CA1229090A - N-(2-hydroxyalkyl)phthalimide monomer for heat curable solventless liquid prepolymer - Google Patents

Abstract

Abstract of the Disclosure A novel monomer of formula:

Description

~ is is ~ divisional applica-tion of copendinq application serial no. 444,411, filed December 29, 1983.

Specification The fabrication of articles from rubber polymers such as isoprene-acrylonitrile copolymers has, in the past, gener-ally involved the evaporation of a solvent. Acrylonitrile rubbers are typically prepared as a solution wherein the polymer is dissolved in an organic solvent. The solvent evaporates, allowing the polymer to dry. The dried rubber polymers are generally so viscous they cannot be applied to a substrate or shaped.
The use of solvent, in this manner, presents two basic problems: cost and health hazards. The solvents them-seLves are expensive. Although they only act as carriers to facilitate use of the polymer, they are major cost factors. In addition the solvent vapors, formed as the solvent evaporates, are pollutants and general health hazards. These vapors must be trapped or eliminated which is also quite expensive~
One way ~o overcome ~he need for a solvent, and to provide a curable polymer, is to form a low molecular weight poLymer, commonly referred to as a prepolymer, which is liquid at room temperature and which can be cured to form a satisfac-tory polymer. Prior art prepoLymers have attempted to accom-plish this by forming liquid prepol~mers having unreacted crosslinkable or reactive terminal groups. Such polymers are known in th~ art. However, they have certain inherent disad-vantages. Primarily, these polymers, in order to cure well and provide good compression set, must have a substantial portion of the end groups made up of the reactive group. For practical reasons, it is difficult to provide a sufficient number of reactive terminaL groups so as to provide a liquid polymer which cures to provide a polymer with suitable compression set.

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~2~(~9~) Summary of the Inventlon This application claims the monomer ~C ~ N-R3-o-C~I2-NH-C-CII-CH2-- la -I

The present invention comprises a novel self-curing rubber prepolymer having low compression set, i.e., about 20-30%, Shore A hardness of about 70 74%, tensile strength of about 410-640 psi, tensile elongation of about 140~, and fuel resistance of about 49-62%. Polymers having these characteris~
tics are considered to be suitable for various applications including, for example, in gaskets~ In a preferred form of the invention, the prepolymer can be used to form strong, smooth rubber sheets suitable ~or use as commercial gaskets and as laminates also useful as gaskets. Furthermore, novel monomers for use in combination with this prepolymer and prepolymer formed from these monomers are disclosed.
A liquid, heat curable, nitrile rubber is formed from a rubber ti.e., rubber forming) monomer such as isoprene, butadiene or alkyl esters of acrylic acid; a nitrile monomer such as acrylonitrile or methacrylonitrile; and an N-(R-oxymethyl) acrylamide monomer. The latter monomers have the following general formula:

ll R1 - O - CH~ - N - C - CH = CH2 Rl can be C3 to C22 alkyl, ether, aldehyde~ ketone, amide, ester, imide or a phthalimide. N-(R-oxymethyl~ acrylamides where R represents C3-C8 alkyl are readily available.
R1 is preferably a substituent such tha-t the com pound Rl-OH has a boiling point greater than the cure temper-ature of the correspondlng pre~ ymer. Ae will be explained, ~ ~9(~

during the cure of the rubber, the Rl group separates rom the prepoLymer to form the corresponding alcohol. If the boiling point of the Rl alcohol is less than the cure tempera-ture of the prepolymer, the alcohol will boil, possibly causing a pitting of the surface of the polymer which in certain applications would be unacceptable, such as in the formation of the gasket material.
Preferably, Rl will be a moiety in which the formed alcohol has a boiling point greater than cure temperature of the polymer in which it i5 employed preferably greater than about 350F. In addition, the Rl group should be polar in order to make the formed poLymer more fuel resistant. Rl must not be a group which will interfere with the chain trans-fer agent. Rl groups which are non-interfering include ketones, esters and ethers, among others. Interfering groups include those with reactive hydrogens such as alcohols and amines.
Specifically, Rl can represent hexyl carbitol, so that the formed acrylamide monomer would have the following formula:

. Il n -C H - O - CH2 ~ CH2 ~ C~2 Where ~1 is a phthalimide, it is preferably an N~alkyl phthalimide so that the N-~R-oxymethyl) acrylamide has the llowing general forrula:

