JPS614710A - Anaerobic adhesive containing polymerizable activator - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel anaerobic curable compositions comprising conventional polymerizable (meth)acrylate monomers, free radical initiators, and polymerizable activators.

The invention also relates to the use of this improved anaerobic composition as adhesives and sealants.

Anaerobic compositions are well known in the industry. They remain uncured for as long as they are exposed to a sufficient air or oxygen supply, but they remain uncured for as long as they are exposed to a sufficient air or oxygen supply; Prepared or treated to polymerize spontaneously when oxygen is removed. Depending on the specific preparation, such compositions can be used as adhesives or sealants.

These anaerobic preparations generally contain peroxy initiators and/or benzosulfonimides (saccharin) as activators. A typical example of such an iJ product is U.S. Patent A 2,895,950 (July 21, 1959, V
, Kr1eble), 43775385 (19
November 27, 1973.

M-Ozono et al.), 165957561 (May 18, 1976, MoM-5koultchi), 16
4054480 (October 18, 1977, ljM,
5koultahi et al.) and A4038475 (197
July 26th, 2017.

J. Frauenglass). Activating side systems of the type disclosed in prior patents are separate components that are simply incorporated into acrylate or methacrylate based anaerobic preparations to provide the necessary free radical source for polymerization.

Therefore, there is a need for monomeric activators that can be copolymerized directly into the backbone of acrylate or methacrylate anaerobic monomers.

(&) at least one polymerizable acrylate or methacrylate monomer; (b) a free radical initiator in a concentration sufficient to initiate cure upon removal of oxygen; (C) a compound having the general formula: R is a hydrogen atom or a methyl group, and W is an alkyl group, an aryl group, or a substituted aryl group. The composition comprises a typical acrylate or methacrylate or mixture thereof, a free radical initiator, a polymerizable activator, and preferably (
(but not essential) small amounts of acidic monomers such as acrylic acid, methacrylic acid and/or citraconic acid, itaconic acid and maleic acid or their anhydrides as stabilizers, chelating agents and/or auxiliary promoters, as well as the customary Prepared in conventional manner with other additives. They are,
Improved performance properties (i.e. superior strength) when cured
Useful as adhesives and sealants. Also,
By incorporating the activator into the polymer backbone rather than leaving it free in the anaerobic formulation, corrosive effects are minimized when the adhesive is coated on metal surfaces.

Preparation of Monomeric Disulfonimide Activators Monomeric disulfonimide activators are made by a multi-step reaction. In the first step, the phenyl alkyl halide is reacted with excess halosulfonic acid, and the resulting product is then reacted with ammonia to form the sulfonamide. The latter two reactions are known and can be used in any conventional way and/or
Reactants can also be used. The resulting sulfonamide is then reacted with an alkyl or aryl sulfonyl chloride followed by acidification to form the shierodisulfonimide. Any alkyl or arylsulfonyl chloride can be used, but those that are commonly available and therefore preferred from a practical standpoint are methanesulfonyl chloride, ethanesulfonyl chloride, inglovirsulfonyl chloride, butanesulfonyl chloride, benzosulfonyl chloride, p-toluene. Examples include sulfonyl chloride and 2-mesitylenesulfonyl chloride. The halodisulfonimide intermediate is then subjected to a dehydrohalogenation reaction to form the monomeric disulfonimide.

Preparation of Anaerobic Compositions The monomers used in the present invention are commonly known anaerobically curable monomers having at least one polymerizable acrylate ester group.

The first class of monomers useful herein corresponds to the general formula. Here "C"'R5 is H, CH3, C2H5, 0H2
0H or cH2-oc(=o)-c(R')=ca2
．． R' is H, C#, CH3 or C2H51R7 is H,
OH, ・nu is OC, (=O)-0(R6)=CH2teashi, m is 1-. 8, preferably 1 to 4, nj-
i1-20. p is 0-1.

Typical monomers of this class include, for example, ethylene glycol dimethyl acrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate,
Included are tetraethylene glycol dimethacrylate, diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, and other polyester diacrylates and dimethacrylates. Monomers of the above class are described in US Patent A'3
043820 (July 10, 1962, R, H6Kr
1eble) described in the specification.

A second class of monomers useful herein corresponds to the general formula 0. Kokote R5 is H, CJ, C13 or C2H
5゜R6 is C-C alkylene, R' ti (OH2)
T.

