JPS58125720A - Manufacture of rubbery elastomer polymer - 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 a process for making solid elastomeric polymers using mercazotane terminated liquid polymers.

There are many terminally reactive liquid polymers available today.
These liquid polymers are cured into solid elastomers.

Mercaptan end groups are useful groups because they react rapidly at room temperature and the sulfur provides resistance to ozone attack.

Examples of mercaptan-terminated liquid polymers are U.S. Pat.
No. 6.963 and No. 2.474,859. However, materials cured from these polymers become brittle and subject to cold flow and fragmentation (fra,
gment). Furthermore, production by this condensation method involves the expense of removing by-products.

Another method is described in US Pat. No. 3,625,925, in which polythiols are reacted with polyolefins to form mercaptan-terminated polyethers. These products are also weak and their preparation involves the use of large excesses of thiols which must be subsequently removed.

A solution that seeks to combine the known strength of polyurethane with the advantages of mercaptan termination is disclosed in U.S. Pat.
No. 46,780 and No. 3,547,986.

However, the products of this reaction were unstable and non-reproducible and were therefore not commercially viable. The products exhibit surface stickiness and contain olefinic residues and hydroxyl groups, these side groups being detrimental to both physical and weather properties.

Yet another solution is described in U.S. Pat. No. 3,662,023, which forms a polyene-thiol co-reaction product in situ and
That is, a urethane-containing olefin is mixed with a polythiol ester, and the final product is a solid elastomer.

This material is also not reproducible and the reaction (field)
d) Forming a large excess of crosslinks in the molecule to ensure proper curing under the conditions. Also, the mercaptan's harmful odor is produced during its use.

Furthermore, the ester bond present in the mercaptoester used in this cited patent is unstable to climate. Furthermore, the tin catalyst used in the formation of the urethane precursor accelerates its decomposition due to hydrolysis that occurs upon exposure to the atmosphere. In general, all known mercamethane-containing polyurethanes are found to be unstable on storage, and also change in viscosity and lose their curing ability.

A crosslinking density of zero is achieved by careful catalyst selection, exclusion of molecular nitrogen, and complete conversion of all end groups to mercaptan groups (no other reactive sites). It has been unexpectedly discovered that polymers can be obtained which give stable, dry and tough elastomeric solids.

For example, a polyoxypropylene diol with a molecular weight of 4,000 has 1 mole of each hydroxyl equivalent of 2,4-
1-Lylene diisocyanate is reacted. An equivalent amount of allyl alcohol is added and the mixture is heated until the reaction is essentially complete. 0.5% peroxide and 0.5%
1 mole of 1,2-ethanedithiol is added along with 1 mol of tetramethylguanisine. 72 at 600C (140°F)
After heating for a period of time, the mixture is cooled and then mixed with lead peroxide paste. The product solidifies to a non-stick, rubbery solid with a Shore A hardness of 10. The products had high elongation with virtually no recovery and exhibited little or no crosslinking.

Under the conditions cited here, the conversion of the material to mercaptan functionality is so effective that a very low crosslinking density results in a uniformly cured product with high hardness and toughness.

In contrast to the uniform cure provided by the present invention, prior art techniques using the same precursor polymeric glycols depend on the relative amounts of olefinic ends to
This results in cured products that vary widely in hardness, surface tack, strength, elongation, etc.

The reason conventional methods produce such a wide variety of cured products is that the precursor polymer system glycols are chain terminated by varying amounts of olefinic ends. For example, when crosslinked by reacting with tolylene diisocyanate,
The glycols give products with completely different physical properties despite using as starting materials polyether glycols with apparently earthen functionality and identical hydroxyl numbers. Statements in the literature regarding the equivalent functionality and hydroxyl value of polyols of molecular weight do not fully characterize them. Typical polyols have a certain number of hydrohR groups and varying degrees of olefinic terminus, such as vinyl, allyl. The amount of olefinic ends can be as high as 75%, but is usually 25% or less.

When the polyglycol is reacted with an excess of diisocyanate and then with an unsaturated alcohol, as is done in the process of the present invention, a polymer is produced in which all end groups are unsaturated. However, since one part of the unsaturation is vinyl and one part is allyl, one would expect its activity to vary.