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~J~ N - R3 - O - CH2 - NH - C -- CEI -- CH2 O
wherein R3 is as Cl to about C10 alkyl and preferably has at least two carbon atoms.
These N~R-oxymethyl) acrylamides can be formed by substituting an Rl group of a monohydric alcohol for the R2 group in an N- ~R-oxymethyl) acrylamide having the general formula:

ll R2 - O -- CH2 -- NH -- C - CH = CH2 Generally, R2 should be an alkyl group having from 1 to 8 carbon atoms. Such starting materials are commercially avail-able. A description of the method of preparation of these commercially available compounds is disclosed in U.S. Patent 3,087,965~
These N-(alkoxymethyl) acrylamides are modified by substituting the alkyL group. For example, a second alcohol, such as hexyl carbitol or ~-hydroxyethyl phthalimide, can be reacted with the N-(alkoxymethyl) acrylamide under acid condi-tions and elevated temperatures to form the compound of the present invention.
When N-~isobutoxymethyl) acrylamide i5 used, theoret-ically equimolar amounts of that compound and a replacement primary alcohol are reacted in the presence of an acid catalyst such as toluene sulfonic acid (for example, 0.5 weight p~rcen~
based on the acrylamide monomer), at as low a temperature as possibl~. The isobutyl alcohol ormed is vacuum distilled ~rom the reaction mixture until the reaction has gone to completion.

_4_ In a successful reaction, near theoretical amounts of isobu,yl alcohol should be obtained. Excess replacement alcohol may be required to react all of the amide present. This method is further described by reference to the following ~wo examples.
Example I - Pre~aration of N-(hexylcarbitoxymethyl) acrylamide Predried hexyl carbitol and isobutoxymethacrylamide (IBM~), containing 200 ppm M~HQ, were mixed. An excess of hexyl carbitol (2.9 mole per mole of IB~) was used. The temperature of the mixture was maintained at less than about 65C. One half weight parcent of toluene sulfonic acid based on the weight of IBMA used was added. Two hundred parts per million of polymeriz~tion inhibitor, MEHQ, was added to supple-ment the 200 parts per million already present in the IBM~.
The ormed isobutyl alcohol was removed by vacuum distillation.
40.8 weight percent of N-(hexylcarbitoxymethyl) acrylamide in excess hexyl carbitol as solvent was formed. The excess hexyl carbitol was not removed due to its high boiling point.
The disadvantage of using N-(hexylcarbitoxymethyl) acrylamide is that in the preparation, excess hexyl carbi~ol is required to shift the equilibrium towards the formation of the N-(hexylcarbitoxymethyl) acrylamide. This requires a second step to remove the excess haxyl carbitol or the use of N-(hexylcarhitoxymethyl) acrylamide containing excess hexyl carbitol. Although the excess hexyl carbitol does not prevent the formation of the polymer or the curing of the prepolymer, it apparently does interfere to a certain extent with the polymerization and cure, and the formed product is not as good as would be expected.

