JPS612719A - Elastomer curable composition and manufacture - 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 This invention relates to polymeric materials, and more particularly to repolymerized compositions which are normally liquid in the uncured state and which, upon polymerization, form highly flexible rubber-like polymers or elastomers. .

Depending on the precise formulation, substances of this type are mainly used as sealing compounds, packing compounds or adhesives.

Rubber-like elasticity is in many respects a unique phenomenon with physical properties that are significantly different from low molecular weight solids, liquids, or gases. Typically, rubber-like materials or elastomers exhibit the following physical properties:

(5) (a) Rapid and significant elongation in tension (achieving high elongation with less attenuation, i.e. energy loss as heat).

(bl High tensile strength and high modulus (stiffness) when fully stretched.

(c) Immediate shrinkage (showing a snapping or repulsion phenomenon). and (dl) completely postgenic upon stress relief (showing resilience and low permanent elongation phenomena).

Regarding this, please refer to F.W. Billmeyer (p, W, Billme, published by John Willy & Son).
yer), Polymer Science Textbook (Textbook)
of PolymerScience) 2nd edition, 19
Please refer to 1 for 1.

Rubber-like materials or elastomers are characterized at the molecular level by the following properties:

f5) (a) Medium to high polymer material.

tb) be higher than its glass transition temperature (To);

(c) Be in a stable (stress-free) state and be amorphous.

and (d) having a crosslinked network that suppresses the total mobility of the chain.

A common characteristic of elastomers is the presence of medium to long polymer chains. These chains are usually interconnected by cross-linking bonds, each consisting of a large number of single bonds, and consisting mainly of one polymer chain interposed between each cross-linking point.

A method of introducing a cross-bond network into a polymeric material to obtain rubber-like elasticity is known as vulcanization.
ion) It is called J. However, "vulcanization" and "curing" are different from "crosslinking".
linking) Sometimes used synonymously with J.

Vulcanization creates a dispersive network of strong primary bonds in the polymeric material with many relatively weak "fixpoints".
ints ) J is given, long-range movement of polymer molecules is suppressed while maintaining local mobility in segment units.

Vulcanization, in a sense, can be thought of as a chemical modification that reduces the flow of a polymeric substance and increases its tensile strength and elasticity while retaining its extensibility.

Generally, most rubber-based materials are prepared in two steps: a first step to prepare a medium to long chain polymeric material, and a second step to convert the polymeric material into a finished product.

Vulcanization occurs in a second step, in which the polymeric material is treated at high temperatures or pressures in the presence of sulfur, oxidizing agents, or free radical generators.

Conventional elastomer curability (cure-1o-elaH
The disadvantage of repolymerized materials is that they must be converted into rubber-based products in processing equipment dedicated to vulcanization.

Elastomeric curable polymerizable materials based on monocomponent polysiloxane cloth copolymers have advantages over conventional rubber-based materials, for example in that they can be cured even in the presence of atmospheric moisture. However, it is a little thick and difficult to apply, and it takes quite a long time to cure, so even after it cures,
Exhibits only moderate elasticity and flexibility.

Accordingly, it is a primary object of the present invention to provide new and improved elastomeric curable repolymerization compositions that overcome the above and other disadvantages associated with prior art materials.

A second object of the present invention is to provide an improved nidistomer-curable polymerizable composition that has a long pot life, is easy to apply, and is vulcanizable in situ.

A sixth object of the invention is that the vulcanized product exhibits excellent elasticity and flexibility at low (room) or moderate temperatures (e.g. 10
The object of the present invention is to provide a single-component elastomeric curable polymerizable composition that can be vulcanized at temperatures (0°C).

Generally speaking, the above and other purposes are: medium- to long-chain complex di- or polyfunctional prepolymers having vinyl-reactive end groups;
) a crosslinking control substance that can be dissolved in or mixed with this;
and tQ a) by an elastomeric curable composition consisting of a repolymerization composition comprised of a li-based polymerized initiator.

The repolymerized composition according to the invention can be rapidly cured at room or moderate temperatures to produce rubber-based materials with high flexibility and moderate tensile strength.

Next, the present invention will be described in detail with reference to experimental examples.

In this specification, the terms "low-temperature vulcanization" and "room-temperature vulcanization" are used to convert a normally liquid material or sol polymer material into a high molecular weight solid having an appropriate crosslinking density under ambient temperature conditions. Refers to the process of curing polymeric materials to give them rubber-like properties, or "rubber-like elasticity."

The elastomeric curable compositions according to the present invention can be considered as polymerizable, flexible, monocomponent block copolymers with wide crosslink spacing, ie, low crosslink density structures.

This low crosslinking density structure combines monofunctional monotonic units with flexible medium- to long-chain complex di- or polyfunctional prepolymers (such as acrylate, methacrylate or allyl functionality).
Neglecting cross-linking by copolymerizing vinyl copolymer chains with cross-links connecting the flexible prepolymer segments (which are "capped" with vinyl-reactive end groups). By introducing a motor pathway that allows monomeric substances to bind one-to-one,
achieved.

The vinyl copolymer thus formed consists of flexible prepolymer cross-linked units spaced sufficiently apart such that external stress causes the vinyl copolymer cross-section to deflect and transmit external strain to the flexible prepolymer cross-section. have.

Polymerizing only a flexible prepolymer without monofunctional monomers results in a product that has some flexibility but shatters when bent.

This is a kind of "cheese" in that, in the absence of monofunctional monomers, the polymerization of the reactive vinyl end groups of the prepolymer creates a tightly cross-linked vinyl polymer backbone. .

This spine-shaped vinyl polymer is substantially fully elongated, with flexible segments extending from the spine adjacent to each other (like teeth extending toward the back of a comb at any angle).
As a result, it is quite rigid due to its 3D density.

Even when external stress is applied to this ridge structure, most of the strain is captured by the vinyl polymer backbone, and only a small amount is absorbed by the flexible cross-linked prepolymer segments. It is.

As a result, the rigid segment breaks and the strain is transferred in an avalanche to another already strained rigid segment, which the flexible segment cannot absorb.

Since the other rigid segments are already strained, the added strain of the failed segment will result in catastrophic failure.

Furthermore, structures with the desired reduced crosslink density can be achieved by using allyl monofunctional monomers or allyl "capped flexible prepolymers.

Allyl groups have the property of copolymerizing (with acrylic or methacrylic esters) and undergoing some degree of random chain transfer and disproportionation.

This random chain transfer reaction and disproportionation increase the distance between the crosslinking points to some extent, so that the allyl-capped bifunctional flexible sol polymer and the methacrylate ester,
Alternatively, a compound blend with an acrylic ester capped trifunctional or multifunctional flexible prepolymer can be optimized to obtain the best elongation and strength properties of the cured product.

In yet another embodiment of the invention, when a difunctional mercaptan chain transfer (i.e., radical chain transfer)-binding agent is used with a dimercaptan ester, such as, for example, the dimercaptoacetic ester of polyethylene diol, the difunctional mercaptan chain transfer (i.e., radical chain transfer)-binding agent is combined with a methacrylic acid ester or an acrylic acid ester. By using the admixture with an ester "capped" prepolymer, the length of the polymerization chain can be shortened while at the same time reducing the
, 2-molecular polymer segments are combined.

In this way, the distance between the cross-linking points increases and the rigid short sections of the flexible sol polymer segment are bonded, thereby increasing the amount of external strain transferred to the flexible sol polymer segment.

This method yielded a low strength elastomer exhibiting an elongation of 1600% or more at break.

The nidistomer curable composition of the present invention reacts with (1) a medium- to long-chain flexible prepolymer as described above, (2) a medium- to long-chain difunctional or polyfunctional prepolymer, and ( ii) a crosslinking control substance that is soluble or miscible therein, and (C) a free radical polymerization initiator system.

The crosslinking control substance preferably consists of one monofunctional short chain monomer or a mixture of such monomers or polymeric chain transfer and binding agents.

Heart-shaped prepolymer (A to long chain-shaped prepolymer) The medium to long chain-shaped prepolymer used in the present invention is preferably prepared by reacting a polyether diol or a polyester diol with a diisocyanate ester, and product and
Formed by reaction with repolymerized acrylic esters, methacrylic esters, or allyl alcohol. +
It consists of OIJ ether-urethane or polyester-urethane derivatives.

Suitable polyester diols include Desmodure J (trade name) 1700 (
Mobay Chemical Company (Mobay Chemical 5)
) (a) Corporation ) 'R).

This polyester diol is derived from a reaction between diethylene glycol and adipic acid (hexanediolic acid).

Another suitable polyester diol is Inolex J (m mark) 1400-120 (
Inolex Company
), which is a derivative obtained by the reaction of neopentyl glycol and 1.6 hexanonol with adipic acid.

Other useful polyester diols are formed by the reaction of glycols having at least 2 carbon atoms with dicarboxylic acids having 6 or more carbon atoms, such as poly1,4-butanediol adipic acid. be done.

Although there are other low molecular weight diisocyanate esters having the following general formula, the preferred one is toluene diisocyanate (TDI).

CI1 formula (0-C-N)2R (wherein, R is a C2 to C20 alkylene group, alkynylene group, or cycloalkylene group, or a C0 to C40 allyl group, alkaryl group, or aralkyl group). ) The reaction ratio of equivalent amounts of polyester diol and diisocyanate/acid ester is generally such that the diisocyanate/acid ester has an isone group equivalent of about 17 to 22, while the hydroxyl group equivalent of the polyester diol is about 10. There must be.

A preferred reaction ratio is 20 (isoan equivalents of the diisocyanate ester) to 10 (hydroxyl equivalents of the polyether diol), which provides a highly flexible and isocyanate-terminated chemical structure. A final composition having the following properties is obtained.

The isocyanate-terminated polyester prepolymer product described above is then reacted with an acrylic or methacrylic ester monomer containing hydroxyl groups to end-cap with acrylic groups or reacted with allyl alcohol, Cap the end with an allyl group.

A useful range for the hydroxyl equivalent weight of the ester or alcohol monomer is about 0.9 to 3.0, preferably 18 to 2.0.
2, optimally 2.0 (relative to the isocyan equivalent of the prepolymer, 20).

The flexible acrylic acid or methacrylic acid ester monomers and reactive vinyl alcohols such as allyl alcohol that cap the Siison anoic acid polyester reaction product may be either monofunctional or difunctional; Polymeric monomers are preferred.

These most effective monofunctional monomers are selected from the group consisting of hydroxyalkyl acrylates, hydroxyalkyl methacrylates, aminoalkyl acrylates, aminoalkyl methacrylates, and allyl alcohols.

The most preferred are hydroxyethyl methacrylate and hydroxypropyl methacrylate, but others that may be useful are represented by the following formula.

(II) Formula % Formula % (wherein, selected from the group consisting of chlorine, methyl and ethyl groups, and R2 is a divalent organic group selected from the group consisting of low molecular weight alkylene groups having 1 to 8 carbon atoms, phenylene groups and naphthylene groups; ) The most preferred allyl alcohol is pro-nyl alcohol, but other useful allyl alcohols are represented by the formula:

R2C= CCH2(X) p (R2) p O
H (wherein X, R' and R2 are as shown above, and P is 0 or 1) Suitable substances containing a hydroxyl group or an amine group include hydroxyethyl acrylate, hydroxyethyl methacrylate, / ethyl, aminoethyl methacrylate, 2-hydroxyzolopyl methacrylate, hydroxypropyl methacrylate,
Aminozolopyl methacrylate, hydroxyhexyl acrylate, t-butylaminoethyl methacrylate, hydroxyoctyl methacrylate, monoacrylic acid or monomethacrylate ester of bisphenol-A, fully hydroxylated derivative of bisphenol-A, cyclohexyldiol, and methacrylated polyethylene glycol.

End-capping reactions can be performed with or without diluent.

Diluents containing hydrocarbons such as aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and aromatic hydrocarbons (e.g., benzene, toluene, cyclohexane, hexane, heptane, etc.) can be used, but methyl isobutyl ketone, Other diluents such as cyamyl ketone, isobutyl methacrylate, and cyclohexyl methacrylate can also be used with advantage.

Other beneficial diluents are represented by the formula:

(I) Formula (wherein R7 is H, a C4 to C4 alkyl group or a hydroxyalkyl group, or FL60CH2-5R9 is a Hl...rogen group or a C1 to C4 alkyl group, R
"HlHlOHl or FL'O-1 几6 is CH2=
CR'C=0, m is an integer (preferably 1 to 8), k is an integer (preferably 1 to 9), and p is 0 or 1.

) or (IV) of the formula (wherein BIG is selected from the group consisting of hydrogen, chlorine, methyl and ethyl groups, and R'' is a small alkylene group having 1 to 8 carbon atoms; a divalent organic group selected from the group consisting of phenylene and naphthylene groups, W is a polyisocyan group, E is an aromatic heterocyclic ring structure, and Z is a polymerized or copolymerized methylene ether or (V) formula%) (wherein, X is -〇- or -R12N-1⇠I2 is H
or lower alkyl groups having 1 to 7 carbon atoms, A is CH,=CR", C0
゜0, -, B+3 is H or CH5, n is an integer from 2 to 6, B is polyvalent and substituted or unsubstituted,
Alkyl group, alkenyl group, cycloalkyl group, allyl group, aralkyl group, alkyloxyalkylene group, allyloxy-arylene group or heterocyclic group (%) (VI) Formula (CH22CR14,CO,O,R16,O, CO,N
H) “几15 (in the formula, R” is J CH3, C2H5 or C, B+5 is 1 to 4 chlorine atoms, or
1 to 6 amino groups or mo1, or diC1 to C1
alkylamino group, or a C2 to C20 alkylene group, alkynylene group, or cycloalkylene group, or a C6 to C40 allyl group, alkaryl group, aralkyl group, or alkyloxyalkyl group, which can be substituted with a C1 to C8 alkoxy group. , or a hydroxyallyl group, and R16 is (5) (a) a C+ to C8 hydroxyalkyl or aminoalkyl group, (b) a C+ to C0 alkylamino-C2 to C8 alkyl group, or (c) a hydroxyphenyl, aminophenyl, hydroxynaphthyl or haaminonaphthyl group which can be substituted with an alkyl, alkylamino or dialkylamino group having up to about 6 carbon atoms, which contains one or more hydrogen atoms; It is a group containing. ) The diluent optionally serves as the short chain monomer of the composition.

The most preferred diluent 1 monomers are hydroxyethyl methacrylate, hydroxyzolopylbisphenol-A monoacrylate methacrylate, and monomethacrylate ester of bisphenol-A.

The acrylic acid, methacrylic acid or allyl-terminated prepolymers used in the present invention can also be prepared by methods other than those described above.

For example, the desired prepolymer product can be produced by reacting a polyisocyanate with a suitable hydroxyacrylic acid or methacrylic ester and reacting the resulting product with a suitable polyester glycol or polyether glycol. .

Alternatively, carboxylic acid-terminated polyesters (e.g., by esterification with additional adipic acid)
[Desmodur J1] formed a carboxylic acid terminal group.
700) with glycidyl metaflurate or allyl glycidyl ether in the presence of triethylamine or a mixture of triethylamine and 2-methyl-imidazole to produce a methacrylic acid-terminated polyester resin having no urethane or urea ring structure. Can produce repolymers.

A suitable polyether diol for preparing polyether-urethane derivatives is "Polymeg".
J (trademark) 2000, (U.S. Quaker Oats Company (Q
ivaker 0ats Company) g)
It is.

This is a polyether with repeating units of 1,4 butylene oxide.

Other polyether-urethane derivatives can be prepared from commercially available polypropylene oxide diols, polypropylene oxide triols, polyethylene oxide diols, and a variety of other diols and triols.

Furthermore, the medium to long mirror image preform IJ according to the present invention is [Desmodule Ji7004! dimaleic acid half ester (MRM) of polydiethylene glycol adipate, formed by the reaction of J ester diol with maleic anhydride, and adipic acid, formed by the reaction of "Desmodur" 1700 polyester diol with methacrylic acid. It consists of a trifunctional monomer such as dimethacrylic acid ester of polydiethylene glycol (MARAM).

/ξ-t (B) Crosslink density control co-reactive monomer / ξ-t (A) medium to long continuous mirror image prepolymer unit's flexible prepolymer crosslinking points are provided with a necessary interval. The co-reactive monofunctional monomer used for this purpose is: (1) copolymerized with the reaction termination group of the prepolymer of It is a short chain mirror monomer that can be used.

Suitable co-reactive monomers have relatively high molecular weights and relatively low volatilities.

Suitable are allyl alcohol, alkyl alcohol, and monomethacrylic esters and monoacrylic esters of allyl alkyl alcohol, as well as glycidyl ethers or 1.2-functional poxyethyl substituted compounds, and acrylic acid, methacrylic acid, aminoalkylacrylic acid. allylamino methacrylic esters, alkylamino methacrylic esters, prepared by reaction with acid esters or aminoalkyl methacrylic esters;
There are allylalkylamino methacrylic esters, allylamino acrylic esters, alkylamino acrylic esters, and allylalkylamino acrylic esters.

The reaction of the alkyl glycidyl ether, allyl glycidyl ether, alkaryl glycidyl ether or 1,2-functional poxyethyl compound with acrylic acid or methacrylic acid is carried out using a suitable catalyst such as 2-methylimidazole or meriethyramine.

The aminoalkyl methacrylate and the aminoalkyl acrylate do not necessarily require a catalyst.

The reaction is preferably diluted at a controlled temperature to produce monomethacrylic acid or monoacrylic ester of fairly high purity such that the catalyst and trace by-products can be easily removed by water washing and vacuum stripping. It is done without drugs.

Among the above monomers, phenyl glycidyl ether, methacrylic acid, acrylic acid, methacrylic acid 6-
Phenoxy-2-hydroxypropyl or acrylic acid 3
- reaction products with phenoxy-2-hydroxyzolopyl, and with methacrylic acid and acrylic acid, para-tert-butylphenyl glycidyl ether, ortho-fresyl glycidyl ether, butyl glycidyl ether, and glycidyl ethers of hytecan and nectadecane. It is a reaction product with

Other co-reactive monomers that can be used in the present invention include methacrylic esters and acrylic esters derived from glycidyl ethers, as well as glycidyl methacrylate and glycidyl acrylate, and 2-ethylhexanoic acid with 2-methylimidazole. or glycerin 1-(2-ethyl)hexanoate-6-methacrylate, and 1-(2-ethyl)hexanoate-6, prepared by reacting with a suitable catalyst such as a trialkylamine.
- Mixed esters such as glyceryl acrylate.

Other acrylic and methacrylic mixed esters can be produced by the reaction of various carboxylic acids with glycidyl acrylate or glycidyl methacrylate or the reaction of aminoethyl esters with glycidyl methacrylate or glycidyl acrylate without a catalyst. It can be prepared by

Preferred secondary short chain mirror monofunctional co-reactive monomers that can be used in the present invention include 1-hydroxyethyl methacrylate, 1-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, or 2-hydroxypropyl acrylate. It is prepared by the reaction of hydroxypropyl with an isocyanate ester.

For example, by reacting the above acrylic ester or methacrylic ester with phenyl incyanate, a luphenylurethane corresponding to the methacrylic acid hydroxy ester or acrylic acid hydroxy ester can be produced.

A preferred monofunctional monomer prepared as described above is 2-methacryloxyethylphenyl urethane, produced by the reaction of 2-hydroxyethyl methacrylate with phenyl isocyanate, but other suitable Co-reactive monomers include methyl alcohol, ethyl alcohol, flobyl alcohol,

- Methyl alcohol, isobutyl alcohol or Vine R
1 equivalent (1 mol) of a lower alcohol such as ethyl alcohol, and 2 equivalents (1 mol) of 2.4 toluene diisocyanate.
2-isocyanato-4-urethane toluene monoisocyanate product.

The obtained monoisocyanate product is then reacted with 1 equivalent (1 mole) of hydroxyacrylate, hydroxymethacrylate, aminoalkyl acrylate, or aminoalkyl methacrylate to form the corresponding urethane acrylate. Produces ester or methacrylic acid urethane ester.

A suitable monofunctional monochamber is 4-methoxycarbonylamino-, which is the reaction product of methanol, 2-hydroxyethyl methacrylate, and toluene diisocyanate.
2-(2-methacryloxy)ethoxycarbonylamino-toluene, as well as yne, is the reaction product of methyl alcohol, 2-hydroxyethyl methacrylate, and toluene diisocyanate. 4-yne is methyloxycarponylamino-2-(2-methacryloxy)ethoxycarbonylaminotoluene.

These preferred vinyl monofunctional methacrylic acid or acrylic acid urethane esters provide the final composition with special wetting and adhesion properties and exhibit low volatility, as well as visibility medium to long run specular prepolymers. Increase the spacing between the cross-linking points of the segments.

Polymerized Chain Transfer Agents Polymerized chain transfer and binding agents that can be beneficially used in the present invention include:
It consists of a difunctional chain transfer/binding agent with a relatively short chain reactive end group that co-reacts with, dissolves in, or is miscible with the medium- to long-chain sol polymer (.ξ-A). ing.

Preferred are triethylene glycol dimercaptoacetate (METEG), formed by the reaction of triethylene glycol and mercaptoacetic acid, dimercaptozolopionic acid, the reaction product of triethylene glycol and mercaptopropionic acid. Triethylene glycol (MPTEG), and [Desmodur J170
Zyl 6-mercaptozolopionic acid ester (H8P) of polydiethylene glycol adipate, which is the reaction product of 0 polyester diol and mercaptozolopionic acid.
dimercaptoacetic esters and substituted mercaptocarboxylic esters of polyether glycols and polyester glycols, such as RPSH).

If desired, other mono- and difunctional polymeric chain transfer and coupling agents as described above, in admixture with one or more co-reactive monomers as described above, may be used to advantage as well.

As noted above, the co-reactive monomer and chain transfer/binding agent must be soluble in or miscible with the medium to long chain polymer.

The degree of solubility or miscibility can be quantified by blending the co-reacting monomer, chain transfer/binding agent, and medium to long chain mirror prepolymer and visual inspection of the degree of solubility or miscibility.

The physical properties of the resulting cured composition can be varied by selection of ingredients and adjustment of component ratios, ranging from highly extensible nidistomers to sticky, relatively hard solid polymers. .

As described above, the components are: (B) at least one medium- to long-chain bifunctional or polyfunctional vinyl pre-, +O+)mer; (B) at least one short-chain mirror monofunctional co-reactive. monomer, or at least one difunctional dimercaptan polymerization chain transfer and binding agent, and a tc+ free radical polymerization initiator.

Additionally, the properties of the polymer can be additionally modified by including other short chain difunctional or polyfunctional monomers, or mercaptans or other chain transfer/binding agents.

The molecular weight of the medium to long-chain acrylic or methacrylic terminated bifunctional pre-, +61J-mer is substantially higher than that of the monofunctional short-chain monomer, and is difunctional or monofunctional. In the absence of mercaptans or other polymerized chain transfer/binding agents, the resulting cured polymer, although flexible, is relatively brittle and exhibits very low burst strength under slight tension.

As the relative amount of monofunctional monomer (methacrylic or acrylic) is increased (up to the maximum amount determined experimentally), the burst strength, shoe and elongation at break increase.

As the proportion of allyl end groups, either as part of the prepolymer part or as monofunctional short chains, increases, the breaking strength at slight elongation increases much more rapidly than at increasing elongation.

As the amount of difunctional chain transfer/binding agent (e.g. mercaptoester of polyethylene glycol or polyester glycol) increases, the strength decreases relatively, but the elongation at break increases rapidly to 1600 degrees (typical (The stress-strain response of a standard comb has been demonstrated).

Typically, the short chain complex monomer or chain transfer/binding agent is present in the range from 50 mol% (1 unit of monofunctional monomer per unit of difunctional prepolymer) to about 98 mol% (1 unit of monofunctional monomer per unit of difunctional prepolymer). 50 units of monofunctional monomer per unit of prepolymer), preferably from about 91 molty (10 units of monofunctional monomer per unit of prepolymer) to 95 molty (20 units of monofunctional monomer per unit of prepolymer).
unit monomer).

Initiator Systems Initiator systems consist of organic peracids, organic hydrogen peroxides, and other free radical initiators.

This also includes substances such as organic peroxides or peresters that decompose to form free radicals, of which sochlorohexylhydroxycyclohexyl peroxide and t-butyl perbenzoate are examples. be.

Although the nature of the free radical initiator is not critical, suitable organic peroxides and hydroperoxides are represented by the following formula.

(■A) 弐几150OR15 and (VIIB) Formula RI500H where R15 contains up to about 18 carbon atoms,
A hydrocarbon group, a carbonyl group or a mixed group thereof,
Substituents are preferably alkyl, allyl, or aralkyl hydrocarbon groups containing about 6 to 12 carbon atoms, and which do not adversely affect the peroxide or hydroperoxide for the purposes described below. , chain groups, hydrocarbon groups, etc.

Representative examples of these organic peroxides include hendyl peroxide, 6-butyl peroxide, and 6-butyl hydroxybenzoate. Examples of organic water peroxides include cumene water peroxide, 6th butyl water peroxide, methyl ethyl ketone water peroxide, and notyl butene, cetane, and cyclohexane, including the compound represented by the above general formula (■B). There are hydroperoxides formed by the oxygenation of seed hydrocarbons, as well as various ketones and ethers.

Typical polymerization initiators are about 10% by weight or less, preferably about 0% by weight or less.
It consists of 1 to 5% by weight of a combination of polymerizable monomer and initiator.

Also, ultraviolet+UV active initiators can be used.

Many UV-active initiators are known and can be beneficially used in the present invention.

For example, the formula Mx(Co)y (M is a metal atom, X is 1
or 2, and y are determined depending on the total valence of metal atoms, and are usually integers of 4 to 10. ) can be selected from metal carbonyls having

Preferred are (a) C+ to C16 linear or branched alkyldiones, and (b) those having the general formula R5(Co)R
6 (about 5 is an alkyl group, aryl group, aralkyl group or alkaryl group of C1 to CIO, R6 is about 5
Or hydrogen. ) is selected from carbonyl compounds having the following.

In addition, R5 or R6 also includes substituents that do not have an adverse effect on the compound that performs its function, such as an alkylalcoquino group,
It can be alpha-substituted with an arylalkoxy group, an alkarylalcoquine group, an alkylaryloxy group, an arylaryloxy group, or an alkarylallyloxy group, or an amine derivative, monoalkylamino derivative, or dialkylamino derivative thereof. All of these substituents contain up to about 6 carbon atoms.

5 and R6 can also be combined with a carbonyl group to form an aromatic or heterocyclic ketone containing up to about 16 carbon atoms.

When using a UV-active initiator, for example, about 500 p
It is desirable to prevent pseudopolymerization of the composition prior to its intended use by adding low levels of well-known free radical or UV stabilizers, up to , p, m.

Suitable free radical stabilizers are hydroquinone, p-benzoquinone, butyrate of hydroxytoluene and butyrate of hydroxyanisole.

Other Ingredients For optimal performance, it is desirable to include chelating agents, crosslinking agents, and inhibitors in the elastomeric curable composition.

Generally, it is desirable to include a small amount (eg, about 0.1 to 1 weight percent) of a metal chelating agent.

These can be selected from those well known for use in anaerobic compositions, but preferred are ethylenediaminetetraff1E acid (EDTA) and its sodium salt, 1,1-ethylenebisnitrilemethylididinedipyridine. and beta-fuketones are the most effective and preferred.

See US Pat. No. 4,068.475 and US Pat. No. 4.262,106 for further details.

The concentration of inhibitor left in the monomer is sufficiently high to obtain good stability.

However, to ensure maximum shelf life, about 0.1 to 1 percent by weight of the composition is desirable.

Among these inhibitors, the useful ones are hydroquinone, benzoquinone, naphthoquinone, phenanthraquinone, a7
traquinone and substituted compounds thereof.

Although various phenols can also be used, a preferred one is 2,6-di-tart-butyl-4-methylphenol.

Particularly when the composition is used as a gasket or adhesive, it is also beneficial to incorporate adhesion promoters, which can be selected from known ones, with silane-based ones being preferred;
It can be used in a proportion of about 0 to 5% by weight.

In addition, cikintropic agents are also useful and can be selected from known ones, such as [Aerosil (A, Eros Mouth) J2
Degussa, USA, under the trade name 00.
Fumed quartz (SiO), commercially available from Sne, )
2) is preferred and is usually used in proportions of about O to 5% by weight.

Also useful are surfactants or primers, but because of their extreme activity and their tendency to destroy the storage stability of elastomeric curable compositions, they are preferred when applied to the composition instead of being included in the composition. It is separately applied to the surface of the substrate to be bonded beforehand.

However, it is also possible to apply the cured portion of the elastomeric curable composition to a substrate and apply the activator thereon. The primer serves to greatly speed up curing.

Two types of activators are preferred.

The first type consists of an aldehyde-amine combination product, preferably butyraldehyde-aniline, and is commercially available from DuPont, USA under the name "Buetene J".
, 1. Dupont de Nemours &
Co., Ltd.).

The second type consists of substituted thioureas, such as those described in U.S. Pat. ing.

EXAMPLES The present invention will now be described in detail with reference to preferred examples.

Process A Polyester formed by the reaction of diethylene glycol and adipic acid in a four-necked resin kettle equipped with a dry air sweep, a stainless steel stirrer, a nitrogen suction tube, a thermometer, a condenser, and an inlet stopcock for evacuation. Desmodur J 1700 (MOBAY Chemical Co., Ltd.) (MOBAY Chemical 5) (a)
Corporation )Ig! ! )
Fill 4114.80 grams of.

Heat the kettle under vacuum to 100-11o0 for 60 minutes.

Start the dry air sweep, cool the kettle to 40'C and add 543.28 grams of MOBAY TDI diisocyanate 2.4 toluene in one shot.

When the TDI addition is complete, heat (') the kettle while stirring.
75℃ for 5 hours), check Nco,
Add constant f (approximately 475 grams) of 2-hydroethyl methacrylate (HEMA) and stir and heat at 75° C. for 4 hours.

Recheck for absence of NCO by IR analysis.

The resulting solution has the general formula (MEMA-TDI-Dl 7
00-TDI-HEMA), approximately 10 (l1%
-M, bis(2-methacryloxyethyl urethane) polydiethylene glycol azide is -polyester (HT
RTH).

Process B: Fill a kettle similar to the above with 1571.2 grams of polyester diol ("Desmodur J 1700") and heat under vacuum to 100-110'C for 60 minutes.

Start the sweeper and cool the kettle to 40°C, 214
, +S grams of MOBAY TDI diisocyanate 2
, 4 Add one shot of toluene.

When the addition is complete, stir and heat the kettle (up to 75°C for 6 hours)
Check the NCO and calculate the amount (approx. 428 grams)
of allyl alcohol and stirred and heated for an additional 4 hours at 75°C before rechecking for the absence of NCOs by IR analysis.

The resulting solution has the general formula (ALLYL-TDI-Dl
700-TD I -ALLYL)K equivalent to polydiethylene glycol at a concentration of substantially 100%>
,? - polyester diallyl urethane (ATRTA
).

Process C A kettle of the type described above, heated in an air sweep (approximately 40° C.), was charged with 165 grams of MOBAY TDI toluene diisocyanate (TDI) and 460 grams of 1,6 hexanediol adipic acid/NeoRn. Tyl glycol (pB) lr Irlux (Inolex) J 14
00-120 polyester) is slowly added over 20 minutes.

After the addition is complete, continue to stir and heat (40-45°C) for 1 hour, and then stir and heat at 100°C for 2 hours.

After completion of the 6 hour reaction period, the bath temperature was lowered to 50°C and 2
'50 grams of 2-hydroxyethyl methacrylate (H
Add EMA).

The reaction mixture was stirred and heated to 50° C. for 2 hours before incubation with 1378 grams of a 10-m end hearth.
hm&Haas) J QM-657 dicyclo methacrylate, tenyloxyethyl (MA), and 146 grams of Rohm and Haas acrylic acid are added with stirring.

The resulting solution consists of polyester methacrylate urethane resin (PEUMA) diluted with monomer.

26146 in a kettle heated by air sweep (60°) according to the manufacturing method.
8 grams of 2-hydroxyethyl methacrylate (HEM
Charge A) and then add 2332.99 grams of phenyl isocyanate at a rate of about 5.97 grams per minute.

The temperature of the reaction mixture is maintained at 58-60°C.

After the addition is complete, stir and heat at 50 to 60°C for 2 hours,
Check Neo content by IR analysis.

Continue stirring and heating until free of NGO, add approximately 10 grams of 2-hydroxyethyl methacrylate (HEMA), then heat and stir until free of NGO (IR analysis).

Solid crystalline product (MP600) i.e. 5007,3
7 grams? 2-Methacryloxyethylphenyl urethane (2MEP) was obtained.

Manufacturing method E: Add 281 to a resin kettle heated by air sweep (40'C).
9.81 grams of phenylcricidyl ether (MPG)
Fill E). 14.08 grams of methylimidacyl, 137.63 grams of triethylamine were added with stirring, followed by 1616.48 grams of methacrylic acid (M
A) is added at a rate of 6.6 grams per minute. After completion,
Raise the kettle temperature to 70° C. and heat and stir until the reaction indicates completion of at least 95·ξ-cents, as determined by gas chromatography from the calibration standard. The reaction is 95・
Once ξ-cent is reached, the reaction vessel is cooled to 4D° C. and the resulting oily liquid is washed sequentially with the following detergents:

(1) distilled water; (2) a saturated aqueous solution of sodium bicarbonate; (3) distilled water; (4) a 1 percent aqueous solution of tetrasodium ethylene cyamine tetraacetate; and (5) distilled water.

Vacuum remove the remaining water and remove 6-phenoxy-methacrylic acid.
A liquid product consisting of 2-hydroxypropyl C5P2HPM) is recovered.

Manufacturing method F 262.
2 grams 0M0BAY TDI, diisocyanic acid 2,
4 Toluene (TDI) was charged, and 48.1 grams of dry methanol was slowly added dropwise over 2.5 hours.
Stir and heat at 9°C for 2 hours.

195 stabilized with 0.25 grams of hydroquinone
．． 2 grams of 2-hydroxyethyl methacrylate (HB
MA) is added slowly at a rate that maintains a temperature of approximately 60°C.

After addition, stir and heat at 82° C. for 6 hours.

Check for absence of NCO by IR analysis and cool to room temperature.

The product obtained is 4-methoxycarbonylamino~2
It was a solid crystal of -(2-methacryloxy)ethoxycarbonylaminotoluene (422MECT).

Manufacturing method G: 261 in a resin kettle heated by air sweep (55°C)
1 gram MOBAY TDI, 2 diisocyanates
．． 4 Toluene (TDI) is charged, methyl alcohol is slowly added dropwise to 1622 grams of dry iso over 15 hours, and the mixture is stirred and heated at 79° C. for 2 hours.

195.2 grams of 2-hydroxyethylene methacrylate (HBMA) are slowly added dropwise over 1,5 hours. After completion, add 0.1 grams of DABCO catalyst and
Stir and heat at 8°C for 5 hours.

Check for absence of NGOs by IR analysis and cool to room temperature.

The obtained product is a solid crystal of 4-isomethoxycarbonylamino 2-(2-methacryloxy)ethoxycarbonylaminotoluene (4221ECT).

Manufacturing method H: Add 1742 to a resin kettle heated by air sweep (60℃).
．． After filling 4 grams of allyl alcohol, 357
3.7 grams of phenyl iso77phosphate at approximately 597 grams per minute.
Add in grams.

The temperature of the reaction mixture is maintained at 58-60°C.

After the addition was complete, stir and heat at 50 to 60°C for 2 hours.
Check the NGO content with R analysis.

Continue stirring and heating until there are no more NGOs left, add about 10 grams of allyl alcohol, and heat until no more NGOs are left (
IR analysis), stir.

5316 grams of a solid crystalline product of allyl phenyl urethane (AP) was obtained.

Method I A resin kettle of the type described above is charged with 1163.8 grams of Tesmodur J1700 Polyester Diol.

Heat with vacuum stirring at 80°C for 65 hours using an aspirator. 9a, 1 gram of maleic anhydride is added in one shot using 0.5 grams of DABCO as a catalyst and stirred and heated at 85° C. for 2.5 hours.

An oily liquid was obtained consisting of dimaleic acid half ester (MRM) of polydiethylene glycol adipate.

Process J A nitrogen-swept resin kettle of the type described above was charged with 150 grams of triethylene glycol, 180 grams of mercazotoacetic acid, 20 milliliters of concentrated sulfuric acid, and 125 milliliters of toluene and dehydrated until the reaction was substantially complete. 2 at 99-126°C until 100% completion.
Heat to reflux with stirring for an hour.

After 100% of the reaction is completed, the toluene is distilled off and cooled, and the resulting liquid product is sequentially washed with the following washing agents.

(1) distilled water; (2) a saturated aqueous solution of sodium bicarbonate; (3) distilled water; vacuum stripped to remove residual water; filtered;
A liquid product was collected.

In a nitrogen-swept resin kettle of the type described above, add 75 grams of triethylene glycol, 106 grams of mercaptopropionic acid, 20 milliliters of concentrated sulfuric acid, and 12 milliliters of concentrated sulfuric acid.
Add 5 milliliters of toluene.

Heat to reflux with stirring at 99-126° C. for 55 hours to recover water. When the recovered water indicates substantially 100-degree reaction completion, the kettle is cooled to room temperature and the resulting liquid product is washed sequentially with the following washes:

(1) distilled water, (2) a saturated aqueous solution of N sodium carbonate, and (3) distilled water.

The residual water was stripped in vacuo and filtered to recover a liquid product consisting of triethylene glycol dimercaptozolopionate (HPTEG).

Manufacturing method: Into a dry, air-swept resin kettle of the mold described above,
Gram's [Desmodule J1700.1'? Fill with lyester glycol.

Continue stirring and heating at 150°C under aspirator vacuum,
Add 6.0 grams of methacrylic acid, 20 milliliters of concentrated sulfuric acid, and 200 milliliters of benzene.

Heat to reflux with stirring at 90° C. for 10 hours.

Collect the mass and continue heating until the reaction is about 97% complete.

After 97% reaction completion, cool to 40°C and add 0.5 grams of hydroquinone to distill off the triene.

The resulting oily liquid product is washed sequentially with the following detergents:

(11 distilled water, (2) a saturated aqueous solution of sodium bicarbonate, and (3) a mixture of water and methanol.

The residual water/methanol was removed under vacuum, and dimethacrylic acid ester of polydiethylene glycol adipate (MARA
An oily liquid product consisting of M) was recovered.

Method M A nitrogen-swept resin kettle of the type described above was charged with 255 grams of "Dumodur J1700.l" IJ Ester Glycol.

Stir and heat at 150°C under aspirator vacuum to 61
Add 8 grams of mercaptopropionic acid, 31 milliliters of concentrated sulfuric acid, and 600 milliliters of toluene.

Heat to reflux with stirring at 115° C. for 75 hours.

Collect the condensate and continue heating with recovered water until substantially 100 ml of reaction is determined to be complete. The resulting liquid product is then cooled to 40° C. and washed with the following washing agent.

(1) distilled water, (2) saturated aqueous solution of IJium bicarbonate, (3) distilled water, and (4) methanol.

The remaining methanol was removed under vacuum to obtain di-6-mercazotopropionate of polydiethylene glycol adipate (
A liquid product consisting of H8PRPSH) was collected.

Preparation N A resin kettle of the type described above is charged with 1232.2 grams of Polymeg J 2000;

Start the dry air sweeper, cool to 40°C, and cool to 214°C.
．． Add 6 grams of MOBAY TDI diisocyanate toluene in one shot.

After TDI polishing, stir and heat (75°C for 3 hours) and NCO
and added a calculated amount (approximately 1604 grams) of 2-hydroxyethyl methacrylate (HEMA);
Stir and heat at 75° C. for 4 hours.

Recheck NCO with IR analysis.

The resulting solution has the general formula (HEMA-TDI-P4O1
Poly-1,4-butylene oxide at a concentration of approximately 100%, corresponding to 0-TDI-HEMA),
) J 2000 bis(2-methacryloxyethylene urethane) (HTPMTH).

Preparation O A resin kettle of the type described above is charged with 1262 grams of 1 Polymeg 2 oooz Reester Diol.

Vacuum heat to 100-110° C. over 60 minutes.

Start the dry air sweeper and cool to 40°C to 215°C.
Grams of MOBAY TDT diisocyanate 2,4
Add one shot of toluene.

After the addition is complete, stir and heat (75°C for 3 hours) to add NGO
, add a calculated amount (about 43 grams) of allyl alcohol, and stir and heat at 75° C. for 4 hours. IR
The analysis rechecks for the absence of an NCO.

The resulting solution has the general formula (allyl-TDI-P4O10
Poly-1,4-butylene oxide, [Polymeg
eg) J 2000, diallyl urethane (ATP)
MTA).

Experimental Example 1 Table j is a nidistomer curable composition formed in accordance with the present invention.

Clothing 1 Product number 1 Ingredients Parts by weight HTRTH43,53ro2MEP 27.4roro3P2
HPM 29.244Na4EDTA
O,100 Satukarin
1.500H201,000 APH1,000 LUPBROX 2.5-2.5 1.00
0HTRTH is prepared according to Manufacturing Method A.

2MEP is prepared according to the manufacturing method.

3P2HPM is prepared according to Preparation E.

Na4EDTAB is a tetrasodium salt of ethylenediaminetetraacetic acid.

APHu, 1-acetyl 2-phenylhydrazine.

LUPEFtOX 2.5-2.5 is manufactured by Wallace & 5 Tiernan (W5) (a) las and T
iernan+ Inc,')'s Lucidor Division (L
2, commercially available from Ucidol Division)'R (Buffalo, New York, USA).
5-dimethylhexane-25-dihydro is a ruoxide.

A lap shear specimen was prepared using a standard base steel plate.

Apply a small amount (approximately 0.2 grams each) of Formulation A61 to separate specimens, align the edges, press lightly with your fingers to spread the coating composition, and apply light pressure to the slug for 12 to 15 minutes. Leave it for a minute.

The bond thickness was approximately 0.5 mils. Specimens of each formulation were prepared as described above.

2. For the formulation B, apply one drop of the active agent [Buetene J (trademark, manufactured by DuPont, USA, amine-aldehyde condensate) on a solid surface.
(approximately 0.05 g) and add a small amount (approximately
0.02 grams each) of Formulation A1 was applied.

Specimens were room temperature cured and room temperature tested to determine shear strength.

Formulation A1 has a shear strength of approximately 7 after curing for 3 hours.
After 24 hours it was approximately 140.9/cr/LC2,000 psi).

[
Poured onto Teflonj™ finished steel plate.

A pressure of 2268 to 9C5000 bond was applied to this steel plate, a gasket was spread and sealed, and the steel plate was left as it was for 1 hour.

Remove the steel plate and install a spring flange (4.54tcy<1o=ynd) around it over the gasket area.
10 to 15 pieces).

By storing the sample board in an upright position for 7 days,
Formulation 1 was completely anaerobically cured 3; other formulations were cured in the same manner, or for up to 1 hour depending on the initiator system.
It was cured by heating at 100°C.

After curing, the resulting polymer sheet was removed and placed on release paper, 0.635 CrrL (0,250 inch) wide, 254
[dogbone (dogbone) of α (1 inch) length
) Using a J die, 6.4 dog bones were cut from each sheet.

The elongation was measured using two wires 2.54 cIn (1 inch) apart on the dogbone.

A dog bone and a paper tape with an inch scale on it.
Dillon Tensile Tester (Dillon Ten5ileT)
ester ), and the elongation rate and tensile strength at the time of 10 no ξ-cent increase and at the time of break are calculated by multiplying by approximately 15 cents per minute.
．． A maximum elongation speed of 9 cm (6,25 inches) was recorded.

The applied tensile force is the load divided by the starting cross-sectional area before loading the dogbone sample. The measurement results are shown in Table 2.
Shown below.

Table 2 1.2 20 20.0 (284) 1.4 40 26.0 (10) 1.6 60 54.0 (484) 1.8 80 41.1 (584) 2.0 100 55.0 ( 78ro) 2.2 120
73.1 (1040) 2.4 14
0 103.1 (1467) 2゜6
160 162.5 (2308)2.
7 170 1772 (2521>*
Rice Breaking Strength Experimental Examples 2-5 Table 6 is a list of ingredients for four elastomer curable compositions formed in accordance with the present invention.

These compositions, with the exception of Formulation 5, were tested at 100 °C for 1
It was heat-cured for 5 hours.

Product 5 is equivalent to Product 2 except that it uses an anaerobic curing system.

Using these compositions, the ability to change the crosslink density due to compositional variation in the preparation of allyl-terminated, methacrylic acid-terminated, and maleic acid-terminated polyester prepolymers was checked.

The cured sample was swelled and extracted with 2-butanone for 48 hours, and its swollen volume, unswelled extracted volume, and extracted/unextracted dry weight were measured. Using these data, gel content and swelling volume division were calculated.

The swollen volume fraction is the swollen volume of the sample divided by the unswollen dry extracted volume and represents the relative crosslink density of a particular crosslinked polymer.

As the number of swollen volume layers of a particular polymeric composition increases (in which case all major chain units are identical to the polymeric units of the polyester prepolymer), the crosslinking density decreases.

Table 6 Product number components Executive department HTRTH61, 1214, 8829, 7561, 22
A, TRTA 38.88 B5,12 1
．． 21 38.88MRM --40,0
4-1'Ja4 BDTA O,1000,10
00,1On 0.100 Saccharin -1-1,000H,O---1,00O APH---1,000 Luperox2.5-2.5
- 1.000Luperso+ 231 1
．． 000 1.000 1.000 -1 Swelling body waste 2.33 3,94 4.26 2.
50ATRTA is prepared according to Production Method B.

MRM is prepared as in Preparation Method I.

Lupersol 231 is manufactured by Wahls & Co., Ltd. in the United States.
Timmerman (W5) (a) lace & tier
Man, Sne)'s Lucidor division (Lucid)
1, commercially available from Ol Division).
1-bis(t-butylhaloxy)3.3.5-)ethylcyclohexane.

Observations Products 2 and 6, in ATRTA and HTRTH,
The relative amount of allyl-terminated prepolymer increases or
Using MRM instead of ATRTA in formulation filter and 4 increases the swelling volume layer.

An increase in swollen volume layer, indicating a decrease in crosslink density, was seen from products 2 to 6 and 4 in a simple tensile test. It also showed an increase in elongation.

Instead of MRM (formulation 4), M A n A, M
Even if (manufacturing method L) is used, similar results are obtained.

Experimental Examples 6-9 Table 4 is a list of ingredients for four other elastomeric curable compositions formed in accordance with the present invention.

Table 4 Product number component Weight part HTI' (TH48, 8038, 5846, 6617,
48ATRTA 46.57 51°95 4
4.55 75.08MATEG 4,63
9,69 8,81 7.44Na+ EDTA
O, 100, 100°10 0.1['Lupe
rsol 251 1.00 1. C101,00
1, Ocl, 4 Naphthoquinone 0.001 0.001
0.001 0.001 swelling volume waste 3,7
8 5,92 4.3,8 12.13 Growth rate (@
/Applied tensile force (kν'm) (psi) (60,6)
(30) (5/) (ILl, 6)
These products were cured anaerobically at room temperature and
Partial curing was carried out for 1 hour at 0°C, and the swelling volume scrap elongation and tensile strength were measured.

The observed decrease in crosslinking density, indicated by the increase in swollen volume layer, is in good relative proportion to the elongation values recorded.

All of the above products, [Irgacur
e) J (trademark) 184 (Ciba-G
It was cured without peroxide with a UV curing activator, such as Eiff Corporation (Artsleigh, NY).

Argacure 184 is an ultraviolet curing activator consisting of 1-benzoylcycohexacul.

These products exhibit reduced crosslink density and are strongly influenced by dimercaptan in producing high elongation elastomers.

Dimercaptan H8PRPS prepared according to Process M
Similar results can be obtained in products 6-9 if H is used in place of MA'rBG at a slightly higher level.

Furthermore, even if MATEG is replaced with MPTEG (manufacturing method K), substantially the same results can be obtained.

Examples 10 to 16 Table 5 Product number 10 11 12 1RO HTRTH43,96--- PEUMA---44,+0ATR
TA-66,5955,97-4221
ECT-35,41---2MEP
--44,0ro 26303P2HPM
56.04 - - 294ONa4.
EDTA O, 100, 100, 100, 1
0 Satsukarin 1,00 1.00 1.
00 1.00H201,001,001,001,
0OAPH1,001,001,001,00 water peroxide coumene 1,00 1.00 1.00 1
．． 00 Elongation at break f@ 170 180 1
90 160 Tensile strength at break 2500 1150
1948 L500 (psi) PEUMA is prepared as in Preparation C.

422 lECT is prepared according to Process G.

These samples were anaerobically cured into polymer sheet samples and tensile and elongation tested as described above.

Observations: Using monofunctional monomers increases the spacing between crosslinked prepolymer segments, reducing crosslink density and increasing elongation and strength.

Prepolymer segment monomer, HT TH1ATRT
A and PEUMA exhibit reduced elongation and strength when self-curing (50 cm and 14 kg/cd, respectively)
l (200psi)). 422 IBCT (Product 11
) can be replaced with 422 MECT (Production method F) to obtain similar results.

Examples 14-17 Table 6 is a list of ingredients for four additional enstomer curable compositions formed in accordance with the present invention.

Table 6 Product number HTRTH-43,3361,24- ATRTA 43.33 - - 40
．． 002MBP 2924 - -
-To AP 2924-
-5P2HPM 27.4ro 27.42
38.76 60.00Irgarure 184
0,27 0,27 0,27 0.277
Yoa A Hardness Meter 93 6B 69 31AP
is an allyl phenyl urethane theal prepared according to the production method (■).

Observations: By varying the level and type of monofunctional monomer (allyl to methacrylate ester) and the UV curable ability of these formulations, softness or hardness can be varied.

These products are tough, flexible, rubber-like polymers and are manufactured using Loctite UV Curing Chamber Part Number 945810.
0(Loct eυ, V, Curing Cham
berPart◆9458100), irradiated with 0.100 watts of ultraviolet light per square inch (approximately 6.5d) and exposed for 30 seconds, at least 0635cII
It was cured to a depth of L (i inches).

Table 7 is a list of ingredients for four additional elastomeric curable compositions formed according to the present invention.

Table 7 Product number Ingredients Part by weight HTPMTH60, 7114, 6349, 1760, 7
1ATPMTA 5924 85.36 50
．． 83 39.29Na, EDTA O, 100
0,1000,1000,100 Satsukarin
- --1,000H20---1,000 APH---1,000 Luperox 2.5-2.5 -
-1. OD 0Lupersol 231 1.
000 1.000 1.000 -HTPMTM is
It is prepared according to the procedure of Production Method N, and ATPMTA is prepared according to the procedure of Production Method 0.

The above product was cured by heating at 100°C as described above, the cured sample was subjected to swelling extraction as described above, and the swollen volume layer was determined as described above.
．． It was found to be in the range of 00.

As can be seen from the above description, the present invention provides a new and improved elastomeric curable composition that has the ability to crosslink and cure large voids;
Moreover, it hardens at room temperature.

When cured, the composition has strong adhesion to plastics, metals, glass, and wood, making it useful as an elastic adhesive for gaskets, as well as being hydrolytically stable and compatible with liquid hydrocarbons. Even when dissolved, it has excellent swelling resistance against hydrocarbons, so it is particularly useful for manufacturing gaskets that come into contact with gasoline, lubricating oil, etc.

Although the present invention has been described in detail above, modifications can be made to the present invention.

For example, the composition can include an ultraviolet initiator, especially if faster fixing times are desired. Additionally, many compositions can be cured anaerobically at room temperature, ie, without external heating.

Of course, various other changes can be made in addition to this.

, 87・

Claims (13)

[Claims] (1) (a) a medium- to long-chain difunctional or multifunctional prepolymer having vinyl-reactive end groups; (b) (i) reacting with said prepolymer; and (ii)
1. An elastomeric curable composition comprising: a crosslink density control material that is soluble or miscible therein; and (c) a free radical catalyst. (2) The crosslinking density controlling substance is a monofunctional short chain monomer,
A composition according to claim 1, characterized in that it consists of a polymeric chain transfer binder or a mixture thereof. (3) The medium to long chain type multifunctional prepolymer is characterized in that it consists of acrylic acid polyether urethane, methacrylic acid polyether urethane, acrylic acid polyester urethane, methacrylic acid polyester urethane, or allyl alcohol derivatives thereof. A composition according to claim (1) or (2). (4) (a) the multifunctional prepolymer is comprised of a difunctional monomer selected from the group consisting of dimaleic acid half ester of polydiethylene glycol adipate, and dimethacrylic acid ester of polydiethylene glycol adipate; (b) the multifunctional prepolymer consists of diallylurethane of polydiethylene glycol adipate polyester; (c) the catalyst is preferably an organic peroxide, a hydroperoxide,
(d) a free radical initiator selected from peresters and peracids, more preferably consisting of t-butyl perbenzoate, or coumene water peroxide, and a free radical polymerization accelerator; an initiator, (e) a polymerization initiator consisting of a combination of 0.1 to 10% by weight of a polymerizable monomer and the initiator, (f) a crosslink density controlling substance, (f1) co-reactive monomer selected from allyl alcohol, monomethacrylic acid ester and monoacrylic acid ester of alkyl alcohol and allyl alkyl alcohol, (f2) allyl amino methacrylic acid ester, alkylamino methacrylic acid ester, allyl alkylamino methacrylate; (f3) 3-phenoxy-2-hydroxypropyl methacrylate, 3-phenoxy-2-hydroxypropyl methacrylate, acrylic acid 3; - a co-reactive monomer selected from the reaction products of phenoxy-2-hydroxypropyl or phenyl glycyl ether with methacrylic acid or acrylic acid, (f4) methacrylic acid or acrylic acid and para-tertiary co-reactive monomers selected from butylphenyl glycidyl ether, ortho-cresyl glycidyl ether, butyl glycidyl ether, and reaction products of decane or octadecane with glycidyl ether, (f5) glycidyl acrylate, glycidyl methacrylate; glycerol 1-(2-ethyl)hexanoate-3-methacrylate prepared by reaction of ester and glycidyl methacrylate or glycidyl acrylate with 2-ethylhexanoic acid; ) co-reactive monomer selected from glycerol hexanoate-3-acrylate and mixed esters; (f6) 1-hydroxyethyl methacrylate, 1-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, or acrylic; acid 2-hydroxypropyl;
Co-reactive monomers selected from the reaction products with isocyanates, (f7) 2-hydroxyethyl methacrylate and methanol and toluene diisocyanate, 2-hydroxypropyl methacrylate and methanol and toluene diisocyanate, methacrylic acid (g) consisting of any co-reactive monomer selected from the reaction products of 2-hydroxyethyl and isopentyl alcohol and 2,4-toluene diisocyanate, and 2-hydroxyethyl methacrylate and phenyl isocyanate; the multifunctional prepolymer comprises a diallylurethane of polydiethylene glycol adipate; (h) optionally includes a chelating agent; and (i) the crosslink density controlling material is about 50 to 98 mole percent.
, preferably about 91 to 95 mol %. (5) (a) the crosslinking density controlling substance comprises a polymeric chain transfer/binding agent selected from dimercaptoacetate esters and substituted dimercaptocarboxylic acid esters of polyether glycols and polyester glycols; (b) a chain transfer/binding agent; (b1) consisting of triethylene glycol dimercaptoacetate, (b2) triethylene glycol dimercaptopropionate, (b3) consisting of any of the dimercaptopropionate esters of polydiethylene glycol adipate, and (c) a short chain monomer. (c1) 4-methoxycarbonylamino-2-(2-methacryloxy)ethoxycarbonylaminotoluene, (c2) 4-isopentoxycarbonylamino-2-(
2-methacryloxy)ethoxycarbonylaminotoluene, (c3) 3(p-tert-butyl)phenoxy-2-hydroxypropyl methacrylate, or 3(p- acrylic acid)
tertiary butyl) phenoxy-2-hydroxypropyl; (d) the polyfunctional prepolymer comprises: (d1) dimaleic acid half ester of polydiethylene glycol adipate; (d2) dimethacrylate of polydiethylene glycol adipate. The composition according to claim (1) or (2), characterized in that it consists of an acid ester, and (e) the monofunctional monomer consists of 2-methacryloxyethylphenyl urethane. thing. (6) (a) The polyester part of the acrylic acid polyester urethane or the methacrylic acid polyester urethane is
Polyester diol, preferably diethylene glycol and adipic acid, or neopentyl glycol, 1,6-
(b) the polyether portion of the acrylic polyether urethane or methacrylic polyether urethane comprises a polyether diol, preferably a 1,4-butylene oxide repeating unit; The composition according to claim 3, characterized in that it consists of a polyether having a (7) (a) at least one medium- to long-chain difunctional or polyfunctional prepolymer having vinyl-reactive end groups;
and (i) preparing an elastomeric curable composition comprising at least one crosslink density control material that is reacted with and (ii) soluble or miscible with said prepolymer; and (b) of a free radical catalyst. A method for producing an elastomer curable composition, comprising the step of curing the composition in the presence of a curable elastomer. (8) The crosslinking density control substance is a monofunctional short chain monomer,
A method according to claim 7, characterized in that it consists of a polymeric chain transfer binder, or a mixture thereof. (9) Claim No. 7, characterized in that the prepolymer consists of acrylic acid polyether urethane, methacrylic acid polyether urethane, acrylic acid polyester urethane, methacrylic acid polyester urethane, or allyl alcohol derivatives thereof. or the method described in paragraph (8). (10) (a) the multifunctional prepolymer is a difunctional monomer selected from the group consisting of (a1) dimaleic acid half ester of polydiethylene glycol adipate and dimethacrylic acid ester of polydiethylene glycol adipate; , or (a2) a diallylurethane of polydiethylene glycol adipate polyester; (b) the free radical catalyst is preferably selected from organic peroxides, water peroxides, peresters and peracids, more preferably (c) the initiator comprises 0.1 to 10% by weight of a polymerizable monomer and a free radical polymerization accelerator; (d) the crosslinking density controlling substance comprises (d1) co-reactive monomers selected from allyl alcohol, alkyl alcohol and monomethacrylic esters and monoacrylic esters of allyl alkyl alcohols; (d2) a co-reactive unit selected from allylaminomethacrylate, alkylaminomethacrylate, allylalkylaminomethacrylate, allylaminoacrylate, alkylaminoacrylate and allylalkylaminoacrylate; (d3) co-reactive selected from 3-phenoxy-2-hydroxypropyl methacrylate, 3-phenoxy-2-hydroxypropyl acrylate, or the reaction product of phenyl glycyl ether with methacrylic acid or acrylic acid; monomer, (d4) a co-reaction selected from the reaction products of methacrylic acid or acrylic acid with para-tert-butylphenyl glycidyl ether, ortho-cresyl glycidyl ether, butyl glycidyl ether and decane to octadecane glycidyl ether; (d5) 1-(2-ethyl) prepared by the reaction of glycidyl acrylate, glycidyl methacrylate, and glycidyl methacrylate or glycidyl acrylate with 2-ethylhexanoic acid; co-reactive monomer selected from mixed esters of glycerol hexanoate-3-methacrylate and glycerol 1-(2-ethyl)hexanoate-3-acrylate, (d6) 1-hydroxyethyl methacrylate, acrylic 1-hydroxyethyl acid, 2-hydroxypropyl methacrylate, or 2-hydroxypropyl acrylate;
co-reactive monomers selected from the reaction products with isocyanates, (d7) 2-hydroxyethyl methacrylate and methanol and toluene diisocyanate, 2-hydroxypropyl methacrylate and methanol and toluene diisocyanate;
consisting of any co-reactive monomer selected from the reaction products of 2-hydroxyethyl methacrylate, isopentyl alcohol and 2,4-merene diisocyanate, and the reaction products of 2-hydroxyethyl methacrylate and phenyl isocyanate, e) the prepolymer comprises a diallylurethane of polydiethylene glycol adipate, (f) the composition optionally comprises a chelating agent, and (g) the composition preferably comprises about 50 to 98 mole %, , about 91 to 95 mol% of the crosslinking control substance.
). (11) (a) the crosslinking density control substance comprises a polymeric chain transfer/binding agent selected from dimercaptoacetates and substituted dimercaptocarboxylates of polyether glycols and polyester glycols; (b) chain transfer/bonding; (b1) triethylene glycol dimercaptoacetate, (b2) triethylene glycol dimercaptopropionate, (b3) dimercaptopropionate ester of polydiethylene glycol adipate, and (c) a short chain monomer. (c1) 4-methoxycarbonylamino-2-(2-methacryloxy)ethoxycarbonylaminotoluene, (c2) 4-isopentoxycarbonylamino-2-(
2-methacryloxy)ethoxycarbonylaminomerene, (c3) 3(p-tert-butyl)phenoxy-2-hydroxypropyl methacrylate or 3(p-tert-butyl)phenoxy-2-hydroxypropyl acrylate (d) the prepolymer consists of (d1) dimaleic acid half ester of polydiethylene glycol adipate, or (d2) dimethacrylic acid ester of polydiethylene glycol adipate, and (e) the monomer is composed of 2 -methacryloxyethyl phenyl urethane. (12) (a) The polyester portion of the acrylic acid polyester urethane or methacrylic acid polyester urethane is (a1) a polyester diol, preferably diethylene glycol and adipic acid, or neopentyl glycol, 1,6-hexanediol and adipic acid. reaction product,
or (a2) a polyether diol, preferably a polyether having repeating units of 1,4 butylene oxide. (13) The free radical initiator is a photoinitiator, and the composition further comprises the step of exposing the composition to light having a wavelength and intensity that cures the composition. The method described in section 7).