When polymers with olefinic double bonds of this type are cured by methods used in the prior art, such as U.S. Pat. No. 3,662,023, the divergent groups (e.g., vinyl and allyl) are completely It reacts at a completely different rate requiring a longer period of time to cure (responcl).
)Will. In such cases, Kokichi is the owner of the U.S. Patent No. 3.
, No. 662,023.

From the above, there is a desire in the art to produce liquid mercaptan terminated polymers that give uniform results upon curing and have high drug heat and photoresistance, day tear strength, adhesion and low toxicity.

The relatively inexpensive and novel liquid mercaptan terminated 1F coalescence used in this invention readily cures into solid elastomers. The cured products according to the invention are tough and elastic and, importantly, exhibit excellent UV stability and have improved water and electrical resistance since salts do not contaminate the polymer.

The liquid mercapcun-terminated polymer used in the present invention is made from a well-known and relatively inexpensive liquid polymer having 2 to 4 reactive (terminal) olefinic double bonds;
True north hydrogen can be produced simply by reacting the polymer with an organic compound having 6 to 6 reactive S'H groups (mercaptan groups) or hydrogen sulfide with 2 to 4 olefinic double bonds. can be reacted with liquid polymers having from 2 to 4 terminal mercaptan groups to form corresponding liquid mercaptan-terminated polymers having from 2 to 4 terminal mercaptan groups.

The amount of hydrogen sulfide used is at least 1 mole for each equivalent of liquid olefin 1", i.e. all olefinic double bonds are reacted with hydrogen sulfide to form a polymer having only terminal or reactive mercaptan groups. .

This reaction is expressed by the following formula: (where q is a positive integer from 2 to 4, and R"
has the same meaning as above).

The mercaptan-terminated liquid polymer can also be reacted with a liquid polymer having 2 to 4 terminal (i.e. reactive) olefinic double bonds with an organic compound containing 2 to 3, preferably 2, mercaptan groups. It can be manufactured by For economic considerations, the organic compound is generally dimercaptan, since this type of compound is more readily available than trimercaptan. Alternatively, a liquid polymer having 2 to 4 terminal olefinic double bonds can be reacted with a polymercaptan liquid polymer. Generally, this reaction is carried out by the following formula: (wherein R, R'', m and q have the same meanings as above).

The raw liquid polymer having 2 to 4 terminal (reactive or functional) olefinic double bonds can be any liquid polymer. The only critical condition for the polymer is that it contains 2 to 4 terminal olefinic double bonds, with 2 to 4 double bonds being preferred. Such polymers include polyethers, polyesters, polyacrylates and polyurethanes.

As mentioned above, if a particular starting polymer does not contain the requisite number of terminal olefinic double bonds, olefinic bi-bonds can be added to the polymer by the methods described above. For example, there are polymers containing many hydroxyl groups (which also contain olefinic ends) that can be used to form liquid polymers with 2 to 4 terminal olefinic double bonds. For example, the raw liquid polymer can be a polyester glycol, which is reacted with an organic compound having at least two (preferably two) incyanate groups, and then one or more olefinic double bonds are removed. An organic olefinic compound containing active hydrogen, such as an organic alcohol or an organic secondary amine, is added. For example, the product of the first step of the reaction between an incyanate group and a polymeric hydroxyl group (which may also contain terminal olefinic groups) would have the following formula; ", rl t, 81n, and p have the same meanings as above).

1 Since the liquid polymer containing terminal hydroxyl groups also contains terminal olefinic double bonds, the resulting compound also contains terminal olefinic double bonds. Since the double bond can be used for reaction with mercaptan-containing compounds, and since an organic compound with at least two incyanate groups was used as one of the starting materials, an organic olefin compound with active hydrogen (e.g. allyl There also remains at least one incyanate group capable of reacting with alcohol, methylallylamine, methylallyl alcohol, sialylamine, hydroxyethyl acrylate, etc.). The organic olefin compound has the following formula; (in the above formula, Alzlx and y have the same meanings as above). This reaction forms the following compound; 2y
s (in the above formula, A,, R', R",
XX 7% 7% rloslt, n and p all have the same meaning as above).

Preferred compounds for the above reaction are A
is O- or N-(lower) aliphatic and D is lower alkylene ester, lower alkylene ether, lower alkylene and lower halogenated alkylene).

From the above, it is possible to use a variety of liquid olefin polymers containing 2 to 4 double bonds, and most importantly, by reacting the terminal hydroxyl group-containing polymer with a diisocyanate compound, the resulting polymer can be It is readily apparent that such polymers can be prepared by the method outlined above by reacting with organic olefin compounds having active hydrogen atoms.

