the invention is substantially free of polyalkylene ether glycols or polyols and reaction rate-controlling acidic, polyamine salt-forming agents.

~.~790913 Accordingly, the polymers of the present lnvention are substant-ially free of the reaction product of an isocyanate and a poly-alkylene ether glycol or polyol and substantially free of salts formed during production of the polymer by reaction of a basic material and an amine salt.
While the process of the present invention permits the production of polymeric materials without need for conventional curative materials, additives of various types employed in the manufacture of polymeric products can desirably be employed in the reaction system hereof for their attending advantages. Thus, catalysts, ultraviolet absorbers~ fillers, plasticizers, blowing agents or the like can be employed where desired.
The following Examples will better illustrate the nature of the present invention. Such Examples are intended, however, to be illustrative and not limitative. All parts or proportions are by weight unless otherwise indicated.
E~AMPLE I
This example illustrates the preparation of an oligomeric di-(p-aminobenzoate) ester of a polytetramethylene oxide diol. A reaction mixture was prepared by the addition to 500 cc. of toluene of the following ingredients: 253.6 g. (0.25 mole) of a polytetramethylene oxide diol having a molecular weight of about 1000 (Polymeg* 1000 available from The Quaker Oats Company, Chicago, Illinois); 60.3 g (o.6 mole) of tri-ethylamine; and 106.3 g. (C.57 mole) of p-nitro-benzoyl chloride.
The reaction mixture was heated and allowed to reflux overnight.
The reaction mixture was cooled, filtered and washed with an aqueous solution (5% by weight) of sodium carbonate. The resulting product was evaporated with recovery of 266 g. of an amber resinO

*Trade Mark .~

~'7~

The resinou~ product, as recovered above, was dissolved in one liter of e~hanol. To the resulting solution was added 5 g. of 5%-palladium-on-carbon catalyst, followed ~y ;Idditiorl of 31.2 g. (0.~ mole) of hydrazine hydrate. The resulting reaction mixtu-e was heated, allowed to reflux for three hours, cooled, filterod and evapor~ted to yield 228 g.
of a cleax resinO Analysis of the resin indicated an amine equivalent of 1.58 milliequivalents per gram o resin (meq./g.).
Completion of the es~erification reaction of the p-nitro-benzoyl chloride with the hydroxyl gxoups of the polyte~ra-me~hylene oxid~ diol was indicated by analysis of the resin product ~or residual acidity (0.02 meq.H /g.). The -esin product was an oligomeric di~p-aminobenzoate) ester of polytetramethyle~e oxide diol, the product being represented by the following structure;
_. .
O . O
2N ~ C-O ~cH2-c~2-c~2 CH20 ~a ~ NH2 EXAMPLE II
This example illustrates the preparation of an oligomeric ~ri-(p-aminobcnzoate) ester of a polypropylene oxidè triolO A reaction mixture was prepared by the addition to 500 cc. of toluene of the following ingredients: 525 g.
o~ ~ polypropylcne oxifle triol having a molecular wei~ht o~

_3 3D

~ ~79098 about 5,000 (available as ~oranol* 4701, from the Dow Chemical Company, Midland, Michigan); 60 g. of p-nitro-benzoyl chloride;
and 40 g. of triethylamine. The reaction mixture was heated and allowed to reflux overnight. The reaction mixture was cooled~
filtered, washed with an aqueous solution (5% by weight) of sodium carbonate and evaporated to yield 514.5 g. of an amber resin.
The amber resin, as recovered above, was dissolved in one liter of ethanol. To the solution was added 5 g. of a 5%
palladium-on-carbon catalyst followed by 40 g. of hydrazine hydrate. The mixture was heated, allowed to reflux for three hours, cooled, filtered and evaporated to yield 228.8 g. of a clear resin product. The product was analyzed for amine equivalents (0.55 meq./g.) and for residual acidity (0.02 meq.H+/
g~)O The resin product was an oligomeric tri-(p-aminobenzoate) ester of polypropylene oxide triol, the product being represented by the following structure:

CH2 - 0~ CH2-CH-0 ~ C~NH2 CH - 0~ CH2- IH-0~ 11 ~3NH2 C 'H2 - o ~ CH2-1H-O ~ C ~ NH2 EX~MPLE III
This example illustrates, like Example I, the preparation of an oligomeric di-(p-aminobenzoate) ester of a polytetramethylene oxide diol, except that, this Example illustrates the utilization of a polytetramethylene oxide *Trade Mark . ~