_5_ ~

Exam~le II - Pre~aration of N-[~2-phthalimidoethoxy)m thyl]
acryLamlde Approximately equimolar amounts of N-(2-hydroxyethyl phthalimide (about 5 molar percent excess) and dried IBMA were mixed together in a reaction flask with 0.5 ~eight percent toluene sulfonic acid, based on the weight of IBMA, and 200 ppm MEHQ added. The nearly dry blend was stirred and heated u~ing an external oil bath. When the temperature reached 65C, a rapid reaction ensued and the reaction mixture partially liquified. After a short period of time,-the reaction rate (as evidenced by the isobutyl alcohol removal) almost stopped, and the reaction mixture solidified. The reaction mixture was then rapidly heated to about 120C, and the reaction again proceeded vigorously, going to near quantitative yields in a few more minutes. The product was a clear, low viscosity liquid at 120C which solidified at about 65C to a wa~y, opaque white solid which was found to be readily soluble in acrylonitrile.
The product was the 2-hydroxyethyl phthalimide ether of N-(hydroxymethyl~ acxylamide Other N-[R-oxymethyl] acrylamides can be made by the transetherification of an alkyloxymethyl acrylamide. An advantage of the use of the 2-hydroxyethyl phthalimide, as opposed to other alcohols, is that there is no need to add excess hydroxyethyl phthalimide to shift the equilibrium over towards the fonmation of the substituted amide. This is a significant factor where the alcohol is a high boiling point alcohol which is difficult to separate from the formed monomer.
The prepolymer of the present invention al50 contains an elasticizing or rubber monomer. These rubber monomers include conjugated diolefins, such as isoprene or butadiene and certain esters of acrylic and methacrylic acid. Specifically, 3 ~9~390 any alkyl ester of acrylic acid having two to ten carbons in the alkyl yroup, and any alkyl ester of me~hacrylic acid with four to eight ~arbons in the alkyl group can be used.
Prepolymer Formation Prepolymers are prepared by mixing from about 65~ to about 75~ rubber monomer, from about 20% to about 30% acrylo-nitrile or methacrylonitrile, and from about 4~ to about 10%
N-(R-oxymethyl) acrylamide. In addition, the polymer should have various other components which are well known to those of ordinary skill in the polymer art. These would include a chain transfer agent, such as t-octyl mercaptan. Other such chain transfer agents include C6-C22 tertiary mercaptans.
The prepolymerization occurs in an aqueous emulsion.
Suitable emulsi iers include fatty acid soaps and anionic sodium dodecylsulphate and commercially available emulsifiers, such a~ EMCOL 4910*, the sodium salt of an unsymmetrical sul~o-succinate produced by Witco Chemical.
Chelators, such as disodium ethylene diamine tetra-acetic acid are also helpful to remove any interfering metal impurities. Other components to initiate reaction or to increase the speed o~ the reaction would include a redox activator such as ferric chloride hexahydrate, a reducing agent such as sodium formaldehyde sulfoxylate and a free radical initiator. Suitable free radical initiators would include organic peroxides such as tertbutyl hydroperoxide, di-tertbutyl peroxide, cumene hydroperoxide, dicumene peroxide, benzoyl peroxide and the like. Organic peroxygen compounds such as tertbutyl peracetate, tertbutyl perbe~zoate, di-tertbutyl perpthalate are also suitable.
To preyare the prepolym~r, the rubber monomer, the acrylonitrile or methacrylonitrile, and the M-(R-oxymethyl) * Trade Mark ,~ 510 acrylamide can be mixed in the desired proportions within the limits set forth ahove, together with sufficient chain transfer agent, emulsifier, chelator, activa~or, reducing agent, free radical initiator and de-ionized, air-free water. The reac-tants are mixed and allowed to react for 20-24 hours at about 20C by which time yields of about 60~85% are obtained.
The temperature of the reaction should be maintained at less than 40C, prefera~ly about 20C. In addition -to maintaining the temperature of the reaction within the above limitations, a sufficient amount of a regulator or chain transfer agent must be added to establish the molecular weight of the prepolymer low enough to maintain the desired viscosity.
Suitable transfer agents or regulators include n-butyl mercap-tan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglyco-late, as well as t-octyl mercaptan, the preferred chain trans-fer agent~
The weight average molecular weight of the prepolymer should be established between S~000 and 25,000, and preferably, between 10,000 and 20,000~ The amount of chain transfer agent required will vary depending on the precise monomer used, how~ver, this will generally be less than about 5 weight percent based on the total weight of the monomers. The viscos-ity of the formed prepolymer desirably should be less than about 50,000 cps at an application temperature of 125C, or between 90,000 and 150,000 cps at room temperature. PoLymers having the above formulation can be fully cured to Eorm a non-flowable solid.

Example 3 - Isoprene, Acrylonitrile, Isobutoxymethacrylamide Prepolymer (IBMA Prepolymer) A prepolymer was formed using the following mater ials:

Material Parts _ ~ Wei~h~

Isoprene 73 Acrylonitrile 23 t~octyl thiol 3.5 EMCOL 4910* 7.5 diNa EDTA 0.015 FeCl 6H O 0.0075 Na formald~hyde sulfoxylate 0.2 Diisopropylbenzene 0.6 hydroperoxide (DIBHP, 50%) H2O (dionized, deaerated~ 210.
pH ad~usted to 9.0 with NaOH.
The prepolymerization used a total of 200 grams of monomers, and was run in a large, sealed glass bottle. The above mater-ials were weighed into the bottle. The bottle was purged with argon and sealed. The prepolymerization was run by rotating the bottle on a thermostatically controlled polymerization apparatus using water as a heat transEer medium. The prepoly-merization was conduted for 24 hours at 20~C. The prepolymer was recovered by chilling the bottle to about 5C, opening, adding several hundred milliliters of methanol and stirring vigorously. The aqueous alcohol layer was decanted and the liquid polymer washed with water, dissolved in methylene chloride, rewashed with water and then ethanol, and vacuum dried at 60~C overnight. Obtained were 110 grams (55~) pre-polymer, hereinafter referred to as IBMA prPpolymer.