Most incyanate compounds have been successfully used. This includes all difunctional products such as tolylene diisocyanate, diphenyl-methane-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. .

Some liquid polymers that have been successfully used include polyoxypropylene polyols, polyoxypropylene-polyoxyethylene coelectropolymer polyols, and polyoxyzolopylene polymers having up to 75% (e.g., 50%) olefin end groups. These include polyprolactone polyols, polyoxytetramethylene polyols, and polyester polyols.

Reacting the olefin-terminated polymer with a polymercaptan organic compound yields a mercaptan-terminated polymer having the following formula: n, p, R
, R', R'' and A have the same meaning as above).

Compounds found to be useful as sources of polymercaptan organic compounds (i.e., organic compounds having 2 to 6 mercaptan groups) include dimercaptoalkanes having 2 to 12 carbon atoms, zomercapto; These include, but are not limited to, aryl ethers, and somercazotoalkyl ethers having 2 to 12 carbon atoms. Specific compounds found to be useful include 1,6-dimercaptohexane; 1,2-somercaptoethane; β, f-somercazotozoethyl ether; and p, p'-mercazoto Contains methylzophenyl oxide.

5 Polymercaptan In addition to using organic compounds, the use of liquid polymers as a source of mercaptan groups is also conceivable, as mentioned above. For example, good efficacy has been obtained with mercaptan-terminated polyethers such as those illustrated in U.S. Pat. No. 5,431,239 and mercaptan-terminated polysulfides such as those presented in column 1 of U.S. Pat. It was done.

The critical reaction condition lies in the unexpected discovery that it is important to prevent molecular silicon from contacting the reaction components during the reaction. This can be accomplished by gradually stirring the reaction components without forming vortices in the liquid reaction components. Thereafter, the temperature is preferably increased and stirring is stopped. This method eliminates substantially all nitrogen from contacting the reaction components except on surfaces that are known not to interfere with the reaction.

It is also important in the above process to use the correct ratio of olefin to merkanotane. It is necessary to use at least about 1 mole of the trimercabutane compound for each olefin light weight. This ratio is necessary to block each first nophic double bond with a specific mercaptan. For example, if less than one mole of mercaptan compound is used for each equivalent of olefin, the resulting polymer is not a mercaptan-terminated polymer, but rather a partially cured thioether. One reason for this result is that one of the mercaptan groups reacts with an olefinic double bond, while the other mercaptan group reacts with another olefinic double bond.

As mentioned above, this reaction consists of a specific proportion of species and %
It must occur in the absence of molecular nitrogen. Additionally, specific compounds are required to initiate and catalyze the reaction.

The most critical requirement of the above process is that it requires the use of a strongly alkaline initiator. Examples of such strong alkaline initiators include organic amines such as heterocyclic tertiary amines (e.g., diazobicyclo(2,2,2)octane) and at least one initiator such as lower alkyl-substituted guanicine.
There are substituted guanidines with tertiary nitrogen atoms. It is particularly important that the alkaline initiator be a base with a pKb of 6.0 or less and without aryl groups. Weak initiators such as weak amines (eg aniline and dimethylaniline) cannot be used. The particular amount of alkaline initiator is critical, and it is generally desirable to use at least about 0.01 weight percent, preferably about 0.05 weight percent. Its maximum shelf life is limited by the stability of the resulting mercaptan polymer during storage and use.

It is usually desirable to use a free radical initiator, such as a peroxide catalyst (eg, tert-butyl perbenzoate), at the same time as the alkaline initiator. The amount of free radical initiation catalyst can vary, but preferably 0.1 to 1.0% by weight, based on the reactants, is used. During the reaction, if used in excess of 1% in combination with an alkaline initiator, the mercaptan groups will be excessively oxidized to disulfides, leading to loss of initial mercaptan, and the final polymer will be excessively oxidized to disulfides, resulting in a loss of product. leading to delification.

In accordance with the present invention, the mercaptan-terminated polymers prepared by the above method are readily cured with oxidizing agents, epoxides, or rubber value additives to form solid elastomer I-mer polymers. By oxidative curing for 5 minutes to 8 hours at room temperature, an elastic elastomer having the following general composition and tube strength can be easily obtained: H s (in the above formula, m, n1p, x, ylz,
r, s, t.

A, R, R', and R" have the same meanings as above)
.

The cured product according to the invention has a diameter of at least 1 o [approximately 24"
C (75° F.)] and preferably have a higher Rex hardness. By measuring the Rex hardness of the final cured product, intermediate products (i.e., non-fm
mercaptan) is satisfactory.

The criticality with which the correct alkaline initiator must be used is shown in Table 1. Here, the mercaptan-terminated polymer obtained by Kokichi, in which 100 g of an olefin-terminated polymer (Example 6) was reacted with 7.2y of β,β'-somercanotozoethyl ether, was cured with lead peroxide paste. I let it happen. In Experiments 1-5, the reaction continued for 5 days, but in Experiments 6-8, the reaction continued for only 1 day. The amount of amine used was 0.1 in Experiments 2 to 5. ! 9 and experiments 6-8
is 0.05.9, and at a concentration of 0.05% t
- used in combination with butyl perbenzoate.

As is clear from the table above, the alkaline reagent must be chosen correctly or the reaction will fail as indicated by the Rex hardness of the final cured product.

The same thing happens when nitrogen is added to the reaction. For example, when the reaction is conducted in the substantial absence of nitrogen, the final cured product has a Rex hardness of 34. In contrast, when nitrogen is added, the final product remains a liquid with a viscosity of 2,000 to 3,000 voids, even using the same conditions and reaction components. It turns out that the absence of alkaline initiators and molecular nitrogen is critical in the present invention.

In order to fully explain the invention, the following preferred embodiments are presented. In this embodiment, parts are by weight unless otherwise stated and M, W represent molecular weight.

Example 1 (Preparation of Starting Compounds) An olefin-terminated product was prepared as follows: a hydroxyl with M, W of 4500, little or no unsaturated ends, and 63.3. 174 g of 2,4-tolylene diisocyanate was added to 1500 I of polyoxypropylene triol having a polyhydric acid. The mixture was left at 45°O (1'20°F) for 24 hours. 58 g of allyl alcohol was mixed with the above prepolymer and the mixture was left at 70° C. (158° F.) for an additional 72 hours. A tri-olefin terminated polymer was obtained.

Example 2 t-butyl perbenzoate 0
．． 5g tetramethylguanidine
The 0.05.9 materials were first slowly stirred together (without forming a vortex) in a polyethylene container. Batch coated and heated at 60°0 (140'F) for 16 hours without stirring.
) when it was open. Infrared analysis showed conversion of all olefinic groups. This product was cured with lead peroxide paste to obtain a product with a viscosity of 1560 Poise and a hardness of 30 Rex.

Example 3 (Production of raw material compound) Polyoxyzolopyrene triol (6,000M, W,
) and polyoxynolopylene diol (4,000
A mixture of equimolar amounts of M, W) 2000. ! 9 was used. Add 2.4-1-lylene diincyanate 166 to this mixture.
g was added. The resulting mixture was heated at 45°C (120°F) for 2
It was left for 4 hours. The produced prepolymer was mixed with allyl alcohol 55.5.9, and the mixture was heated at 71°C (
160'F).

An olefin-terminated polymer was obtained.

Example 4 Olefin terminated polymer from Example 6 1
00g β, β'-cymercanotodiethyl ether
7.2! jt-butyl perbenzoate
0.5g tetramethylguanidine
After heating in the same manner as 0.05g Example 6, infrared analysis showed 100% conversion of the olefin groups. This product with a viscosity of 2500 voids was cured with lead peroxide to give a cured product with a final Rex hardness of 35.

Example 5 2,4-Tolylene diisocyanate 17 was added to the trifunctional polyoxypropylene triol 1500,9 used in Example 1.
Added 4g. After 24 hours at 45°C (120″F), the mixture was blended with 116.9 g of hydroxyethyl acrylate to produce acrylic terminations. 145 g of zoethyl ether were mixed with the polymer and kept at 45°0 (120”l?) overnight without stirring. The resulting polymer was rapidly cured using lead peroxide paste and barium oxide catalyst paste to yield a tough polysulfide rubber with a Rex hardness of 40.

Example 6 Polyoxytetramethylene diol (M, W=2.00
0)1000. V was mixed with 174 g of 2,4-tolylene diisocyanate at a temperature of 45°C (120"'F?). After 24 hours, allyl alcohol 58I was added and the mixture was heated at 70°C (158'F) for 72 hours. The resulting product was converted to β,/-somercaptozoethyl ether 1
45 g of t-butyl perbenzoate and 0.6 g of tetramethylguanisine (without forming a vortex). 70° without stirring the product
G (158'F) for 48 hours. Example 2 of this product
of lead dioxide paste to give a non-tacky rubbery solid.

Example 7 Thiocol d? 'lJ Zalphide, LP-18700,!
Added i'. 100 g of toluene, an immiscible mixture;
It was gradually blended with 9 g of t-butyl perbenzoate and tetramethylguanisine o, s, p. The mixture was heated at 60°C (140'F) for 72 hours without stirring. At the end of this period, the bath agent was removed in a wipe film evaporator at 149°0 (300°F). The product was a very viscous, homogeneous liquid. No olefins were found by IR analysis. This product was cured using lead dioxide and barium oxide dispersed in hydrogenated biphenyl. A soft polysulfide rubber was obtained.

Example 8 1732 g of the olefin-terminated product prepared in Example 1 was added to 1.
94 g of 2-dimercaptoethane, 9 g of t-butyl perbenzoate, and 0.99 g of tetramethylguanisine were added. The mixture was heated to 60°C (140°C) without stirring.
F) for 48 hours.

The resulting liquid is treated with a lead dioxide and barium oxide catalyst to produce a product with a Rex fI of 40! I! Polysulfide was obtained by curing until it had a certain degree of hardness.

In the preferred embodiment described above, the diisocyanate compound used was tolylene diisocyanate. However, other diisocyanate compounds can be used to form corresponding incyanate-terminated polymers.
It is also possible to react with a starting liquid polymer having terminal hydroxyl groups and reacting the IIM with an alcohol or amine having active hydrogen and an olefinic double bond. Examples of such organic polyisocyanate compounds include 1,6-hexamethylene diisocyanate, diphenylmethane-4,4'
-zoisocyanate, 4,4'-biphenylene diisocyanate, dicyclohexylmeth 7-4,4'-diisocyanate, inphorone diisocyanate and diphenyl 6,6'-zomethoxy 4,4'-diisocyanate. From the above it is clear that R'' in the above formula can be a variety of substituents, including aliphatic, cycloaliphatic and aryl of 2 to 12 carbon atoms.

The mercazotane-terminated liquid polymer used in the present invention is about 1o
It has a molecular weight varying from 0 to 15,000 and a viscosity of less than 10,000 voids, preferably less than 5000 voids at 25°C.

These mercazotane terminated liquid polymers are readily cured according to the present invention at room temperature into solid rubbery polysulfide elastomers having a Rex hardness of at least 10. Curing can be carried out using oxidizing agents such as lead dioxide, zinc peroxide, barium peroxide, manganese dioxide, and 8 alkali or alkaline earth metal zochromates. Such oxidizing agents can be used in amounts of from 2 to 20 parts by weight, preferably from about 6 to 1 O--Ni parts, per 100 parts by weight of the liquid mercaptan polymer.

Another type of curing agent useful in the method of the invention is an epoxide, such as an epoxy resin formed by the condensation of shrimp chlorohydrin and bisphenol A.

The properties of epoxides for room temperature curing are approximately stoichiometric.

Another type of curing agent useful in curing liquid mercaptan terminated polymers to solid, viscous, rubbery elastomeric polymers are rubber vulcanizing compounds such as sulfur and zinc oxide. Rapid curing can be achieved by simply mixing the vulcanizing agent with the liquid mercaptan-terminated polymer. The sensitivity of the vulcanizing agent required to provide good cure is not critical.

The liquid mercaptan-terminated polymer is cured as a two-component system or a one-component system using the above-mentioned curing agent. In a one-part system, the polymer can be used in accordance with US Pat. No. 3,255,017 as a one-part stable liquid composition that can be completely cured without stirring. An example of a one-component system is shown below: Example 9 The mercaptan-terminated polymer prepared in Example 4 was mixed with 1" acidic acid (by weight) as follows: Part by weight mercaptan polymer, (Example 4)
100 precipitated calcium carbonate
10 Titanium dioxide
10 Mercazotosilane, A-1891 Calcium Peroxide Paste, 50% in Arocloar 20 Barium Oxide Paste, 50% in HB-4[1] 5 This composition is a stable single packaging material, exposed to moisture in the air and hardens into a good rubber with the following properties: through, 1/8";
72 hours RTs 5o%RH Rex hardness 4
0 Weatherability Excellent, no cracking or discoloration.

(6 week weather tester) Adhesion Good to glass, aluminum, Example 10 The following composition does not require water exclusion for stability, but curing is near 1 [M] dependent on atmospheric oxygen. mercaptan polymer, (Example 4')
1 r) [1 Precipitated calcium carbonate
100 titanium dioxide
10tetramethylguanidine
0.5 oxidation catalyst
. , 51 The above composition, which is also a stable single packaging material, cured more rapidly on exposure to the atmosphere than the n1 composition of Example 9, giving a tough and elastic rubber with excellent UV stability.

Example 11 An example of a two-part system is shown below: Part by weight Part A: Mercabutane polymer, (Example 7) 1
00 Precipitated calcium carbonate 200 Plasticizer 100 Titanium dioxide 10 Water
2 part B
: Calcium peroxide 1° Hydrogenated biphenyl 1° Calcium hydroxide 2 The mixture of Part A and Part B was cured overnight to give a product with good elasticity and remarkable weatherability.

Example 12 2 Storage ridge portion A: Mercaptan polymer, (Example 8)
100 Calcium carbonate 20
0 plasticizer 1o[titanium oxide 1゜DABC
O1 water 10
Part B = Epoxy (Evo: /828)
'10 The above two parts were mixed together and cured overnight at room temperature to yield a solid product with good elasticity and adhesion.

Example 16 Polymercaptan polymer, (Example 8) 100 Zinc oxide 40 Sulfur
4 rice Tetron A (accelerator)
1. Tetron A is zopentamethylene-thiura-tetrasulfone.

The mixture cured well in 16 hours at room temperature to a product having a hardness of 10-15 lex and an elongation of 2[]0%.

In the one-component yarn illustrated in Example 9, a latent curing agent in the polymer phase that is activated by the presence of moisture is dispersed throughout the polymer. Similarly, a water-soluble deliquescent accelerator selected to attract and adsorb moisture from the surroundings and promote curing of the polymer by the curing agent is dispersed throughout the polymer. The polymer can be first dried to remove moisture, or, preferably, the deliquescent promoter can also be a desiccant that dries the polymer. Alternatively, a single drying, deliquescent, latent curing and accelerating agent may be dispersed throughout the polymer, in which case the curing and accelerating agent dries the polymer and removes moisture from the surroundings. When activated by the presence of moisture, it cures and accelerates polymer curing. The environment can include moisture or bodies containing essentially only moisture, such as atmospheric air of normal humidity.

The present invention encompasses the following embodiments; ( ]) Formula: Hs (wherein each XNY and 2 are hydrogen, hydrocarbon, alkoxy, phenoxy or a halogenated derivative thereof; each r, s and t is hydrogen or lower alkyl; m is an integer of 1 to 2; n is an integer of 1 to 4; p is an integer of 0 to 6; the sum of n and p is 2 to 4; ;R' is a divalent organic group;R
" is the backbone of a liquid polymeric precursor: R is a group of a polymercapto organic compound R, -(SH)m; and A is an organic olefinic precursor having active hydrogen.
Compound: A solid, viscous, elastomeric polysulfide polymer having a grouping of 5.

Agent Akira Asamura 1 other person 6

Claims (1)

[Claims] Formula (in the above formula, each x, y and 2 are hydrogen, hydrocarbon, alkoxy, phenoxy, or a halogenated conductor thereof; each r, s and t is hydrogen or lower alkyl) m is an integer of 1 to 2; n is an integer of 1 to 4; p is an integer of 0 to 6; the sum of n and p is 2 to 4; y is a divalent organic B is the backbone of the liquid polymer precursor; R is the group of the polymercapto organic compound R-(SH)m; and A
is an organic olefinic silica containing active hydrogen, does not contain reactive olefinic double bonds, and cures into a solid poly->norphide at 3 parts by weight per 100 parts by weight of the liquid polymer. a solid cured polymer having a Rex hardness of at least 10; and a solid cured polymer having a Rex hardness of at least 10. A method for producing a solid, non-tacky, rubbery elastomeric polymer, characterized in that the mixture is allowed to stand until the formation of a solid, non-tacky, rubbery elastomeric polymer.