30~38 diol of lowex molecular weight. A reaction mixture was prepared by additio~ to 500 cc. of toluene of ~he following in~redients: 165.5 g. o~ a polytetramethylen~ oxide diol having a molecular weight of about 650 (available as Polymeg S G50, from the Quaker Oats Company, Chicago, Illinois);
106.3 g. of p-nitrobenzoyl chloride; and 60.3 g. of tri-ethylamine. The reaction mixture was heated and allowed to reflux overnight. The reaction mixture was cooled, filtered, washed witA an aqueous (5% by weight) solution o~ sodium carbonate and evaporated to yield 225 g. of an amber resin.
The ambex resin, as recovered above, was dissolved in one liter of ethanol. To the resulting solu~ion was added S g. of a 5~ palladium-o~-~axbon catalyst, followed by 51.6 g.
of hydrazine hydrate. The reaction mixture was heated, allowed to reflux for three hours, cooled, filtered and evaporated to yield 18~ g. of a clear resin product. The product was analyzed for amine equivalents (2.32 meq./g.) and for residual acidity (0.02 meq.H+/g.). The resin product was an oligomeric di-(p-aminobenæoate) ester of polytetra-methylene oxide diol, the product being represented by the following structure:
O O
H2N~ C O ~ CH2-CH2-CH2 C~120 ~C~NH2 EXAMPLE IV
This Example illustrates the prepaxation o~ an oligomeric di-(m-aminobenzoate)ester o~ a polytetramethylene oxide diol. A reaction mixture was prepared by addi ion to 500 cc. o~ toluene of the following ingredients. 103 g. of a polytetramethylene oxide diol having a molecular weight of about lOOOo ~available a~ Polym2g 1000, from The QuaXer ~1~790~3 Oats Company, Chicago, Illinois ); 103 g. o~ m-nitrobenzoyl chloride; and 60.3 g. o~ triethylamine. The reaction mixture was heated and allowed to reflux overnight. The reaction mixture was cooled, filtered, washed with an aqueous (5% by weight) solution of sodium carbonate and evaporated to yield a yellow resin.
The yellow resin, as recovered above, was dissolved in one liter of ethanol. To the resul~ing solution was added

5 g. of a 5~ palladium-on-carbon ca~alyst, followed by 31.2 g.
of hydrazine hydrate. The reac~ion mixture was heated, allowed to reflux fox three hours, cooled, filtered and evaporated to yield 243.8 g. of a clear resin product. The product ~as analyzed ~or amine e~uivalents (1.55 meq./g.) and for residual acidity (0.03 meq.H+/gO). The resin product was an oligomeric di~(m-aminobenzoate) ester of polytetra-methylene oxide diol, the product being represented by the followin~ structure:

C-O ~ C~2-CH2~CH2 C~2 ~a EX~MPL13 V
This example illustrates the preparation of an oligomeric di-t3,5-diaminobanzoate) ester of a polytetra-methylene oxide diol. A reac~ion mixture was prepared by addition to 500 cc. of toluene of the following ingredients:
246.3 g. of a polytetramethylene oxide diol having a molecular weight o~ about lOOO (available as Polymeg lOOO, ~rom ~rhe Quaker Oats Company, Chicago, Illinois); 125 g.
of 3,5-dinitrobenzoyl chloride; and 55.6 g. o~ triethylamine.
The reaction mixture was heated and allowed to reflux over-~ 7 9 0 night. The reaction mixture was cooled and 500 cc. o~
cyclohexane were added~ Following filtration, the solution was evaporated to yield 230 g. of a dark resin.
Th~ dark resin, as recovered above, was dissolved in one liter o~ isopropanol. To the resulting solution was added S g. of a 5~ palladium on-carbon catalyst, ~ollowed by 56 g. of hydrazine hydrate. The reaction mixture was heated, allowed to reflux for three hours, cool~d, filtered, and evapoxated to yield 160 g. of a resin product. The product was analyzed for amine equivalents (~.1 meq./g.) and ~or residual acidity (0.01 meq.H+/g.). The resin product was an oligomeric di-(3,5-diaminobenzoate) ester of poly-~tramethylene oxi~e diol, the product being represented by the following structure:

~N ~ c-Q ~ CH2-CH2-C~2 CX2 ~a ~ N~
~N NH2 EX~LE VI
.
TAis example illustrates the production by the polyaddition process o~ a cast elastomer utilizing oligomeric di-~p-aminobe~zoate) este~ of polytetramethylene oxide diol and a liquid polyisocyanate. A reaction mixture was prepared by mixing the tollowing ingredients: 66 g. o~ an oligomeric di-(p-aminobenzoate~ este~ of polytetramethylene oxide diol, prepared utilizir.g the procedur~ set forth in Example I and having an amine e~uivalent value of 588 g.~eq.;
and 15.7 g. of a liquid polyisocyanate h ving an isocyanat~
equivalents value of 1~.7 g./eq. and comprising MDI and polymeric MDI (available as PaPI 901 from The Upjoh~ Company, -37~