Exam~Le 4 - Isoprene, Acrylonitrile, N-(hexylcarbi~oxymethyl) acrylamlde Prepolymer (HCMA Prepolymer) The following components were reacted according to the method descri~ed in Example 3;
Material Parts_by Weigh-t Isoprene 73 Acrylonitrile 23 HCMA 6.8 t-octyl thiol 3.5 EMCOL 4~10* 7.5 DiNa EDTA 0.015 FeCL 6H O 0.G075 Na f~rmald~hyde suLfoxylate 0.2 * Trade ~la~k iisopropylbenzene 0.6 hydroperoxide ~DIBHP, 50~) H2O (dionized, deaerat~d) 210.0 pH adjusted to 9.0 with NaOH.
70 grams (35~) of N-(hexylcarbitoxymethyl) acrylamide prepoLy-mer were formed, hereinafter referred to as HCMA prepolymer.
- Isoprene, Acrylonitrile, N-[(2-phthalimido ethoxy) methyl] Acrylamide Prepolymer (HP~A Prepolymer) The following components were reacted according to the method described in Example 3:
Material Parts by Weight Isoprene 73 Acrylonitrile 23 HPMA 6.9 ..
t-octyl mercaptan 3.5 EMCOL 4910* 7-5 diNa EDTA 0.015 FeC13 6H2O 0 0075 , Na formaldehyde sulfoxylate 0.2 D.iisopropylbenzene 0.6 hydroperoxide (DIBHP, 50~) H2O (deionized, deaerated) 210.0 pH adjusted to 9.0 with NaOH.
160 grams ~80~) of the N-[(2-phthalimidoethoxy~
methyl] acrylamide prepolymer, (hereinafter HPMA prepolymer) were obtained.
Characterization of The Formed Prepo~ymers The molecular weight of the formed prepolymers is given below in Table 1.

I _:~o_ ¦* Trade Mark ~1 1223~)90 1;

PREPOLYMER MOLECULAR WEIG~TS(a) :,~
GPC Mol cular Wei~hts CompositionMw Mn _ Mw/Mn IBMA Prepolymer 14,400 5,000 2~9 HCMA Prepolymer 8,700 4,800 1.8 HPMA Prepolymer 13,800 s,aoo 2.4 (a) Gel Permeation Chromatography (GPC), Waters 50~, THF solvent at 25C; 500, 103, 104 A~ columns, 7 polystyrene standards -790 to 50,000 ~w h~, , All the prepolymers were extremely viscous liquids. However, they were flowable at room temperature and at elevated tempera-tures such as about 100C, the viscoslty was substantially reduced~ _.
. Cuxe oE The Prep~ymers _~
The prepolymers can be further cured to form solid polymers having excellent compression sets, hardness and other physical characteristics required for use as gaskets, coatings and similar applications. Further, the prepolymexs can be combined with other materials, such as carbon black, pigments, antioxidants, etc.
The prepoLymers are cured by an acid catalyzed method conducted under heat, In order to cure the poLymer of the :~ ~

present invention, about 5 weight percent of an acid catalyst, based on the weight of the polymer, is added. Suitable acid catalysts include alkyl or aryl sulfonic acids, mono-alkyl phosphates such a monobutyl phosphate, and trichloro- and trifluoroacetic aclds~ The catalyst and other components, such as carbon black, are mixed by means such as a rubber mill at room temperature. The mixed composition is then molded and cured by heatinq to about 360F, and optionally placed under elevated pressure, until the formed rubber is completely cured Example 6 - Cure of The Prepolymer The prepolymers formed in the Examples 3, 4 and 5, were each formulated in a 3:2 ratio of prepolymer to carbon black. Five weight percent of p-toluene sulfonic acid was added~ The mixture was further compounded in a two roll rubber mill at room temperature for approximately 15 minutes. Each compounded mat~rial was molded under heat (360F) for 20 minutes in a 6" by 6" by 0.075" mold~ Each cured slab was evaluated for the following properties: compression set ~70~C
for 22 hours), hardness, tensile strength, elongation and fuel resistance~ The results are presanted in Table 2, Summary of Ph~sical Property Characteriæation.
It should be noted that the cured IBMA polymer h~d a pitted surface.

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Gasket Pre~aration The polymers of the present invention can be used, for example, to form gaskets. Gaskets are formed by coating both sides oE a substrate or base of metal, paper or synthetic material such as cloth, nylon, polye~hylene terephthalate, or other suitable materials, with the desired prepolymer formula~
tion. The applied prepolymer is then cured in situ on the base according to the method set forth in Example 6.
The prepolymer and method of formulating the prepoly-mer of the present invention enables one to prepare a heat-curable polymeric material, which is liquid at application temperatures of 125C and less. Furthermore, these prepolymers are curable to form a form polymers which exhibit compression sets which are comparable to other rubber materials suitable for gaskets. This thereby avoids any need for use of a solvent carrier although in certain applications it may be desirable to add a small amount of solvent or a solvent which reacts to form part of the polymer.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A monomer of formula: