JPH08852B2 - Polymer composition, method for producing the same, and curable composition thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid polymer composition and a method for producing the same, and particularly to a liquid composition which is excellent in compatibility with a plasticizer, remarkably shortens the synthesis time, and can be synthesized at a low temperature. The present invention relates to a polymer composition and a method for producing the same. Further, the present invention can be blended with a small amount of the plasticizer, and when a coating material is applied to the cured product, the migration of the plasticizer to the coating film is small and the coating film does not soften, which is suitable for a sealing material. It relates to a curable composition. Further, the present invention relates to a polymer composition that can be obtained as a curing agent for an epoxy resin and has a high curing rate and good durability, and a curable composition using the same.

[0002]

2. Description of the Related Art A polymer having two or more thiol groups in one molecule is easily cured when mixed with an oxidizing agent, and the thiol group is not limited to epoxy groups, isocyanate groups, etc. It is widely used in sealing materials, paints, adhesives, etc. because it reacts easily and becomes high molecular weight.

On the other hand, polysulfide polymers, polysulfide in a molecule binding _-S x - to include structure (x = 1 to 5), high polarity, only limited plasticizers can not be used. That is, since a general-purpose inexpensive plasticizer cannot be used, the cost increases when a compound such as a sealing material is formed. In addition, since the viscosity is higher than the molecular weight of the polymer,
In order to improve the workability of the compound, it is necessary to add a large amount of plasticizer. For this reason, when a paint is applied to a cured product of a sealing material made of a polysulfide polymer, there is a problem that a coating film is softened due to seepage of a plasticizer.

Japanese Patent Application No. 1-271265 describes a polymer composition comprising a polysulfide polymer and a thiol group-containing polyether polymer, which is compatible with a general-purpose and inexpensive plasticizer. It is excellent and suitable for sealing materials, and the amount of plasticizer added can be reduced.
However, since there are many low molecular weight components, the elongation of the cured product is not always sufficient when cured with an oxidizing agent or the like.

Further, the polysulfide polymer described in Japanese Patent Application No. 2-109461 has excellent compatibility with a general-purpose and inexpensive plasticizer, the amount of the plasticizer added can be reduced, and the low molecular weight component is reduced. The elongation of the cured product was also improved when it was cured with an oxidizing agent or the like. However, this polymer must have a long reaction time in order to reduce low molecular weight components having a molecular weight of 500 or less, and when this polymer is used in a sealant, the viscosity stability of the formulation upon storage There was a drawback that was not good.

Therefore, the object of the present invention is to have excellent compatibility with a plasticizer and viscosity stability upon storage when compounded with a sealant, etc., and to significantly reduce the synthesis time for reducing the low molecular weight component in the polymer. It is an object of the present invention to provide a shortened polysulfide polyether polymer composition and a method for producing the same.

Another object of the present invention is to provide a curable composition in which the coating film does not soften even when a coating material is applied to the cured product by reducing the amount of the plasticizer used for the polymer composition. It is to be.

Still another object of the present invention is to provide a curable composition which, when used together with an epoxy resin, has good adhesiveness and water resistance and a high curing rate.

[0009]

As a result of earnest research in view of the above object, the present inventors have found that a polysulfide polyether polymer in which a polyether chain is introduced into the main chain of the polysulfide polymer has a small polarity of the polymer, In the case of only polysulfide polymer, it becomes compatible with the plasticizer that was not compatible, the viscosity also decreases, the amount of plasticizer used can be reduced, and when the cured product is coated with a paint, It has been found that the migration of plasticizer to the membrane is reduced, the fouling property is improved, and the viscosity stability of the compound upon storage is improved even when compounded in a sealant or the like.

Further, by adding an acid when introducing the polyether chain into the main chain of the polysulfide polymer, it is possible to reduce the low molecular weight component having a molecular weight of 500 or less in a short time at room temperature, and therefore, to cure the same. It was found that the elongation of the product was good. Furthermore, it has been found that when this polysulfide polyether polymer is used together with an epoxy resin, it cures rapidly at low temperature and has sufficient adhesive strength and water resistance. The present invention has been made based on the above.

That is, the polymer composition of the present invention comprises (a) in the main chain, (i)-(R ₁ O) _n- (wherein R ₁ is an alkylene group having 2 to 4 carbon atoms, and n is a polyether moiety represented by an integer of _{6~200), (ii) -C 2} H 4 OCH 2 OC 2 H 4 -S x -. and _{-CH 2 CH (OH) CH 2} -S x - (. here, x is an integer of 1 to 5) contains a structural unit represented by, and the _{end, (iii) -C 2 H 4} OCH 2 OC 2 H 4 -SH and / or - It is characterized by comprising a polysulfide polyether polymer having a thiol group represented by CH ₂ CH (OH) CH ₂ —SH, and (b) an acid.

The first method for producing the above polymer composition is (c) HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ S _x ) _m C _{2
H 4 OCH 2 OC 2 H 4} SH ( where, x is an integer from 1 to 5, m is an integer of 1 to 50.) And polysulfide polymer represented by, in (d) the main chain, - ( R _{1 O) n} - (where, _{R 1} is an alkylene group having 2 to 4 carbon atoms, n represents a show) an integer of _{6~200, -CH 2 CH (OH)} CH 2 -S x -. ( However, x has a structural unit represented by is an integer of 1-5.), and, at the _end, a polyether polymer having a thiol group represented by _{-CH 2 CH (OH) CH 2} -SH, (C) / (d) = 95/5 to 5/95 When the reaction is carried out at a weight ratio, (b) an acid is added.

The second method for producing the above polymer composition is (c) HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ S _x ) _m C _{2
H 4 OCH 2 OC 2 H 4} SH ( where, x is an integer from 1 to 5, m is an integer of 1 to 50.) And polysulfide polymer represented by, in (e) the main chain - (R ₁ O) _n- (wherein R ₁ is an alkylene group having 2 to 4 carbon atoms, n is an integer of 6 to 200) and a polyol having two or more hydroxyl groups is reacted with epihalohydrin. The resulting halogen-terminated prepolymer and (f) MSH and / or M ₂ S _x (M is an alkali metal atom, x is an integer of 1 to 5) are (c) / (e) = 95/5. (B) Acids are added when the reaction is carried out at a weight ratio of 5/95 and as (f) 1 to 50 parts by weight with respect to 100 parts by weight of (c) + (e).

Further, the first curable composition of the present invention comprises
It is characterized by containing the above-mentioned polymer composition and (h) an oxidizing agent.

The second curable composition of the present invention comprises the above polymer composition, (i) an epoxy resin containing two or more epoxy groups in the molecule, and (j) an amine. It is characterized by containing.

The present invention will be described in detail below. Polysulfide polyether polymers of the present invention, in the main chain, (i) - indicating (but, _{R 1} represents an alkylene group having 2 to 4 carbon atoms, n represents an integer of _{6~200 - (R 1 O) n} . a polyether moiety represented _{by), (ii) - (C} 2 H 4 OCH 2 OC 2 H 4 -S x) -
And - Table with (where, x is 1-5, preferably an integer of 1 to 3, the average is _{1.5~2.5.) - (CH 2 CH} (OH) CH 2 -S x) It is the containing structural units, and the _{terminal, (iii) -C 2 H 4} OCH 2 OC 2 H 4 -SH and /
Alternatively, it has a thiol group represented by —CH ₂ CH (OH) CH ₂ —SH.

In the above polysulfide polyether polymer, the polyether moiety of (i) and the structural unit represented by (ii) may be bonded in any sequence, and the ratio thereof is-(R ₁ O). _n - component 2 to 95 _{wt%, (C 2 H 4 OCH} 2 OC 2 H 4) component 3 to 70 _{wt%, (CH 2 CH (OH} ) CH 2) of component is 1 to 50 wt% Is preferred.

When the content of the-(R ₁ O) _n -component is less than 2% by weight, the effect of improving the compatibility with the plasticizer is poor, while when it exceeds 95% by weight, the weather resistance of the cured polymer becomes poor. . (C ₂ H ₄ OCH ₂ OC ₂ H ₄ ) component 3% by weight
If it is less than 70, the weather resistance of the cured product of the polymer is poor, while the
When the content is more than weight%, the effect of improving the compatibility with the plasticizer is poor. Also, the (CH ₂ CH (OH) CH ₂ ) component is 1
If it is less than 50% by weight, the effect of improving the compatibility with the plasticizer is poor, whereas if it exceeds 50% by weight, the water resistance of the cured polymer becomes poor.

The polysulfide polymer (c) in the production method of the present invention has fluidity at room temperature and has a molecular weight of 1
00 to 200,000, preferably 400 to 50,000
0. Preferred examples of such polysulfide polymers are described in U.S. Pat. No. 2,466,963.

The thiol group-containing polyether polymer (d) in the production method of the present invention contains-(R ₁ O) _n- as a polyether moiety in the main chain. Wherein, _{R 1} is an alkylene group having 2 to 4 carbon atoms, n is an integer of 6 to 200. The molecular weight of such a polyether moiety is 4
A range of 00 to 10,000 is preferable. When the molecular weight is less than 400, the effect of improving the compatibility with the plasticizer when reacted with the polysulfide polymer is small, while 10,000
When it exceeds, the viscosity of the polymer increases, which is not preferable.

This thiol group-containing polyether polymer has (CH ₂ CH (OH) CH ₂ ) in its main chain.
-S _x) -. (Where x is an integer from 1 to 5 containing the structural unit represented by), and the terminal, a thiol group represented by _{-CH 2 CH (OH) CH 2} -SH Have.

Further, the weight ratio of sulfur content / thiol group content in the polymer is preferably 1.06 or more. When the weight ratio of sulfur content / thiol group content is less than 1.06,
The proportion of polysulfide bonds is small, and the compatibility between the polymers (a) and (b) is poor.

A preferred example of such a thiol group-containing polyether polymer can be synthesized by utilizing a known method described in JP-B-47-48279. That is, after adding epihalohydrin such as epichlorohydrin and epibromohydrin to polyalkylene glycol such as polypropylene glycol and polyethylene glycol, alkali hydrosulfide (MSH, where M is an alkali metal) such as sodium hydrosulfide and potassium hydrosulfide. ,
And / or by reacting with an alkali metal sulfide (M ₂ S _x , where x represents an integer of 1 to 5), for example, a thiol group is added to the end of the structure represented by the following general formula (1). A polyether polymer having is obtained. The main chain of the polymer thus obtained partially contains a polysulfide bond, and is suitable as the thiol group-containing polyether polymer of the present invention.

Embedded image (However, R ₃ is hydrogen or a methyl group, and n is 6 to 20.
Is an integer of 0, m is 0 to 5, and x is an integer of 1 to 5. )

As the acids of the present invention, both inorganic and organic acids can be used. If necessary, a solvent such as water or ethanol may be used.

The mixing ratio of the (c) polysulfide polymer of the present invention and the (d) thiol group-containing polyether polymer is 95/5 to 5/95, preferably 90 by weight.
/ 10 to 10/90. If the content of the polysulfide polymer (c) is less than 5% by weight based on the total weight, the weather resistance of the cured product deteriorates. Further, if the amount of the thiol group-containing polyether polymer is less than 5% by weight, the effect of improving the compatibility with the plasticizer is small.

The reaction conditions of (a) the polysulfide polymer according to the present invention and (b) the thiol group-containing polyether polymer are 10 to 100 ° C., preferably 20 to 80 ° C.
Then, it may be stirred for 1 to 60 minutes.

At this time, with respect to 100 parts by weight of the above reaction product,
If necessary, 0.01 to 10 parts by weight of acids are dissolved in a solvent such as water or ethanol and added. If the addition amount of the acids is less than 0.01 parts by weight, the reaction promoting effect is low, and if it exceeds 10 parts by weight, the pH of the obtained polymer is low, which is not preferable.

The reaction between the (a) polysulfide polymer and the (b) thiol group-containing polyether polymer in the present invention is considered to occur as follows.

Embedded image The polyether chain is introduced into the main chain of the polysulfide polymer by the exchange reaction of the polysulfide bond as shown in. that time,

[Chemical 3] A low molecular weight component represented by (q is an integer of 0 to 2 and x is an integer of 1 to 5) is produced. Therefore, in the present invention, by adding an acid to shift the pH of the reaction system to the acidic side, the cleavage of the S _x portion in the low molecular cyclic compound represented by the formula (3) is promoted, and the subsequent addition reaction is performed. Thereby, the molecular weight distribution is averaged, and the low molecular weight component represented by the formula (3) can be 10% by weight or less.

The second production method of the present invention is characterized in that (a) a polysulfide polymer is added when the thiol group-containing polyether polymer is synthesized by the above-mentioned method.

That is, the main chain is-(R ₁ O) _n- (wherein R ₁ is an alkylene group having 2 to 4 carbon atoms, and n is 6
Indicates an integer of ˜200. ), A halogen-terminated prepolymer obtained by adding epihalohydrin such as epichlorohydrin or epibromohydrin to polyalkylene glycol such as polypropylene glycol or polyethylene glycol having two or more hydroxyl groups at the terminal, M
Sodium hydrosulfide represented by SH (M is an alkali metal atom), alkali hydrosulfide such as potassium hydrosulfide and / or sodium sulfide represented by M ₂ S _X (x represents an integer of 1 to 5), and When a terminal thiolation reaction is carried out by reacting with an alkali sulfide such as sodium sulfide or an alkali polysulfide, HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ S _x ) _m
C ₂ H ₄ OCH ₂ OC ₂ H ₄ SH (provided that x is an integer of 1 to 5 and m is an integer of 1 to 50) is reacted with a halogen-terminated end while being added. It is carried out by adding 0.01 to 10 parts by weight of acids to 100 parts by weight of the prepolymer + polysulfide polymer.

The weight ratio of halogen-terminated prepolymer to polysulfide polymer is 95/5 to 5/95,
It is preferably 90/10 to 10/90. If the polysulfide polymer content is less than 5% by weight, the weather resistance of the cured product will be poor. Also, the halogen-terminated prepolymer is 5% by weight.
When the amount is less than the above, the effect of improving the compatibility with the plasticizer is small.

As the alkali hydrosulfide in the present invention,
Industrially produced flake sodium hydrosulfide is preferred. This sodium hydrosulfide has a purity of about 70% and contains a trace amount of sodium polysulfide component. In the reaction according to the method of the present invention, when the halogen-terminated prepolymer is thiolated, a polysulfide polymer is also added at the same time to carry out the reaction of the formula (2). Decomposition of molecular weight components,
It becomes possible to reuse.

By mixing the polysulfide polyether polymer obtained in the present invention with an oxidizing agent, it can be easily cured at room temperature to give a curable composition which is good as a sealing material, an adhesive or the like.

As the oxidizing agent in the present invention, a substance which has been conventionally used as a curing agent for a thiol group-containing polymer can be used. Specific examples of these oxidizing agents include ZnO ₂ , FeO ₂ , PbO ₂ , MgO ₂ ,
CaO ₂ , BaO ₂ , MnO ₂ , TeO ₂ , SeO ₂ ,
Inorganic peroxides such as Pb ₃ O ₄ , SrO ₂ and LiO ₂ , Z
nO, FeO, PbO, Fe ₂ O ₃ , Sb ₂ O ₃ , Mg
Inorganic oxides such as O, CoO, CaO, CuO, BaO,
Na ₂ CrO ₄ , K ₂ CrO ₄ , Na ₂ Cr ₂ O ₇ , K
₂ Cr ₂ O ₇ , NaClO ₄ , NaBO ₂ .H ₂ O ₂ ,
K ₂ C ₂ O ₆ , KMnO ₄ , sodium percarbonate (2Na ₂ C
O ₃ + 3H ₂ O ₂ ) and other inorganic oxidants, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t
-Butyl perbenzoate, sodium peracetic acid, organic peroxides such as urea peroxide, organic oxidants such as nitrobenzene, dinitrobenzene, paraquinone dioxime, and the like, but PbO ₂ is most widely used. In the composition of the present invention, the blending amount of these oxidizing agents varies depending on the type of the oxidizing agent, but is generally 1 to 50 parts by weight with respect to 100 parts by weight of the polysulfide polyether polymer.

The curable composition of the present invention contains calcium carbonate, talc, clay, titanium oxide, silica and the like for the purpose of further improving economy, workability in applying the composition and physical properties after curing. Fillers can be added. Further, the curable composition of the present invention cannot be used in the case of only polysulfide polymer, dioctyl phthalate (DOP), diheptyl phthalate (DH).
Since inexpensive phthalic acid esters such as P) are compatible, these can be added. Further, a plasticizer such as chlorinated paraffin and hydrogenated terphenyl can also be added. Since the polysulfide polyether polymer according to the present invention has a lower viscosity than the conventional polysulfide polymer alone, even if the amount of the plasticizer added is 40 parts by weight or less relative to 100 parts by weight of the polymer, sufficient workability is obtained. can get.

A curable composition obtained by adding an epoxy resin having two or more epoxy groups in one molecule and amines to the novel polysulfide polyether polymer according to the present invention has a lower temperature than conventional polysulfide polymers. In this way, a cured product can be obtained which has a fast curing speed, has good flexibility as compared with the case of using only the thiol group-containing polyether polymer, and has sufficient water-resistant adhesiveness.

The epoxy resin used in the present invention includes:
Bisphenol A, halogenated bisphenol A, bisphenol F, halogenated bisphenol F, resorcinol, hydroquinone, pyrocatechol, 4,4'-
Epoxy resin obtained by adding epichlorohydrin to polyhydric phenol such as dihydroxybiphenyl and 1,5-hydroxynaphthalene, obtained by adding epichlorohydrin to polyhydric alcohol such as ethylene glycol, propylene glycol and glycerin And epoxy resins obtained by adding epichlorohydrin to aromatic dicarboxylic acids such as oxybenzoic acid and phthalic acid.

The amines used in the present invention are preferably those used as a curing accelerator when a thiol group-containing polymer is used as a curing agent in an epoxy resin. Specifically, N, N-dimethylpropylamine, N, N,
Aliphatic tertiary amines such as N ′, N′-tetramethylhexamethylenediamine, N-methylpiperidine, N,
Alicyclic tertiary amines such as N′-dimethylpiperazine,
Examples include aromatic tertiary amines such as benzyldimethylamine, dimethylaminomethylphenol, and 2,4,6-tris (dimethylaminomethyl) phenol.

The ratio of the epoxy resin and amines to be blended with the polysulfide polyether polymer is wide, but generally 5 to 10 parts by weight of the polysulfide polyether polymer are added to 100 parts by weight of the epoxy resin.
0 parts by weight and 2 to 30 parts by weight of amines.

[0040]

The present invention will be described in more detail by the following examples. Synthesis Example 1 1000 g of a bifunctional polypropylene glycol (OH number 162) obtained by adding propylene oxide to propylene glycol, 278.3 g of epichlorohydrin, and 2.0 g of stannic chloride pentahydrate. Was charged into a 2-liter reaction vessel and stirred at 100 ° C. for 3 hours. Further, 240.7 g of sodium hydrosulfide (purity 70%) was added, and the mixture was stirred at 100 ° C. for 1.5 hours. Then, the salt was removed to obtain a pale yellow transparent liquid polymer. The obtained polymer had a sulfur content of 6.0% by weight and a thiol group content of 4.3.
% By weight. When the obtained polymer was analyzed by ¹³ C-NMR, it was confirmed that a disulfide bond was present.

Synthesis Example 2 Trifunctional polypropylene glycol (OH value 394) obtained by adding propylene oxide to glycerin 1
000g and 715.9g epichlorohydrin,
2.0 g of stannic chloride pentahydrate was charged into a 2-liter reaction vessel and stirred at 100 ° C. for 3 hours. In addition, 61
Add 9.1 g of sodium hydrosulfide (purity 70%) and add 100
Stirred at 1.5 ° C for 1.5 hours. Then, the salt was removed to obtain a pale yellow transparent liquid casting polymer. The obtained polymer had a sulfur content of 12.0% by weight and a thiol group content of 9.6% by weight. When the obtained polymer was analyzed by ¹³ C-NMR, it was confirmed that a disulfide bond was present.

Examples 1 to 5 300 g of the polymer obtained in Synthesis Example 1 and 300 g of polysulfide polymer (trade name "Thiocol LP55" manufactured by Toray Thiokol Co., Ltd.) were placed in a 1-liter reaction vessel and stirred at room temperature. Then, various acids shown in Table 1 were added (the addition amount is shown in Table 1), and the mixture was stirred for 15 minutes.

The thiol group content of the obtained polymer was 3.
It was 2% by weight and had a viscosity of 50 poise (25 ° C.) and was transparent and brown. When this polymer was analyzed by gel permeation chromatography, the amount of components having a number average molecular weight of 500 or less was 7% by weight or less. Polymer 20 obtained
3.5 g of a curing agent was added to g in a proportion shown in Table 2, poured into a mold having a thickness of 2 mm, and cured at 20 ° C. for 20 hours to obtain a sheet-shaped cured product.

About this sheet-shaped cured product,
According to the standard of D638-84 TYPE IV, a tensile test (pulling speed 500 mm / min) was performed and 10
The 0% modulus, breaking strength and elongation were measured. Also,
The A hardness was also measured according to JIS K6301. The results are also shown in Table 1. Further, various plasticizers were mixed with each of the obtained polymers so that the weight ratio of polymer / plasticizer was 10/5, and compatibility was examined. Table 3 shows the results.

Comparative Example 1 The polymer obtained in Synthesis Example 1 and a polysulfide polymer (manufactured by Toray Thiokol Ltd., trade name “Thiocol L”)
P55 ″) was mixed at room temperature with a weight ratio of 1/1 for 15 minutes to obtain a polymer. This was analyzed by gel permeation chromatography in the same manner as in Examples 1 to 5, and the polymer had a number average molecular weight of 500. The following ingredients are 35.0% by weight
Met. Further, a sheet-like cured product was prepared in the same manner as in Example 1, and 100% modulus, breaking strength, elongation and A hardness were measured. The results are also shown in Table 1.

Comparative Example 2 The polymer obtained in Synthesis Example 1 and a polysulfide polymer (manufactured by Toray Thiokol Co., Ltd., trade name “Thiocol L”)
P55 ″) was mixed at 90 ° C. in a weight ratio of 1/1 for 15 minutes to obtain a polymer. When the polymer was analyzed by gel permeation chromatography in the same manner as in Examples 1 to 5, the number average molecular weight was The content of components of 500 or less was 35.0% by weight, and a sheet-like cured product was prepared in the same manner as in Example 1, and 100% modulus, breaking strength, elongation and A hardness were measured. It is shown together with 1.

Example 6 Bifunctional polypropylene glycol obtained by adding polypropylene oxide to propylene glycol (O
1000 g of H value 162), 278.3 g of epichlorohydrin and 2.0 g of stannic chloride pentahydrate were charged into a 3 liter reaction vessel and stirred at 100 ° C. for 3 hours. Further, 1280 g of polysulfide polymer (trade name “Thiocol LP55” manufactured by Toray Thiokol Co., Ltd.),
240.7 g of sodium hydrosulfide (purity 70%) was added and stirred for 2 hours. To this was added 5.12 g of a 50% aqueous solution of citric acid, the mixture was stirred for 15 minutes, and then dehydrated under reduced pressure. Further, salts were removed to obtain a pale yellow transparent polymer. The obtained polymer had a thiol group content of 3.2% by weight and a viscosity of 50 poise (25 ° C.). When this polymer was analyzed by gel permeation chromatography, the content of components having a number average molecular weight of 500 or less was 10% by weight or less.
A sheet-shaped cured product was prepared in the same manner as in Example 1, and 10
The 0% modulus, breaking strength, elongation and A hardness were measured. The results are also shown in Table 1. Further, various plasticizers were added to the obtained polymer in the same manner as in Examples 1 to 5.
The plasticizers were mixed so that the weight ratio was 10/5, and compatibility was examined. The results are also shown in Table 3.

Comparative Example 3 Bifunctional polypropylene glycol obtained by adding polypropylene oxide to propylene glycol (O
1000 g of H value 162), 278.3 g of epichlorohydrin and 2.0 g of stannic chloride pentahydrate were charged into a 2 liter reaction vessel and stirred at 100 ° C. for 3 hours. Furthermore, 1280 g of polysulfide polymer (Toray Thiokol Co., Ltd., trade name "Thiocol LP55")
Then, 240.7 g of sodium hydrosulfide (purity 70%) was added and stirred for 2 hours. Then, the salt was removed and the mixture was stirred for 15 minutes to obtain a pale yellow transparent polymer. The thiol group content of the obtained polymer was 3.5% by weight, and the viscosity was 50 poise (25 ° C.). When this polymer was analyzed by gel permeation chromatography, the content of components having a number average molecular weight of 500 or less was 35% by weight. Example 1
A sheet-like cured product was prepared in the same manner as in 1. and 100% modulus, breaking strength, elongation and A hardness were measured. The results are also shown in Table 1.

Example 7 Bifunctional polypropylene glycol obtained by adding polypropylene oxide to propylene glycol (O
H value 56) of 1000 g, 114 g of epichlorohydrin and 1.3 g of stannic chloride pentahydrate were charged into a 3 liter reaction vessel and stirred at 100 ° C. for 3 hours. 9 more
95 g of 11 g of polysulfide polymer (trade name "Thiocol LP55" manufactured by Toray Thiokol Co., Ltd.)
Sodium hydrosulfide (purity 70%) was added and stirred for 3 hours.
Thereafter, 4.1 g of a 50% aqueous solution of citric acid was added, the mixture was stirred for 15 minutes, and then dehydrated under reduced pressure. Further, salts were removed to obtain a pale yellow transparent liquid polymer. The polymer obtained had a thiol group content of 2.2% by weight and a viscosity of 82 poise (25
℃). When this polymer was analyzed by gel permeation chromatography, the component having a number average molecular weight of 500 or less was 7.5% by weight. Example 1
The same method as described above (20 g of this polymer was used as the curing agent 2.
4 g) was used to prepare a sheet-shaped cured product, and 100% modulus, breaking strength, elongation and A hardness were measured. The results are shown in Table 1.
Are shown together with. In addition to the polymer obtained, Example 1
As in the case of No. 5, various plasticizers were mixed so that the weight ratio of polymer / plasticizer was 10/5, and compatibility was examined. The results are also shown in Table 3.

Example 8 Bifunctional polypropylene glycol obtained by adding polypropylene oxide to propylene glycol (O
H-value 56) 1000 g, 111 g epichlorohydrin and 1.7 g stannic chloride pentahydrate were charged into a 3 liter reaction vessel and stirred at 100 ° C. for 3 hours. 2 more
73 g of polysulfide polymer (trade name “Thiocol LP55” manufactured by Toray Thiokol Co., Ltd.) and 8.9
g of sodium hydrosulfide (purity 70%) and 31.6 g of sodium sulfide (purity 31%) were added and stirred for 3 hours. Thereafter, 6.0 g of a 50% aqueous citric acid solution was added, and the mixture was stirred for 15 minutes and then dehydrated under reduced pressure to remove salts to obtain a pale yellow transparent liquid polymer. The thiol group content of the obtained polymer was 1.
It was 5% by weight and the viscosity was 130 poise (25 ° C.). When this polymer was analyzed by gel permeation chromatography, the component having a number average molecular weight of 500 or less was 7.5% by weight. A sheet-like cured product was prepared in the same manner as in Example 1 (curing agent 1.7 g for 20 g of this polymer), and 100% modulus, breaking strength, elongation and A hardness were measured. The results are also shown in Table 1. Further, various plasticizers were mixed with the obtained polymer in the same manner as in Examples 1 to 5 so that the polymer / plasticizer weight ratio was 10/5, and the compatibility was examined. The results are also shown in Table 3.

Comparative Example 4 A polysulfide polymer (“Thiocol LP55” manufactured by Toray Thiokol Ltd.) and various plasticizers were used in a weight ratio of 10.
Mixed at / 5. The compatibility is shown in Table 3.

[0052]

[0053]

[0054]

[0055]

Example 9 The polymer of Example 4 was blended with a plasticizer and a filler in the proportions shown in Table 4 to obtain a main agent. On the other hand, PbO ₂ (oxidizer),
A plasticizer and a vulcanization aid were blended in a ratio shown in Table 5 to obtain a curing agent. The base resin and the curing agent are mixed and poured into a mold having a thickness of 5 mm to prepare a sheet-shaped cured product, which is cured at 20 ° C. for 7 days, and then a coating containing vinyl chloride resin as a main component (Kansai Paint Co., Ltd.) Manufactured by "Vinybon") and a paint mainly composed of polyacrylic acid ester ("Vinii Deluxe" manufactured by Kansai Paint Co., Ltd., "Hedyne" manufactured by Daido Paint Co., Ltd.), and after 14 days at 20 ° C. The state of each coating film was observed. The results are shown in Table 6.

Example 10 A cured product was prepared in the same manner as in Example 7 except that the polymer of Example 6 was used, and the same coating material as described above was applied, and the state of each coating film was observed. The results are shown in Table 6.

Comparative Example 5 A polysulfide polymer (“Thiocol LP55” manufactured by Toray Thiokol Co., Ltd.) was used as a main polymer,
Using butylbenzyl phthalate (plasticizer) as a curing agent and 7.5 parts by weight of an oxidizing agent (PbO ₂ ), these main components and the curing agent were mixed and poured into a mold having a thickness of 5 mm to obtain a sheet-shaped cured product. . The state of the coating film was observed with the same paint using this sheet-shaped cured product. The results are shown in Table 6.

[0059]

[0060]

[0061]

Example 11, Comparative Examples 6 and 7 600 g of the polymer obtained in Synthesis Example 2 and 200 g of polysulfide polymer (trade name “Thiocol LP3” manufactured by Toray Thiokol Co., Ltd.) were charged into a 1-liter reaction vessel. , Stirred at room temperature, 50% aqueous citric acid 0.16
When g was added and the mixture was stirred for 15 minutes, a brown transparent polymer having a thiol group content of 8.2% by weight and a viscosity of 125 poise (25 ° C.) was obtained. When the obtained polymer was analyzed by gel permeation chromatography, the content of components having a number average molecular weight of 500 or less was 9.4% by weight.

Further, 80 g of the obtained polymer was mixed with a bisphenol A type epoxy resin (Asahi Denka Kogyo Co., Ltd.).
Made, trade name "EP-4100") 100g, 2, 4,
6-tris (dimethylaminomethyl) phenol 10g
And are mixed and cold rolled steel plate (1.6 mm x 25 mm x 1
00 mm), and the mixture was aged at 20 ° C. for 14 days, and after being aged at 20 ° C. for 7 days, water immersion (20
Tensile-shear adhesive strength was measured about what was aged for 7 days. The formulation was also mixed on a 20 g scale and the cure rate at 20 ° C. was measured. At this time, the time when the fluidity disappeared was recorded as the gel time, and the time when the tack disappeared was recorded as the tack free time as a standard for curing. The results are shown in Table 7.

A comparative example 6 in which a polysulfide polymer (trade name "Thiocol LP3" manufactured by Toray Thiokol Co., Ltd.) was used in place of the polymer of Example 11 was used, and a commercially available thiol group-containing polyether polymer (oil Product name "Cup Cure 3-8"
00LC ″) was used as Comparative Example 7, and the tensile shear adhesive strength and the curing rate were measured with the same formulation. The results are also shown in Table 7.

[0065]

[0066]

INDUSTRIAL APPLICABILITY As described above in detail, in the method for producing a polysulfide polyether polymer of the present invention, the temperature is lower and the temperature is shorter than the conventional case where the polysulfide polymer and the thiol group-containing polyether are heated and mixed. Since the average molecular weight of the polymer can be increased by reacting the low-molecular weight component with time, the synthesis time can be remarkably shortened. Further, in the polysulfide polyether polymer obtained by the production method of the present invention, dioctyl phthalate (DOP) which was not compatible with the conventional polysulfide polymer alone.
Since inexpensive phthalic acid esters such as the above become compatible with each other and the polymer viscosity is low, the amount of the plasticizer used can be reduced.

Further, the storage stability of the polymer is improved,
In addition, when the coating material is applied to the surface of the cured product cured by the oxidizing agent, the softening of the coating film due to the migration of the plasticizer to the coating material surface is reduced. Further, when an epoxy resin and an amine are used in combination, a low temperature curing is fast and a cured product having sufficient water resistant adhesion is provided. Such a polymer composition is suitable for use as a sealing material, a potting agent, an adhesive or the like.

Claims (5)

[Claims] 1. In the main chain of (a), (i)-(R ₁ O) _n — (wherein R ₁ is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 6 to 200). in the polyether moiety _{represented, (ii) -C 2 H 4} OCH 2 OC 2 H 4 -S x -, and _{-CH 2 CH (OH) CH 2} -S x - ( where, x is 1 to 5 of an integer. contains a structural unit represented by), and, at the _{end, (iii) -C 2 H 4} OCH 2 OC 2 H 4 -SH and / or -CH ₂ CH (OH) CH ₂ A polymer composition comprising a polysulfide polyether polymer having a thiol group represented by —SH, and (b) an acid. 2. The method for producing the polymer composition according to claim 1, wherein (c) HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ S _x ) _m C _{2
H 4 OCH 2 OC 2 H 4} SH ( where, x is an integer from 1 to 5, m is an integer of 1 to 50.) And polysulfide polymer represented by, in (d) the main chain, - ( R _{1 O) n} - (where, _{R 1} is an alkylene group having 2 to 4 carbon atoms, n represents a) an integer of _{6~200, CH 2 CH (OH)} CH 2 -S x -. ( here, x has a structural unit represented by is an integer of 1-5.), and, at the _end, a polyether polymer having a thiol group represented by _{-CH 2 CH (OH) CH 2} -SH, ( c) / (d) = (b) Acids are added when the reaction is carried out at a weight ratio of 95/5 to 5/95. 3. The method for producing the polymer composition according to claim 1, wherein (c) HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ S _x ) _m C _{2
H 4 OCH 2 OC 2 H 4} SH ( where, x is an integer from 1 to 5, m is an integer of 1 to 50.) And polysulfide polymer represented by the main chain (e) - _{(R 1} O) _n- (however, R ₁ has 2 carbon atoms)
~ 4 alkylene group, n represents an integer of 6 to 200. )
And a halogen-terminated prepolymer obtained by reacting a polyol having two or more hydroxyl groups with epihalohydrin, and (f) MSH and / or M ₂
S _x (M is an alkali metal atom, x represents an integer of 1 to 5) in a weight ratio of (c) / (e) = 95/5 to 5/95, and (c) + (e ) In the case of reacting (f) 1 to 50 parts by weight with respect to 100 parts by weight, (b) an acid is added. 4. A curable composition comprising (g) the polymer composition according to claim 1 and (h) an oxidizing agent. 5. A composition comprising (g) the polymer composition according to claim 1, (i) an epoxy resin having two or more epoxy groups in the molecule, and (j) an amine. A characteristic curable composition.