HHHHcH3 ~8.

Typical examples of this class of monomers include dimethyl acrylate of bis(ethylene glycol) acylate, bis(ethylene glycol) acylate,
ethylene glycol) sebacate dimethacrylate,
Examples include dimethacrylate of bis(ethylene glycol) phthalate, dimethacrylate of bis(tetraethylene glycol) maleate, and diacrylates and α-chloroacrylates corresponding to these dimethacrylates. Monomers of the above class are described in US Patent A3457
212 (July 22, 1969, Y, Fukuoka
et al.) stated in the specification.

A third class of monomers useful herein can be characterized as acrylate terminated polyurethanes and polyureids or polyureas. Incyanate-hydroxyacrylate or incyanate-aminoacrylate reaction product. These monomers correspond to the general formula. Here, X is O or N (R5), R5
is H or a C4-C7 alkyl group, A is an organic residue of an acrylate ester containing active hydrogen, provided that the active hydrogen is removed, and the ester is substituted with hydroxy or amino at its alkyl moiety. Oshi and its methyl, ethyl and chlorine congeners. B is alkyl, alkylene, alkenyl, alkenylene, cycloalkyl, Schiff alkylene, aryl, arylene, 7ralkyl, acylkylene, alkaryl, acylkylene, poly(oxyalkylene), poly(carboalkoxyalkylene), and heterocyclic residue (which may be substituted or unsubstituted). n is 1-6.

Typical of this group of monomers are, for example, the reaction products of mono- or polyisocyanates (e.g. toluene diisocyanate or methylene bis-phenyl diincyanate) with acrylate esters containing hydroxyl or amino groups in the non-acrylate moiety (e.g. hydroxyethyl methacrylate). It is. This class of monomers is disclosed in U.S. Pat.
J, W-Gorman et al.).

A fourth class of monomers useful in the present invention corresponds to acrylate diesters of and suitenol type compounds. These monomers correspond to the general formula. Here, R8 is OH3
, C, R5, C0OH, or H, R is H, (j(
3 or C2H5, R is H, CH3 or OH, R11 is H, cI! , OH3 or C2H5, n
is 0-8.

Examples of this type of hexamer include dimethacrylate and diacrylate esters of 4,41-bishydroxy-ethoxy-bisphenol A, and dimethacrylate and diacrylate esters of bisphenols. These monomers are
-1.5640 (1970, K, 0rits, M,
Natsume and N, ShimadI! L) K is listed.

The fifth class of 7-mers includes -functional acrylate and methacrylate esters and their hydroxy, amide,
Consists of cyano, chloro, and silane substituted derivatives. Examples of such seven polymers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hydroxyethyl methacrylate, hydroxyglobyl acrylate, hydroxyl 7° lobyl methacrylate, butyl acrylate, n-octyl acrylate, and 2-ethyl acrylate. Xyl acrylate, decyl methacrylate, dotesyl methacrylate, cyclohexyl methacrylate, t-butyl methacrylate, acrylamide, N-methylol acrylamide, diacetone acrylamide, N-t-butylacrylamide, N
-t-octylacrylamide, N-butyloxyacrylamide, γ-methacryloxyglobyltrimethoxysilane, 2-cyanoethyl acrylate, 3-cyanopropyl acrylate, tetrahydrofurfuryl chloroacrylate, glycidyl acrylate, and glycidyl methacrylate.

The monomers useful in this invention have a common unifying characteristic:
or an anaerobically curable monomer having two or more polymerizable acrylate or substituted acrylate ester groups. Preferred monomers are monomers of the first to fifth classes mentioned above.

In the production of anaerobic curable adhesive compositions characterized by an unusually high adhesive strength of the resulting cured polymer, the particular monomers used may contain substituted alcohols, carboxyl or other relatively Can be chosen to contain polar groups. Examples of such polar groups include hydroxyl and carboxyl groups, as well as amino, amido, cyano, mercapto, and halogen polar groups. Monomers containing hydroxyl groups and/or labile hydrogen atoms are preferred.

Examples of suitable monomers include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, diacetone acrylamide, 2-cyanoethyl acrylate, 2-chloroethyl acrylate, 2-hydroxy-3-chloroglupyr methacrylate, ( Meta)
Mention may be made of acrylic acid, itaconic acid, citraconic acid and maleic acid. Hydroxy-containing monomers range from 5 to 95%
Preferably used in an amount of 25-50%, carboxyl-containing monomer FiO, 1-15%, preferably 0.5-1
Used in an amount of 0%. Both percentages herein are based on the total composition weight.

For best results in terms of adhesive activity, the monomers are preferably used in purified form.

However, the monomers may also be of commercial grade in which inhibitors, stabilizers, other additives or impurities may be present. However, if the activity and/or stability of the adhesive is unacceptably reduced, it will not pore.

In the production of the anaerobic curable composition in the present invention,
Mixtures of acrylate ester monomers can be used. In combination therewith, other non-acrylic ethylenically unsaturated copolymerizable comonomers such as unsaturated hydrocarbons, unsaturated esters and ethers, and vinyl esters can also be used. Typical optional comonomers include vinyl acetate, methyl vinyl ether, methyl vinyl ketone, poly(ethylene maleate), allyl alcohol, allyl acetate, 1-octene, and styrene. Preferably, the total of the optional non-acrylic yarn threads does not exceed about 50% by weight of the monomer composition, and most preferably does not exceed about 60%.

The anaerobic compositions of the present invention are made using conventional methods. Useful free radical initiators include hydrogen peroxide, peroxy compounds such as organic hydroperoxides (such as cumene, t-butyl and methyl ethyl ketone hydroperoxides) -oxides (such as benzoyl, cyclohexyl and hydroxyl hexyl peroxides). ),
and peresters (such as #it-butylhachenzoate and t-butyl peracetate); diazosulfones; α-aminosulfones (e.g. N-(o- or p-carboethoxyphenyl)-(p-tolylsulfonemethyl)amine ); or an azo compound (for example, 2,2'-azobis-(isobutyronitrile)).

Alternatively, an anaerobic system can be created in which the necessary active oxygen is generated in situ without the need for a peroxy initiator.

The activators disclosed herein are added to the anaerobic preparations in conventional amounts, ie, on the order of 0.01 to 12% (dry) of the total composition weight. Although monomeric disulfonimides give best results when used as the only activator in the anaerobic preparation, it is also within the scope of the present invention to additionally add known activators such as saccharins and sulfonamides of the prior art. to go into.

In order to improve the storage stability of the composition, it is preferable (but not essential) that the composition contains stabilizers such as free radical polymerization inhibitors. Suitable inhibitors include the customary ones such as hydroquinone, benzoquinone, naphthoquinone, pt-butylcatechol, phenothiazines and sterically hindered phenols. Inhibitor Q used
i depends, for example, on the type of monomer used and on the free radical initiator used.

Generally it is 0.0001 to 0.1 for seven months
% by weight, preferably in the range JO025-0.05%. The monomers will normally be obtained with an amount of inhibitor therein, but additional inhibitor can be added if necessary to increase the amount to the required level. If the monomers are to be exposed to elevated temperatures, the required amount of inhibitor must be present before heating the mixture.

The presence of a chelator is also preferred, but not essential, and provides better stability to the composition. A chelator is defined in the present invention as a compound that can be complexed with a metal to form a heterocycle due to the coordination bond between the metal and the ligand atom of the chelator. Although many chelating agents are suitable, preferred chelators are oxalic acid and
Compounds with a combination of oxygen and nitrogen ligand atoms such as hydroxyquinoline and β-aminocarboxylates such as ethylenediaminetetraacetate (N, 41
CDTA).

Generally, chelators useful in the present invention are preferably soluble in the monomer.

An example of a type of chelator that cannot be useful in the present invention is one in which all the ligand atoms are nitrogen atoms, such as dipyridyl (see US Pat. No. 4,058,475, July 26, 1977, JFreunglass et al.).

The amount of chelator used depends primarily on the type of chelator, but also to some extent on the amounts and types of other ingredients in the composition. Depending on the particular chelator added, Jo 001% to 0.00% of the total weight of the composition.
An amount of 1% can be used. It must be noted that in order to obtain adhesives with good properties, the amount of chelators should not exceed about 0.01% by weight. When more of these chelators are added than this limit, the adhesive strength of the adhesive decreases rapidly. Those skilled in the art will readily find out which chelators and in what amounts to add for best results. The lower limit for the chelator is determined by the minimum stability desired in the composition. The preferred range of the chelator is [1001 to 0.02
Weight%.

Because the initiators, inhibitors, and chelators used in the present invention are generally highly soluble in the acrylate- and methacrylate-based monomers, it is usually necessary to use a solvent or diluent to create a satisfactory anaerobic composition. do not have. However, if the presence of a solvent is desired, any solvent or diluent that dissolves the initiators, inhibitors, and chelators, as well as any promoters (which may be present and which are soluble in the monomers) may be used. Common solvents are described in the literature and include alkanols such as methanol, ethanol and butanol, ketones, substituted and unsubstituted formamides such as formamide, N,N-dimethylformamide and polyester diluents.

In preparing the novel anaerobically curable compositions of the present invention, it is also desirable to use conventional antioxidants to further extend the shelf life of the compositions.

In particular, sterically hindered phenols such as butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), or 10NOX 220 (5he11)
, 5ANTONOX R (Mon5anto), Engineering R
GANOX 1010 and RGANOX 1076
(C1ba-Ge1g7) (all trademarks) is preferably added.

The compositions of the invention also contain organic acids, preferably organic monocarboxylic acids, such as benzoic acid, p
- Toluic acid or 7-tyl acetic acid or their corresponding anhydrides Kanakura Miru.

Anhydrides of dibasic aromatic acids such as phthalic acid or terephthalic acid may also be used. Aliphatic acids are generally less satisfactory as promoters for the compositions when the compositions are used on many non-ferrous metal surfaces. However, these acids have some utility when the composition is used on ferrous metals, and can also be conveniently used in combination with aromatic acids to bond non-ferrous surfaces.

Plasticizers such as dibutyl or dioctyl phthalate, triethylene glycol, or polyethylene glycol dilaurate may be present in the composition. Adhesive trees such as styrene/α-methylstyrene copolymer (H
Kr1stalex (Trademark) from Ercules, Inc., and inorganic thickeners are usually not required but can be included if desired. Other optional ingredients include adhesives, cut glass fibers and visible or ultraviolet fluorescent dyes and/or
Or a fluorescent agent can be mentioned. Dyes serve to enhance the visibility of otherwise colorless or very light colored compositions so that treated surfaces can be easily distinguished from untreated surfaces. Typical dyes include anthraquinone dyes such as 1,4-dimonomethylaminoanthraquinone. Dyes containing unsubstituted hydroxyl groups or unsubstituted amino groups exhibit the effect of significantly inhibiting polymerization of the composition and should generally be avoided.

Depending on the particular ingredients and the temperature and time allowed for heating and/or agitation, the compositions of the present invention may remain for many months at room temperature before actual use without evidence of gelation. Can be stored for years. It is necessary that a suitable amount of air or oxygen be present, which can be achieved by introducing a small amount of air into a suitably shaped container, preferably made of polyethylene or a similar material that is permeable to air. It is easily given. However, when the air is excluded by displacement between adjacent surfaces, the composition quickly polymerizes to form a strong bond. This polymerization can be further accelerated by increasing the temperature. However, the use of elevated temperatures is not necessary as the composition creates a strong bond within minutes.

Anaerobic polymerization of the compositions of the present invention is facilitated by metal surfaces comprising iron, mild steel, cadmium, cobalt, and manganese. Other metals, including aluminum and zinc, have relatively low catalytic activity. Non-metallic surfaces such as glass do not catalyze polymerization. In the adhesion of surfaces with low catalytic activity, primers such as aldehyde-amine condensates (eg US Pat. No. 3,616,040).

It may be advantageous to use derivatives of catalytic metals such as ferric chloride, cobalt nathanate or manganese resinate.

The following examples further illustrate embodiments of the invention. In the examples, all parts and percentages are by weight and all temperatures are in degrees Celsius, unless otherwise noted.

Determination of storage stability (gel time) in which the following test procedure was used in the Examples A 5 cc sample of the composition was placed in a test tube, which was then injected into 82 t.
Place in a bath heated to 11' for a minimum of 30 minutes.

As an approximate correlation between heat aging and room temperature aging, samples that are still free of gelation after aging for 24 hours or more are considered stable at ambient temperature in the presence of oxygen for at least about 1 year.

Breaking torque and average torque Measure the strength of the bond of the threaded mass as follows: Approximately 2-3 drops of each composition are applied to a separate % x 24 mild steel class 1 mating bolt (degreased). ), then immediately place the dowel-threaded nut (
(degreased) onto the bolt so that the nut is directly within the area of the thread where the composition has been applied.

The sealant is allowed to set and cure for a specified period of time, usually 0.5.1 or 24 hours, at room temperature, and the strength of the bond formed between the nut and bolt is then measured. The breaking torque of the bond is the amount of torque required by the wrench to initially move the nut on the thread. The average torque for gluing is % rotation, % rotation, % rotation and 1
It is the average value of the torque required by the wrench to rotate. On the market, average torque 67 after 24 hours curing
cm, kg (12 inch-bond) is considered satisfactory.

Measurement of Tear Shear and Impact Strength These strength properties of adhesives are determined according to ASTM Standard
dMethod of Te5t Designi
on D 950-72 (1973) (for impact strength) and D 1002-72 (f973) (for tear shear strength).

Example 1 This example describes the preparation of N-mesyl-4-vinylbenzenesulfonamide, one of the polymerizable activators useful in the anaerobic preparations of the present invention.

A 2J multi-necked round bottom flask equipped with a mechanical stirrer (equipped with a glass stirring bar and a Tear 07M blade), a reflux condenser, an isobaric addition funnel, and a thermometer is placed under a flow of argon.

The system exits a trap containing a 50% sodium hydroxide solution. Put 6254.9 (j4 moles) of chlorosulfonic acid in a flask, and add 20011 (1,
0.8 mol) of phenylethyl bromide is added dropwise at a rate of 15° C. to keep the reaction temperature below 27 p.m. with external ice-water bath cooling. After the addition is complete, the mixture is stirred for an additional hour and then carefully poured onto a large amount of ice to precipitate the crude sulfonyl chloride. Decant the lot on ice and convert the product to about 12 ml of Toluev (fcfjm 4-(2-bromoethyl)).
This solution of benzenesulfonyl chloride is dried over anhydrous 1M magnesium acid, filtered and used without further purification.

32 multi-neck round bottom flasks with equipment as described above,
Maintain argon pressure above atmospheric pressure. 7 Last:y
A toluene solution of di'4-(2-bromoethyl)henzenesulfonic acid chloride is charged, cooled in an ice-water bath, and 200 rILl of 58% ammonium hydroxide is added dropwise. After the addition was complete, the mixture was cooled to room temperature, the crude sulfonamide was collected, and dried in a planner funnel to give 2641
1 (1 mole, 93% based on phenylethyl bromite)
) (7) 4-(2-bromoethyl)benzenesulfonamide is obtained, which is used without further purification.

500 with a mechanical stirrer, a thermometer, a glass electrode connected to a suitable voice meter and two 601 isobaric addition funnels.
200 g of distilled water and 40 g of distilled water in 1 multi-necked round bottom flask
I! (0.15 mol) of crude 4-(2-bromoethyl)benzenesulfonamide is added. Slurry in an ice water bath
Cool to 15C and add a sufficient amount of 2 from one of the addition funnels.
Add 5% sodium hydroxide to make a voice of 12-12.5. From the second addition funnel, 4411 (I], sab moles) of methanesulfonyl chloride was added dropwise at a rate such that the temperature of the slurry was maintained at 10-15C, and simultaneously 25
% hydroxide) and maintain at around 12-12.5. After the addition of methanesulfonyl chloride was completed, the slurry was stirred at 10"r (pH 1'2) for 0.5 hours,
Bring to room temperature and make slightly acidic (pH > 5) with concentrated hydrochloric acid. At this point, any unreacted starting material is filtered and the filtrate is cooled to ioc in an ice-water bath. With vigorous stirring, add the r solution to concentrated hydrochloric acid. The crude product was collected in a planner funnel and dried overnight in a vacuum open at 50C to give N-mesyl-4(2-bromoethyl)benzenesulfonamide 4.
09 (0-12 mol, 80% yield based on 4-(2-bromoethyl)benzenesulfonamide) is obtained.

500 equipped with reflux condenser, thermometer and mechanical stirring device
120 g (0.35 mol) of crude N-mesyl-4(2-bromoethyl)benzenesulfonamide, 112.8 ml (0.70 mol) of 2
Charge 5% sodium hydroxide and 150 d of distilled water.

The solution was heated to 7QC for 0.75 h and then heated in an ice water bath for approximately 10'
C. and then made highly acidic with concentrated hydrochloric acid. The resulting mixture was stirred for 1 hour and the precipitated product was collected by filtration. The crude product N-mesyl-4-vinylbenzenesulfonamide 7B& (0,50 mol) was dissolved in warm toluene (approx. 0.17 mol, 50%) of pure monomer are obtained. It has a melting point of 98-100C and 259.9
It has a neutralization equivalent of 2 (theoretical value 261). The elemental analysis and calculated composition values of c, Hl, and No4s2 are too small as shown below.

Analysis 41,084,415,1923.47 Calculated value 4
1j8 4.21 5,36 24.52 Example 2 This example describes the use of the monomeric activator of Example 1 to make an anaerobic adhesive formulation. Adhesives are evaluated according to the test procedure previously described. Add 82.4 parts of tetraethylene glycol dimethacrylate and 15.0 parts of hydroxyethyl methacrylate to a 500i high density polyethylene beaker with stirring. The temperature is 75
It will be raised to ~aoC. The mixture was kept at this temperature for 2 hours and then dissolved in methanol-water (5% solution) (1≠
Diaminetetramine tetraacetate (Na4EDTA
) of 100 ppm f. Reduce the temperature to 60-65C and add 2.1 parts of N-mesyl-4-vinylbenzenesulfonamide.

The mixture is held for 1 hour and 0.54 parts of N,N-dimethyltoluidine are added slowly in 0.2 parts every 50 minutes. After the addition is complete, the mixture is held overnight. Then add 3 parts of cumene hydroperoxide. The resulting anaerobic adhesive preparation was cooled to room temperature and 5oO+a7! Place in a polyethylene bottle.

The test results are as below.

60 minutes 24 hours Breaking torque N-m (inch bond) 2.285
(25) 6.554 (58) Average torque N8
m (inch pound) 14272 (144) 2B
, 250 (250) gel time > 70 minutes Example 6 Using the same procedure as Example 2, other anaerobic preparations were made using the ingredients and amounts shown in Table 1.

The test results are shown in Table 2.

Procedural amendment January 1980/Ototsu Day

Claims (1)

Claims: 1. (a) at least one polymerizable acrylate or methacrylate monomer; (b) a free radical initiator in a concentration sufficient to initiate cure upon removal of oxygen; (c) Polymerization containing monomeric disulfonimide having the general formula ▲ Numerical formulas, chemical formulas, tables, etc. An anaerobic composition containing a moisturizing activator. 2. A composition according to claim 1, wherein the monomeric disulfonimide is present in an amount of 0.01 to 12% by weight (dry basis) relative to the total weight of the composition. 3. The composition of claim 1 further comprising free radical polymerization stabilizers, auxiliary promoters for free radical polymerization, chelating agents, and mixtures thereof. 4. Polymerizable acrylate or methacrylate monomer has the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R^5 is H, CH_3, C_2H_5 or CH
_2OC(=O)C(R^6)=CH_2, and R^
6 is H, Cl, CH_3 or C_2H_5, R^
7 is H, OH or OC(=O)C(R^6)=CH_2
, m is an integer of 1 to 8, n is an integer of 1 to 20, and p is 0 or 1. 2. The composition according to claim 1, which is a polyfunctional acrylate or methacrylate having the following properties. 5. The polymerizable acrylate or methacrylate monomer has the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, , A is the organic residue of an acrylate ester containing active hydrogen, provided that the active hydrogen has been removed, the ester is hydroxy- or amino-substituted at its alkyl moiety, and its methyl, ethyl, and chlorine congeners. Yes, B is alkyl, alkylene, alkenyl, alkenylene, cycloalkyl, cycloalkylene, aryl, arylene, aralkyl, aralkylene, alkaryl, alkaryl, poly(oxyalkylene), poly(carboalkoxyalkylene), and heterocyclic residue monovalent or polyvalent organic residues selected from the group consisting of groups (which may be substituted or unsubstituted), where n is from 1 to 6. Composition of. 6. The composition according to claim 1, wherein R' of the polymerizable activator is a C_1 to C_4 alkyl group. 7. The composition according to claim 1, wherein R' of the polymerizable activator is a benzene or toluene residue. 8. The composition according to claim 1, wherein R of the polymerizable activator is a hydrogen atom, and R' is a methyl group or a benzene residue. 9. The composition of claim 1, further comprising acrylic acid and/or methacrylic acid in an amount of about 0.5 to 10% by weight relative to the total composition weight.