o~

Kalamazoo, Michigan). The resulting mixture~ which exhibited a pot life of seven minutes, was poured into a mold which had been pre-heated to a temperature of 110C and was retained in the mold at this temperature for one-half hour. A firm and non-cheesy elastomeric material was then demolded and maintained at a temperature of 110C overnight and was aged for one week at room temperature and 50% relative humidity. The following table sets forth properties of the resulting polymer.
Table 1 Shore A Hardness (ASTM D2240-75) 92 Elongation at Break (ASTM D412-68) 303%
100% Modulus (ASTM D412~68) 1071 p.s.i.
300% Modulus (ASTM D412-68) 2689 p.s.i.
Tensile Strength (ASTM D412-68)2831 p.s.i.
Split Tear (ASTM D624-73) 43/61 p.l.i.
Bashore Rebound (ASTM D2632-75) 43 EXAMPLE VII
This example illustrates the production by the poly-addition process of a liquid-cast elastomer utilizing a liquid polyisocyanate and an admixture of oligomeric di-(p-aminobenzoate) and di-(3~5~diaminobenzoate) esters of polytetramethylene oxide diol. A mixture of 64.6 g. of the di-(p-aminobenzoate) ester of polytetramethylene oxide diol, prepared as described in Example I
and having an amine equivalent value of 588 g./eq., and 1.4 g. of a di~(3,5-diaminobenzoate) ester of' polytetramethylene oxide diol, prepared as described in Example ~ and having an amine equivalent value of 244 gO/eq., was prepared and degassed with nitrogen. The degassed mixture was then mixed with 17 g. of a liquid polyisocyanate comprising MDI and a tri-functional cyclo-adduct thereof (available as Isonate~ 143L

*Trade Mark ~7~09l3 from The Upjohn Company, Kalamazoo, Michigan). The resulting mixture, which exhibited a pot life of five minutes, was poured into a mold which had been pre-heated to a temperature of 110C.
After 15 minutes, a firm and non-cheesy elastomer was demolded and maintained overnight at a temperature of 100C. After a one~
week aging period, at room temperature and 50% relative humidity, the elastomer exhibited the following physical properties, set forth in Table 2.
Table 2 Shore A Hardness (ASTM D2240-75)92 Elongation at Break (ASTM D412-68) 400%
100% Modulus (ASTM D412-68) 1284 p.s.i.
300% Modulus (ASTM D412-68) 2157 p.s.i.
Tensile Strength (ASTM D412-68)3973 p.s.i.
Split Tear (ASTM D624-73) 60/110 p.l.i.
Bashore Rebound (ASTM D2632-75) 50 EXAMPLE VIII
This example illustrates the production by the polyaddition process of a cast elastomer utilizing MDI and an oligomeric di(p-aminobenzoate) ester of polytetramethylene oxide diol. An oligomeric di(p-aminobenzoate) ester of poly-tetramethylene oxide diol, (66 g. of the product prepared as described in Example I) was heated to a temperature of 50C and mixed with 14.4 g. of MDI (available as Mondur M* from Mobay Chemical Corporation, Pittsburgh, Pennsylvania) which had been heated to a temperature of 50C. The resulting mixture, which exhibited a pot life of four minutes, was poured into a mold which had been pre-heated to 100C. After one-half hour, a ~'irm and non-cheesy elastomeric piece was demolded and was maintained overnight at a temperature of 100C.

*Trade Mark ~ 9 ~ ~

The elastomeric piece was aged ~ox one week at 50% relative humidity and at room temperature and exhibited the following properties, set forth in Table 3.
Table 3 Shore A Hardness (ASTM D2240-75) 92 Elongation at Break (ASTM D412-68)630~
lO0~ Modulus (ASTM D412-68) 1058 p.s.i.
300~ Modulus (ASTM D412-68) 1235 p.s.i.
Tens~le Strength (ASTM D~12-68)310G p.s.i.
5plit ~ear (ASTM D624-73) 1724 p.l.i.

Bashore Rebound (ASTM D2632-75) 50 EXAMPLE IX
This example illustrates the production by the polyad~ition process o~ a cast elastomer utilizing a liquid polyisocyanate and a~ oligomeric tri-(p-aminobenzoate~ ester of a polypropylene oxide triol. An amount of 70 g. of a tri-(p-aminobenzoate) ester of polypropylene oxide triol, prepared as described in Example II herein, was mixed at room tempcra-turc with 6 . 2 g. of a liquid polyisocyanate comprising MDI
and a tri-functional cycloadduct thereof (available as Isonate 143L rom ~he Upjohn Company, Xalamazoo, Michigan).
The resulting mixture, which exhibited a pot li~e o~ ten minu~es, was poured into a mold which had been pre-heated to a temperature o~ 135C and was retained in the mold at ~his temperature for 16 hours. The elastomer, a firm and non-cheesy piece, was then demolded and aged ~or one week at room temperature and 50~ relative humidity. The following physical properties, set forth in Ta~le 4, were obtained:

~L~7'-30~8 Table 4 ~hore A Hardness (AS'~M D~240 75) 35 ~longation at ~reaX lASTM D412 ~8)480%
100% Modulus (ASTM D41~-68) 76 p.s.i.
300~ ~odulus ~ASTM D412-68) 160 p.s.i.
Tensile Stxength (ASTM D412-6R) 320 p.s.i.
Split Tear (AST~ D624-73) 69 p.l.i.
Ba-chore ~ebound ~ASTM D2632-7$) 38 This example illustrates the produc~ion by the polyaddition process of a liquid-cast elastomer utilizing a liquid polyisocyanate and an admixture of oligomeric di-~p-aminobenzoate) and di-(m-aminobenzoate) esters o~ polytetra-methylene oxide diol. A mixture of 52.8 g. o~ the di-(p-aminobenzoate) es~er of polyte~ramethylene oxide diol prepared as described in Example I, ~nd 13 g. of the di~m-aminobenzoate) ester of polytetramethylene oxide diol, prepared as described in Example IV, was prepared and degassed with ~itrogen. The degassed mixture was then mixed at room temperature witn 15.4 g. of a liquid polyisocyanate comprising MDI an~ a tri-functional cycloadduct thereof (available as Isonate 143L
from the Upjohn Company, Ralamazoo, Michlgan). Tl~ re~uitlng mixture, which exhibited a po~ lifa of eight minutes, was poured i~to a mold which had been pre-heated to a temperature of 110C. After 15 minutes, the resulting firm and non-cheesy elastomer was demolded and maintained overnight at a tempera-ture o~ 110C. After a one week aging period, at room tempera ture and 50~ relative humidity, the elastomer exhibited the following physical properties, set ~orth in Table 5.

