JPH03134058A - Polymer composition - Google Patents

Abstract

PURPOSE:To improve the compatibility of a liquid polysulfide polymer with a plastisizer and to make it possible to lower the amount of use by blending the polysulfide polymer with a thiol-group-containing polyeter polymer which has disulfide linkages in the main chain. CONSTITUTION:The title composition comprises a polysulfide polymer (a) and a tiol group-containing polyether polymer (b) wherein -(R1 O)n-(wherein R1 is a 2-4C alkylene group; and n is an integer of 6-200) and disulfide linkages are present in the main chain, a thiol group is present at the end and the ratio of the sulfur content to the mercaptane content in the polymer is 1.06 or more with the weight ratio of a to b of 95/5-5/95. When an oxidizing agent (e.g. preferably PbO2) is further mixed with the composition, the composition is easily cured at ordinary temperatures. The obtained composition is suitable for a sealing material, an adhesive, etc. When the composition of the components (a) and (b) is mixed with an epoxy resin having 2 or more epoxy groups in the molecule and an amine, a cured product which is cured rapidly at low temperature and has enough water-resistant adhesion can be obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polymer composition, and in particular provides a sealing material that has good compatibility with a plasticizer and can be formulated with a small amount of plasticizer. The present invention also relates to a polymer composition that can be used as a curing agent for epoxy resins and can provide a cured product with a fast curing speed and good durability.

[Conventional technology]

Polymers containing two or more thiol groups in one molecule are easily cured when mixed with an oxidizing agent, and thiol groups easily react with epoxy groups, isocyanate groups, etc. to increase the molecular weight, so they are useful for sealing. Widely used in materials, paints, adhesives, etc.

Among these thiol group-containing polymers, U.S. Pat.
．． The polysulfide polymer described in No. 466,963 has been used as a raw material for sealants for many years because it has excellent oil resistance, chemical resistance, flexibility, etc. Further, the above polysulfide polymer can impart flexibility to the epoxy resin by using it together with an epoxy resin containing two or more epoxy groups in one molecule.

[Problem to be solved by the invention]

Polysulfide polymer has -88-(x=
Although it is a unique polymer containing structures 1 to 5), only a limited number of plasticizers can be used because it is highly polar. That is, since general-purpose, inexpensive plasticizers cannot be used, the cost increases when compounding sealants and the like. Furthermore, since the viscosity is higher than the molecular weight of the polymer, it is necessary to add a large amount of plasticizer to improve the workability of the compound. For this reason, when a paint is applied to a cured product of a polysulfide polymer sealant, there is a problem in that the plasticizer oozes out and softens the paint film.

Furthermore, when used with an epoxy resin, the adhesive strength and water-resistant adhesiveness are good, but there is a problem that curing is slow at low temperatures.

On the other hand, the thiol group-containing polyether polymer described in Japanese Patent Publication No. 47-48279 has a problem of poor water-resistant adhesion, although it has fast curing properties at low temperatures.

Therefore, an object of the present invention is to improve the compatibility between a liquid polysulfide polymer and a plasticizer, and to reduce the amount used, thereby creating a polymer composition that does not soften the paint film even when applied to a cured product. It is about providing something.

Another object of the present invention is to have flexibility, which is an advantage of polysulfides, when used with epoxy resins;
It is an object of the present invention to provide a polymer composition that has sufficient adhesive strength and water resistance, and has a fast curing speed.

[Means to solve the problem]

As a result of intensive research in view of the above objectives, the present inventors discovered that by mixing a thiol group-containing polyether polymer containing disulfide bonds in the main chain with a polysulfide polymer, they were found to be incompatible with the polysulfide polymer alone. The plasticizers become compatible and the viscosity of the polymer after mixing is reduced, so the amount of plasticizer used can be reduced.Furthermore, when a paint is applied to a cured product, the transfer of plasticizer to the paint film is prevented. It has been found that the contamination property is improved.

It has also been found that when used with an epoxy resin, it cures quickly at low temperatures and has sufficient adhesive strength and water resistance. The present invention was conceived based on these discoveries.