~ ~ 7 ~

Table 5 Shore A Hardness (ASTM D2240-75)92 Elongation at BreaX (ASTM D412-68) 596%
100% Modulus (ASTM D~12-68~ 1260 p.s.i.
300% Modulus (ASTM M 12-68) 1600 p.s.i.
Tensile Strength (ASTM D412-6~)7975 p.s.i.
Split Tear ~ASTM D62~-73)166/308 p.l.i.
Rashore Rebound (ASTM D2632-75) 50 EXAMPLE XI
This example illustrates the production by the polyaddition process of a liquid-cast elastomer utilizing a liquid polyisocyanate a~d a~ admixture of oligomeric di-(p-aminobenzoate) esters of polytetramethylene oxide diols.
A mixture of 60.3 g. of the oligomeric di-(p-aminobenzoate) ester of Polymeg 1000, prepared as set forth i~ Example I, and 10.1 g. of the oligomeric di-(p-aminobenzoate) ester of Polymeg 650, prepared as set ~orth in Example III, was degassed with nitrogen gas. The degassed mixture was then mixed with 17.7 g. of a liquid polyisocyanate comprising MDI
and a tri-functional cycloadduct thereof (available as Isonate 143L from The Upjohn Company, Kalamazoo, Michigan).
The resulting mixture, which exhibited a pot life of nine minutes, was poured into a mold which had been pre-heated to a temperature o~ 110C. After one-half hour, the resulting 25. firm and non-cheesy elastomer was demolded and maintained overnight at a temperature of 110C. After a one-week aging period, at room temperature and 50% relative humidity, the elas-tomer exhibited the followi~g physical propertiPs, set forth in Table 6.

79(;~9~
Table 6 Shore A Hardness (ASTM D224 0- 75) 95 Elongation at Break (ASTM D412~68) 570%
100% Modulus (ASTM D412-68) 1510 p.s.i.
300% Modulus (ASTM D412-68) 2043 p.s.i.
Tensile Strength (ASTM D412-68) 8090 p.s.i.
Split Tear (ASTM D624-73) 257/384 p.l.i.
Bashore Rebound (ASTM D2632-75) 55 EXAMPLE XII
An oligomeric di-(ortho-aminobenzoate) ester of polytetramethylene oxide diol was prepared in the following manner.
A suspension of 3.0 g. of powdered sodium hydroxide in 250.1 g. (0.25 mole) of a polytetramethylene oxide diol having a molecular weight of about 1000 (Teracol 1000~, available from E.I. DuPont de Nemours and Company, Wilmington, Delaware) was heated to 90C and 130 g. (0.80 mole) of isatoic anhydride added gradually over five hours at 30-minute intervals. The reaction was completed by heating to 130C for 15 minutes and was cooled to 35C. Methylene chloride (250 ml.) was added to the reaction solution and the solution was filtered. The filtrate was washed with 500 ml. of deionized water (saturated with carbon dioxide) to remove residual sodium hydroxide. The reaction mixture was extracted three times, each with a 500-ml. quantity of deionized water. Methylene chloride solvent was removed from the reaction product under vacuum, yielding an amber-yellow viscous liquid product.
Analysis of the products indicated an amine equivalent of 1.45 milliequivalents per gram of product (meq./g.).

~Trade Mark ~i ~1790g~
Infrared spectral analysis conrirmed the structure of the oligomeric product, represented by the following for~ula:

O O
~- C - o~ CH2-CH2-CH2-cH2 ~
NH2 ~I2N

EXAMPLE XIII
This example illustrates the production by the poly-addition process of a cast elastomer utilizing MDI and an oligomeric di(p-aminobenzoate) ester of polytetramethylene oxide diol. Fifty grams (0O07 equivalent) of an oligomeric di(p-aminobenzoate) ester of polytetramethylene oxide diol (prepared substantially as described in Example I) was heated to a temperature o~ 50C and mixed with 8.8 q. of MDI (available as Mondur Mx from Mobay Chemical Corporation, Pittsburgh, Pennsylvania) which had been heated to a temperature o~ 50C.
The resulting mixture, which exhibited a pot life of seven minutes~ was poured into a mold which has been pre-heated to 110C. The mold was then placed under a pressure of 2000 p.s.i.
~or one hour at a temperature of 110C. The mold was placed into an aging oven for 18 hours at a temperature of 110C and the mold was disassembled. The resulting elastomeric piece, firm and non-cheesy, was aged for one week at 50% relative humidity and atroom temperature and exhibited the following properties~ set forth in Table 7.

~Trade Mark 1~'7'~'3C~

Table 7 Shore A Hardness (ASTM D2240-75) 92 Elongation at Break (ASTM D412-68) 543%
100~ Modulus (ASTM D412-6g) 1307 p.s.i.
300% Modulus (ASTM D412-68) 1924 p.s.i.
Tensile Strength (ASTM D412-68) g249 p.s.i.
Compression Set (ASTM D395-65, Method B) 69 Bashore Rebou~d (ASTM D2632-75) 59 Split Tear Maximum 568 p.l.i.
EXAMPLE XIV
For purposes o~ comparison with the elastomeric material prepared as described in EXAMPLE XIII, a polymeric material was prepared u~ilizing an oligomeric di(o-aminobenzoate) ester of a polytetramethylene oxide diol as follows. Fifty grams (0.07 equivalent) of di(o~aminobenzoate) ester of polytetra-methylene oxide diol (the diester prepared in EXAMPLE XII
herein) was heated to a temperature of 50C and mixed with 8.8 g. (0.07 equivalent) Ot ~DI (~.ondur M from Mobay Chemical Corporation, Pittsburgh, Pennsylvania) which had been heated to a temperature of 50C. The resulting mixture, which exhibited a pot life of seven minutes, was poured into a mold which had been pre-heated to llO~C. The mold was then placed under a pressure o~ 2000 p.s.i. for one hour at a temperature o~ 110C. The mold was placed into an aging oven for 18 hours at a temperature of 110C and the mold was disassembled. The resulting product could not be demolded as a si~gle sheet owing to the soft and ~ummy nature o~ the material. Examination oE the resulting product after several hours at ambient temperature, showed the pol~meric material to flow in the nature of a viscous li~uid. Even after a few days, the ~7~ O 9~

casting had not hardened and remained so~t and sticky.
The product had a Shore A Hardness of 5. The remaining properties outlined in Table 7 could not be measured.
From the pre~eding results, it will be appreciated that the product of this Example, based upon the utiliza-tion of an oligomexic di(ortho-aminobenzoate) es~er of tetramethylene oxide diol, exhibited inferior physical proper-ties relative to the ela~tomeric material of EXAMPLE XIII, based upon the utilization of an oligomeric di(para-amino-benzoate) ester of tetramethylene oxide diol.
EXAMPLE XV
This example illustrates the production by tne polyaddition process of polymeric materials utilizing a liquid polyisocyanate and an oligomeric di~aminoben20ate) ester o~ a polytetr~methylene oxide diol. In one case (Polymer XV A), the oligomeric di(aminobenzoate) ester of polytetramethylene oxide diol was the di(p-aminobenzoate) ester utilized in EXAMPLE XIII. In the case of the production of Polymer XV ~, the oligomeric di(aminobenzoate) ester was the di(o-amino-benzoate) ester o~ EXAMPLE XII. The polymeric materials were prepared in the following manner. A reaction mixture was pre-pared in each case by mixing the following ingredients: 50g.
(O.07 equivalent~ o~ the appropriate oligomeric di-(amino-benzoate) ester o~ polytetramethylene oxide diol; and 9.3 g.
(0.07 equivalent) of a li~uid polyisocyanate comprising MDI
and polymaric MDI (available as PaPI 901 from The Upjohn Company, ~alamazoo, Michigan). The resulting mixture was in each case poured into a mold which had been pre-hea~cd to temperature of 110C and was retained in the mold at this temperature for one hour. The resulting polymeric material ~ ~ 7~

was then in each case ~emolded, maintained at a temperature of 110C overnight and aged for one week at room temperature and 50% relative humidity. The following table (Table 8)sets for~h t~e results of the physical properties of the resulting polynters.
Table_8 Poly~er XV A Polymer XV B
Shore A Hardness (AS~M D2240-75) 87 50 Elongation at Break (ASTM M12-68) 300% 398%
100% Modulus (ASTM D412-68)1204 p.s.i. 120 p.s.i.
300% Modulus (ASTM D412-6~)4415 p.s.i. 245 p.s.i.
Tensile Strength (ASTM D412-68) 4415 p.s.i. 476 p.s.i.

Split Tear, Initial/Average (ASTM D624-73) 60.~/62.3 p.l.i. 15.8/20.7 p.l.i.
Compression Set(AsTM ~395-65,Method B) 66 25 Bashore Rebound (ASTM D26~2-75) 52 14 From inspection of the data set forth in Table 8, it will be seen that ~he physical proper~ies of Polymer XV B, based upon utilization of the ortho- isomeric oligomer, were in~erior to those of Polymer XV A, based upon utilization of the para- isomeric oligomer, i.e., the di-~p-benzoate) ester of polytetramethylene oxide diol.

EXAMPLE XVI
For purposes of evaluating the thermal stability of an elastomer prepared from an oligomeric di-(ortho-aminobenzoate ester of a polyal~ylene ether glycol, the ollowing was conducted. ~i~ty grams ~0.07 equivalent) of th~ di-(o-aminoben20a~.e) ester of polytetramethylene oxide diol (the product of Example XII) and 9.3 g. (0.07 equiYal~nt) of a liquid polyisocyanate comprising MDI and pol~meric L~DI
(PaPI 901 ~rom the Upjohn Company, Ralamazoo, Michigan) were ~. ~ 79V~

. . .
mixed and~poured into a mold at r.oom temperature. The mold was then placed under 2000 p.s.i. pressure overnight at room temperature. The following day, the polymeric material was demolded and cut in half along a diagonal. One half of the polymeric material (Polymer XVI-R.T.) was aged Eor one week at room temperature (R.T.) and 50~ relative humidity. The second hal~ (Polymer XVI-110C) was heated to a temperature of 110C overnight and was then aged at room temperature and 50% relative humidity for the remainder 10` o one-week period. Physical properties of the two pol~meric materials subjected to the respective hea4 histories aforedescribed, were measured and are reported as follows in Table 9, Table 9 Polymer XV A Polymer XV B
Shore A Hardness (ASTM D2240-75)65 60 Elongation at Break (ASTM D412-68) 383% 360%
100% Modulus (ASTM D412-68) 197 p.s.i. 74 p.s.i.
300~ Modulus ~ASTM D412-68) 555 p.s.i. 155 p.s.i.
Tensile Strength (ASTM D412 68)1428 p.s.i.219 p.s.i.

Compression Set (ASTM D395-69, Method B) 24 34 Bashore Rebound (ASTM D2632-75)31 22 From the results reported in Table 9, it will be seen that the physical properties of the polymer prepared rom the di(o~aminobenzoate)ester of polytetramethylene oxide diol showed appreciable deterioration (Polymer XVI-110C) as the result of subjection to heat relative to the same polymeric material aged only at room temperature (Polymer XVI-R~T.). It will also be noted from a comparison of ~48-~ i ~9 ~ ~ ~

the physical properties of the polymeric material of Example XV tPolymer XV A), prepared from an oligomeric di~
(p-aminobenzoate) ester of polytetramethylene oxide diol and aged at 110C, that the physical properties of Polymer XV A
were superior to those of polymer XVI-110C.

Claims

6397 What is claimed is:

1. A synthetic polymer substantially free of the reaction product of an isocyanate and a polyalkylene ether glycol or polyol and substantially free of salts formed during production of the polymer by reaction of a basic material and an amine salt and comprising the reaction product of a polyisocyanate and substantially an equivalent amount of an oligomeric aminobenzoic acid ester or amide having the formula wherein n is an integer from 2 to 4; each x is one or two;
each benzoyl nucleus is para-, meta- or di-meta-amino-substituted;
each Z is -0- or -?-; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000.

2. The synthetic polymer of Claim 1 wherein said polyisocyanate comprises from about 0.9 to about 1.2 equivalents per equivalent of said oligomeric amino-benzoic acid ester or amide.

3. The synthetic polymer of Claim 2 wherein said polyisocyanate comprises from about 1.0 to about 1.15 equivalents per equivalent of said oligomeric aminobenzoic acid ester or amide.

4. The synthetic polymer of Claim 1 wherein said oligomeric aminobenzoic acid or amide has the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl or amino groups from an oligomeric polyol or polyamine having a molecular weight in the range of about 400 to about 6,000.

5. The synthetic polymer of Claim 4 wherein said molecular weight is in the range of from about 650 to about 2,000.

6. The synthetic polymer of Claim 4 wherein each said Z is -O- and said divalent radical G is obtained by removal of two hydroxyl groups from a polyalkyleneether glycol wherein the alkylene moiety thereof has up to ten carbon atoms.

7. The synthetic polymer of Claim 6 wherein said alkylene moiety of said polyalkyleneether glycol has from two to four carbon atoms.

8. The synthetic polymer of Claim 7 wherein said alkylene moiety is from polytetramethylene ether glycol having a molecular weight of about 1000.

9. The synthetic polymer of Claim 1 in the form of a cast elastomer.

10. The synthetic polymer of Claim 8 in the form of a cast elastomer.

11. The synthetic polymer of Claim 1 in the form of a cellular foam.

12. The synthetic polymer of Claim 8 in the form of a cellular foam.

13. The synthetic polymer of Claim 1 wherein said oligomeric aminobenzoic acid ester or amide has the formula wherein G represents a trivalent radical obtained by the removal of three hydroxyl or amino groups from an oligomeric polyol or polyamine having a molecular weight in the range of from about 400 to about 6,000.

14. The synthetic polymer of Claim 13 wherein said molecular weight is in the range of from about 650 to about 2,000.

15. The synthetic polymer of Claim 13 wherein each said Z is -O- and said trivalent radical G is obtained by removal of three hydroxyl groups from a polyoxyalkylene-ether glycerol.

16. The synthetic polymer of Claim 15 wherein said alkylene moiety of said polyoxyalkyleneether glycol has from two to four carbon atoms.

17. The synthetic polymer of Claim 16 wherein said alkylene moiety is from polytetramethylene ether glycol having a molecular weight of about 1000.

18. The synthetic polymer of Claim 17 in the form of a cast elastomer.

19. The synthetic polymer of Claim 17 in the form of a cellular foam.

20. The synthetic polymer of Claim 1 wherein said polyisocyanate comprises a liquid polyisocyanate.

21. The synthetic polymer of Claim 20 wherein said liquid polyisocyanate includes 4,4'-diphenylmethane diisocyanate.

22. The synthetic polymer of Claim 20 wherein said liquid polyisocyanate includes a polymeric polyiso-cyanate having from about 4 to about 15 isocyanate groups per molecular.

23. The synthetic polymer of Claim 1 which comprises the reaction product of a polyisocyanate and substantially an equivalent amount of a mixture of oligomeric aminobenzoic acid esters, said mixture comprising a di-(4-aminobenzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of about 400 to about 6,000; and from about 1% to about 50% by weight of said di-(4-aminobenzoate) ester, of a di-(3-aminobenzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of fram about 400 to about 6,000.

24. The synthetic polymer of Claim 23 wherein each said G is a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 650 to about 2,000.

25. The synthetic polymer of Claim 23 wherein each said G is a divalent radical obtained by the removal of two hydroxyl groups from a polyoxyalkyleneether glycol.

26. The synthetic polymer of Claim 1 which comprises the reaction product of a polyisocyanate and substantially an equivalent amount of a mixture of oligomeric aminobenzoic acid esters, said mixture comprising a di-(4-aminobenzoate)ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 400 to about 6,000; and from about 1% to about 15% by weight of said di-(4-aminobenzoate) ester, of a di-(3,5-diamino-benzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 400 to about 6,000.

27. The synthetic polymer of claim 26 wherein each said G is a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 650 to about 6,000.

28. The synthetic polymer of Claim 26 wherein each said G is a divalent radical obtained by the removal of two hydroxyl groups from a polyalkyleneether glycol.

29. The synthetic polymer of Claim 1 which comprises the reaction product of a polyisocyanate and substantially an equivalent amount of a mixture of oligomeric p-aminobenzoic acid esters, said mixture comprising a di-(p-aminobenzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of about 400 to about 6,000, and from about 1% to about 20% be weight of said di-(p-aminobenzoate) ester, of a tri-(p-amino-benzoate) ester having the formula wherein G represents a trivalent radical obtained by the removal of three hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 400 to about 6,000.

30. A process for preparing a synthetic polymer from a reaction mixture substantially free of polyalkylene ether glycols or polyols and acidic reaction rate-controlling amine salt-forming agents, said process comprising reacting a polyisocyanate with substantially an equivalent amount of an oligomeric p-aminobenzoic acid or amide having the formula wherein n is an integer 2 to 4; each x is one or two; each benzoyl nucleus is para-, meta- or di-meta-amino-substituted; each Z is -O- or -?-; and G is an n-valent radical obtained by removal of hydroxyl groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000.

31. The process of Claim 30 wherein said poly-isocyanate comprises from about 0.9 to about 1.2 equiva-lents per equivalent of said oligomeric aminobenzoic acid ester of amide.

32. The process of Claim 31 wherein said poly-isocyanate comprises from about 1.0 to about 1.15 equiva-lents per equivalent of said oligomeric aminobenzic acid ester or amide.

33. The process of Claim 31 wherein said oligomeric aminobenzoic acid ester or amide has the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl or amino groups from an oligomeric polyol or polyamine having a molecular weight in the range of about 400 to about 6,000.

34. The process of Claim 33 wherein said molecular weight is in the range of from about 650 to about 2,000.

35. The process of Claim 33 wherein each said Z
is -O- and said divalent radical G is obtained by removal of two hydroxyl groups from a polyalkyleneether glycol wherein the alkylene moiety thereof has up to ten carbon atoms.

36. The process of Claim 35 wherein said alkylene moiety of said polyalkyleneether glycol has from two to four carbon atoms.

37. The process of Claim 36 wherein said alkylene moiety is from polytetramethylene ether clycol having a molecular weight of about 1000.

38. The process of Claim 30 wherein said reaction mixture includes a blowing agent.

39. The process of Claim 30 wherein said oligomeric aminobenzoic acid ester or amide has the formula wherein G represents a trivalent radical obtained by the removal of three hydroxyl or amino groups from an oligomeric polyol or polyamine having a molecular weight in the range of from about 400 to about 6,000.

40. The process of Claim 39 wherein each said Z
is -O- and said trivalent radical G is obtained by removal of three hydroxyl groups from a polyoxyalkyleneether glycerol.

41. The process of Claim 40 wherein said alkylene moiety of said polyoxyalkyleneether glycol has from two to four carbon atoms.

42. The process of Claim 41 wherein each said alkylene moiety is from polytetramethylene ether glycol having a molecular weight of about 1000.

43. The process of Claim 42 wherein said reaction mixture includes a blowing agent.

44. The process of Claim 30 wherein said poly-isocyanate comprises a liquid polyisocyanate.

45. The process of Claim 44 wherein said poly-isocyanate comprises 4,4'-diphenylmethane diisocyanate.

46. The process of Claim 44 wherein said liquid polyisocyanate comprises a polymeric polyisocyanate having from about 4 to about 15 isocyanate groups per molecule.

47. The process of Claim 30 which comprises reacting said polyisocyanate with substantially an equivalent amount of a mixture of oligomeric aminobenzoic acid esters, said mixture comprising a di-(4-aminobenzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of about 400 to about 6,000; and from about 1% to about 50% by weight of said di-(4-aminobenzoate ester), of a di-(3-aminobenzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 400 to about 6,000.

48. The process of Claim 47 wherein each said G
is a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 650 to about 2,000

49. The process of Claim 47 wherein each said G
is a divalent radical obtained by the removal of two hydroxyl groups from a polyoxyalkyleneether glycol.

50. The process of Claim 30 which comprises reacting said polyisocyanate with substantially an equivalent amount of a mixture of oligomeric aminobenzoic acid esters, said mixture comprising a di-(4-aminobenzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 400 to about 6,000; and from about 1% to about 15% by weight of said di-(4-aminobenzoate) ester, of a di-(3,5-diamino-benzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 400 to about 6,000.

51. The process of Claim 50 wherein each said G
is a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 650 to about 2,000.

52. The process of Claim 50 wherein each said G
is a divalent radical obtained by the removal of two hydroxyl groups from a polyalkyleneether glycol.

53. The process of Claim 30 wherein said oligomeric aminobenzoic acid ester comprises a mixture of a di-(p-aminobenzoate) ester having the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl groups from an oligomeric polyol having a molecular weight in the range of about 400 to about 6,000; and from about 1% to about 20% by weight of said di-(aminobenzoate) ester, of a tri-(aminobenzoate) ester having the formula wherein G represents a trivalent radical obtained by the removal of three hydroxyl groups from an oligomeric polyol having a molecular weight in the range of from about 400 to about 6,000.

54. A synthetic polymer which consists essentially of the reaction product of a polyisocyanate and substantially an equivalent amount of an oligomeric aminobenzoic acid ester or amide having the formula wherein n is an integer from 2 to 4; each x is one or two; each benzoyl nucleus is para-, meta- or di-meta-amino-substituted;
each Z is -O- or ; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000.

55. The synthetic polymer of Claim 54 wherein said poly-isocyanate comprises from about 0.9 to about 1.2 equivalents per equivalent of said oligomeric aminobenzoic acid ester of amide.

56. The synthetic polymer of Claim 54 wherein said polyisocyanate comprises from about 1.0 to about 1.15 equivalents per equivalent of said oligomeric amino-benzoic acid ester or amide.

57. The synthetic polymer of Claim 54 wherein said oligomeric aminobenzoic acid ester or amide has the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl or amino groups from an oligomeric polyol or polyamine having a molecular weight in the range of about 400 to about 6,000.

58. The synthetic polymer of Claim 57 wherein said molecular weight is in the range of from about 650 to about 2,000.

59. The synthetic polymer of Claim 57 wherein each said Z is -O- and said divalent radical G is obtained by removal of two hydroxyl groups from a polyalkyleneether glycol wherein the alkylene moiety thereof has up to ten carbon atoms.

60. The synthetic polymer of Claim 59 wherein said alkylene moiety of said polyalkyleneether glycol has from two to four carbon atoms.

61. The synthetic polymer of Claim 60 wherein said alkylene moiety is from polytetramethylene ether glycol having a molecular weight of about 1000.

62. The synthetic polymer of Claim 54 in the form of a cast elastomer.

63. The synthetic polymer of Claim 54 in the form of a cellular foam.

64. A process for preparing a synthetic polymer which comprises reacting a mixture which consists essen-tially of a polyisocyanate and substantially an equivalent amount of an oligomeric aminobenzoic acid or amide having the formula wherein n is an integer from 2 to 4; each x is one or two;
each benzoyl nucleus is para-, meta- or di-meta- amino-substituted; each Z is -O- or ; and G is an n-valent radical obtained by removal of hydroxy groups or amino groups from an n-valent polyol or polyamine having a molecular weight of from about 400 to about 6,000.

65. The process of Claim 64 wherein said poly isocyanate comprises from about 0.9 to about 1,2 equiva-lents per equivalent of said oligomeric aminobenzoic acid ester or amide.

66. The process of Claim 65 wherein said poly-isocyanate comprises from about 1.0 to about 1.15 equiva-lents per equivalent of said oligomeric aminobenzoic acid ester or amide.

67. The process of Claim 65 wherein said oligo-meric aminobenzoic acid ester or amide has the formula wherein G represents a divalent radical obtained by the removal of two hydroxyl or amino groups from an oligomeric polyol or polyamine having a molecular weight in the range of about 400 to about 6,000.

68. The process of Claim 64 wherein said molecu-lar weight is in the range of from about 650 to about 2,000.

69. The process of Claim 64 wherein each said Z
is -O- and said divalent radical G is obtained by removal of two hydroxyl groups from a polyalkyleneether glycol wherein the alkylene moiety thereof has up to ten carbon atoms.

70. The process of Claim 69 wherein said alkylene moiety of said polyalkyleneether glycol has from two to four carbon atoms.

71. The process of Claim 70 wherein said alkylene moiety is from polytetramethylene ether glycol having a molecular weight of about 1,000.

72. The process of Claim 64 wherein said reaction mixture includes a blowing agent.