That is, the polymer composition of the present invention includes (a) a polysulfide polymer, and (5) -(R,0) in the main chain. -However, R3 has 2 carbon atoms
~4 alkylene group, n represents an integer of 6 to 200. )
and (a)/(b)-9515, a thiol group-containing polyether polymer containing disulfide bonds and having a thiol group at the end, and having a ratio of sulfur content/mercaptan content in the polymer of 1.06 or more. It is characterized by being mixed at a weight ratio of ~5/95.

The present invention will be explained in detail below.

The polysulfide polymer in the composition of the invention is
It is represented by the following general formula [1].

Its (R, S,), R, SH... (1) In the above general formula, X is an integer from 1 to 5, and its average value is 2. m is an integer from 1 to 50.

Also, Lit-CH2CH2-1-C2H,0C211
,-1-C2)I40CII20C21(4-1CJe
l] An organic residue such as C-Ha-.

The polysulfide polymer of the present invention has fluidity at room temperature and has a molecular weight of 100 to 200,000, preferably
400 to 50,000.

Preferred examples of such polysulfide polymers are described in US Pat. No. 2,466,953.

The thiol group-containing polyether polymer 〇) in the present invention has -(R) as a polyether moiety in the main chain.

0), -. Here, R3 represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 6 to 200. The molecular weight of this polyether portion is preferably 400 to 10,000. If the molecular weight is less than 400, the effect of improving compatibility with a plasticizer when mixed with a polysulfide polymer is small, and if it exceeds 10.000, the viscosity of the polymer increases, which is not preferable.

Also, does this thiol group-containing polyether polymer contain disulfide bonds in its main chain? , has a thiol group at the end, and the weight ratio of sulfur content/mercaptan content in the polymer is 1.06 or more. When the ratio of sulfur content/mercaptan content is less than 1.06, the proportion of disulfide bonds is small and the compatibility with the polysulfide polymer is poor.

Preferred examples of such thiol group-containing polyether polymers include those synthesized by the known method described in Japanese Patent Publication No. 47-48279. That is, after adding shrimp halohydrin such as shrimp chlorohydrin and shrimp bromohydrin to a polyalkylene glycol such as polypropylene glycol and polyethylene glycol, it is hydrosulfurized. A polyether polymer having a functional group represented by the following general formula (2) is obtained. The main chain of the polymer thus obtained contains a portion of disulfide bonds, and is suitable as the thiol group-containing polyether polymer of the present invention.

Other known compounds include U.S. Patent No. 3,923;
A mercaptan-terminated liquid polymer having a structure represented by the following general formula (3) described in U.S. Pat. The following general formula (4) described in No. 092.293 and Japanese Patent Publication No. 46-3389
An example is a polymercaptan having a structure represented by the following, in which a portion of the thiol group is similarly oxidized with an oxidizing agent to introduce a disulfide bond.

-(CH2Cl-0), -CH2-C11-C112
-3R・ ・ ・(2) R3 Kano (CDCl2-0) r-CH2CH2CH, -3t(・
・ ・ ・(4) L (However, R3 is hydrogen or a methyl group, and p, q, r are integers of 6 to 200.) The polysulfide polymer (a) of the present invention and the thiol group-containing polyether polymer (b ) is 9515 to 5/95 by weight. If the amount of polysulfide polymer is less than 5% by weight of the whole, the weather resistance of the cured product will be poor. In addition, thiol group-containing polyether polymer
If it is less than % by weight, the effect of improving compatibility with the plasticizer will be small.

In the present invention, by mixing an oxidizing agent into a polymer composition consisting of the above-mentioned polysulfide polymer and thiol group-containing polyether polymer, the composition can be easily cured at room temperature and is suitable for sealing materials, adhesives, etc. be able to.

As the oxidizing agent in the composition of the present invention, substances conventionally used as curing agents for thiol group-containing polymers can be used. Specific examples of these oxidizing agents include Xn0a
, FeL, Pb0z, MgL, Ca0z, BaO3, M
nL, Te0t, Sem2, Pb, Ot, SrL, Li
Inorganic peroxides such as 2O2, ZnO, FeO, PbO, F
eJa, 5b203, MgO1C00, Can, Cu
Inorganic oxides such as O1BaO, Na2CrOa, Kz[:
ro<, Na2Cr2L, Cr, 0. , NaCj
! Oa, NaBO2' H2O2, K2C2O4, KM
nD, , Soda percarbonate (2Na2CO3+ 3820
2) Inorganic oxidizing agents such as benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide,
Examples include organic peroxides such as t-butyl hydroperoxide, t-buty9rubarbenzoate, sodium peracetate, and urea peroxide, and organic oxidizing agents such as nitrobenzene, dinitrobenzene, and paraquinone dioxime. Most widely used. In the composition of the present invention, the blending amount of these oxidizing agents varies depending on the type of oxidizing agent, but for boat fishing, 1 part by weight of the mixture of polysulfide polymer and thiol group-containing polyether polymer is used. Preferably, the amount is 50 parts by weight.

The polymer composition of the present invention further includes the following for the purpose of improving economic efficiency, workability when applying the composition, and physical properties after curing.
Fillers such as calcium carbonate, talc, clay titanium oxide, silica, etc. can be added. In addition, the polymer composition of the present invention also contains dioctyl phthalate (
Since inexpensive phthalate esters such as DOP) and dioctyl phthalate (DHP) are compatible, they can be added.Plasticizers such as chlorinated paraffin and hydrogenated terphenyl can also be added. In addition, since the polymer composition composed of the polysulfide polymer and the thiol group-containing polyether polymer according to the present invention has a lower viscosity than a polysulfide polymer alone, the amount of plasticizer added is 40 parts by weight per 100 parts by weight of the polymer. Sufficient workability can be obtained even if the

Furthermore, by blending an epoxy resin containing two or more epoxy groups in one molecule and an amine into a polymer composition consisting of a polysulfide polymer and a thiol group-containing polyether polymer according to the present invention, it is possible to form a polysulfide polymer alone. It cures faster at low temperatures compared to thiol group-containing polyether polymers, has more flexibility than thiol group-containing polyether polymers, and has sufficient A cured product with excellent water-resistant adhesive properties can be obtained.

The epoxy resin used in the present invention includes bisphenol A1, halogenated bisphenol A1, bisphenol F1, halogenated bisphenol F, polyhydric phenols such as lusorcinol, hydronone, pyrocatechol, 4.4'-dihydroxybiphenyl, and 1.5-hydroxynaphthalene. Epoxy resins obtained by adding shrimp chlorohydrin to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, and fragrances such as oxybenzoic acid and phthalic acid. Examples include epoxy resins obtained by adding shrimp chlorohydrin to group dicarboxylic acids.

The amines used in the present invention are preferably those used as curing accelerators when a thiol group-containing polymer is used as a curing agent in an epoxy resin.

Specifically, N,N-dimethylpropylamine, NIN
IN"Nl ~ aliphatic tertiary amines such as tetramethylhexamethylene diamine, N-methylpiperidine, N,
ring group tertiary amines such as N'-dimethylpiperazine,
Examples include aromatic tertiary amines such as benzyldimethylamine, dimethylaminomethylphenol, and 2.4.6-tris(dimethylaminomethyl)phenol.

[For production]

When mixed with an oxidizing agent, polysulfide polymers are easily cured at room temperature, providing a cured product with oil resistance, chemical resistance, and excellent flexibility. However, due to the high polarity of the polymer, only limited plasticizers can be used. Therefore, the main chain is -(R.

0), , -, contains a disulfide bond, has a thiol group at the end, and has a thiol group-containing polyether polymer in which the weight ratio of sulfur content/mercaptan content in the polymer is 1.06 or more. , polysulfide polymer/thiol group-containing polyether polymer = 9
By mixing the composition in a ratio of 515 to 5/95, the polarity of the polymer is lowered and the viscosity is also lowered.

Therefore, inexpensive phthalate esters such as dioctyl phthalate (DOP) and diheptyl phthalate (DHP), which were not compatible with polysulfide polymer alone, become compatible. Furthermore, since the viscosity of the polymer is lower, less plasticizer can be used.

In addition, by mixing polysulfide polymer and thiol group-containing polyether polymer, when used with epoxy resin and amines, curing is fast at low temperatures.
A cured product having sufficient water-resistant adhesive properties is obtained. this is,
Polysulfide polymer alone has good water-resistant adhesion but low-temperature curing is insufficient, while thiol group-containing polyether polymer alone has fast low-temperature curing but insufficient water-resistant adhesion. However, by mixing two types of polymers having such characteristics, the shortcomings of each are covered, resulting in a composition that has the advantages of both.

〔Example〕

The present invention will be explained in further detail by the following examples.

Synthesis Example 1 1000 g of bifunctional polypropylene glycol (08 valence 162) obtained by adding propylene oxide to propylene glycol, 294.4 g of shrimp chlorohydrin, 2.0 g of stannic chloride trihydrate, and was charged into a 21 reaction vessel and stirred at 110°C for 3 hours. moreover,
Add 254.6g of sodium hydrogen sulfide (purity 70%),
The temperature was raised to 00°C and stirred for 1.5 hours.

Thereafter, the salt was removed to obtain a pale yellow transparent liquid polymer. The resulting polymer had a sulfur content of 7.0% and a mercaptan content of 5.7%.

Synthesis Example 2 A bifunctional polypropylene glycol obtained by adding propylene oxide to propylene glycol (OH value 112>1000 g, 203.5 g of shrimp chlorohydrin, and 2.0 g of stannic chloride pentasaline) 21 was charged into a reaction vessel and stirred at 110°C for 3 hours.Furthermore, 1
Add 76.0g of sodium hydrogen sulfide (purity 70%) and
The temperature was raised to 0°C and stirred for 1.5 hours.

Thereafter, the salt was removed to obtain a pale yellow transparent liquid polymer. The resulting polymer had a sulfur content of 5.0% and a mercaptan content of 3.8%.

Synthesis Example 3 Trifunctional polypropylene glycol (OH value 394) obtained by adding propylene oxide to glycerin
1000 g, 715.9 g of shrimp chlorohydrin, and 2.0 g of stannic chloride pentasaline for 2f! The mixture was charged into a reaction vessel and stirred at 110°C for 3 hours. Furthermore, 619.
1 g of sodium hydrogen sulfide (purity 70%) was added, the temperature was raised to 100°C, and the mixture was stirred for 1.5 hours. Thereafter, the salt was removed to obtain a pale yellow transparent liquid polymer. The resulting polymer had a sulfur content of 12% and a mercaptan content of 9.5%.

Example 1 and Comparative Example 1 The polymer obtained in Synthesis Example 1 and the polysulfide polymer (manufactured by Toshi Thiokol ■, trade name "Thiokol LP55")
) at a weight ratio of 1/l, and the mercaptan content was 3.5.
% and a viscosity of 60 voids (25° C.), a brown transparent polymer was obtained.

100 parts by weight of the obtained polymer and 116 parts by weight of PbO were mixed, poured into a mold with a thickness of 2 mm, and cured at 20° C. for 20 hours to obtain a sheet-like cured product. Regarding this sheet-shaped cured product, ASTM 0638-84TYP[!
Tensile test (pulling speed 500 m) according to the rV standard
m/m1n), the breaking strength was 5.7kg/
ctl, elongation of 500% was obtained. Also, JIS 63
When the A hardness was measured according to 01, a hardness of 20 was obtained.

Further, the obtained polymer and various plasticizers shown in Table 1 were mixed at a weight ratio of 1015 to examine compatibility.

The results are shown in Table 1.

Table 1 also shows the compatibility of a mixture of polysulfide polymer ("Thiokol LP55" manufactured by Toshi Thiokol Co., Ltd.) and a plasticizer at a weight ratio of 1015 as Comparative Example 1.

Example 2 The polymer obtained in Synthesis Example 2 and the polysulfide polymer (manufactured by Toshi Thiokol ■, product name "Thiokol LP55")
) at a weight ratio of 7/3, and the mercaptan content was 2.4.
% and a viscosity of 120 voids (at 25° C.), a brown transparent polymer was obtained. 100 parts by weight of the obtained polymer and Pbozl
1 part by weight and poured into a mold with a thickness of 2 mm.
A cured sheet was obtained by curing at 20° C. for 20 hours. Regarding this sheet-like cured product, ΔSTM D 638-84
When a tensile test (pulling speed 500mm/m1n) was conducted according to the TYP81V standard, the breaking strength was 4.0.
A kg/cl elongation of 400% was obtained. Also, JIS K
When A hardness was measured according to 2SO3, a hardness of 14 was obtained.

Example 3 and Comparative Example 2 A base material was obtained by blending a plasticizer and a filler with the polymer of Example 1 in the proportions shown in Table 2. On the other hand, a curing agent was obtained by blending Pb02 (oxidizing agent), a plasticizer, and a vulcanization aid in the proportions shown in Table 3.

Regarding this formulation, 5 according to JIS A-5758
An extrudability test was conducted at °C. In addition, an aluminum plate was used as the adherend, and after curing at 20℃ for 7 days, it was further heated to 50℃.
After curing for 7 days, tensile adhesion was tested according to JIS A-5758. In addition, as a comparative example 2, the polymer was polysulfide polymer "Thiokol LP 55".
using butylbenzyl phthalate for plasticity,
A similar test was conducted using 7.5 parts by weight of the oxidizing agent (PbO).

Furthermore, the base material and curing agent were mixed and poured into a mold with a thickness of 5 mm to obtain a sheet-like cured product. After curing this sheet-like cured product for 7 days at 20°C, the surface is coated with a paint whose main component is vinyl chloride resin (“Vinibon” manufactured by Kansai Paint) and a paint whose main component is polyacrylic ester (manufactured by Kansai Paint). “Vini Deluxe”, “Hekidyne” made by Daido Paint ■
) was applied and the state of each coating film was observed after 14 days had passed at 20°C.A similar test was also conducted for the main ingredient and curing agent of Comparative Example 2.

The results are shown in Table 4.

Table 2 Table 3 Composition of main agent Composition of hardening agent Table 4 Paint A: Vinybon paint B: Vinydeluxe paint C: Hekidyne Example 4 The polymer obtained in Synthesis Example 1 and the polysulfide polymer (manufactured by Toshi Thiokol ■) Product name “Thiokol LP3”)
When these were mixed at a weight ratio of 3/1, a brown transparent polymer composition with a mercaptan content of 9.0% and a viscosity of 112 poise (25° C.) was obtained.

Example 5 and Comparative Example 3.4 Bisphenol A type epoxy resin (Asahi Denka Kogyo ■
80 weight parts of the polymer composition of Example 4, and 2.4 weight parts of the polymer composition of Example 4, and
．． 6-tris(dimethylaminomethyl)phenol 10
Add the weight part and make a cold rolled steel plate (1.6mm x 25m
The above mixture was sandwiched between 20° C.
After curing for 14 days at , and after curing for 7 days at 20℃,
Furthermore, for those cured in water (20℃) for 7 days,
The tensile shear adhesive strength of each was measured.

This formulation was also mixed on a 20g scale and the curing rate at 20°C was measured. As a measure of curing, the time when fluidity disappeared was recorded as gel time, and the time when tack disappeared was recorded as tack-free time.

On the other hand, Comparative Example 3 was prepared by using only a polysulfide polymer (product name "Thiokol LP3" manufactured by Toshi Thiokol ■) instead of the polymer composition of Example 4. Made of epoxy (Product name: “Cup Cure 3-800LC”)
Comparative Example 4 was prepared using the same composition as in Example 5, and the tensile shear adhesive strength and curing speed were measured.

The results are shown in Table 5.

〔Effect of the invention〕

The polymer composition of the present invention contains dioctyl phthalate (
Inexpensive phthalate esters such as DOP) and dioctyl phthalate (DHP) become compatible, and the viscosity of the polymer is low, so the amount of plasticizer used can be reduced. Furthermore, when a paint is applied to the surface of a cured product cured with an oxidizing agent, there is little softening of the paint film due to migration of the plasticizer. Furthermore, when used together with an epoxy resin and amines, it provides a cured product that cures quickly at low temperatures and has sufficient water-resistant adhesive properties. Such polymer compositions are suitable for use in sealants, botting materials, adhesives, and the like.

Application: Hitoh Rethiokol Co., Ltd.

Claims (3)

[Claims] (1) (a) polysulfide polymer, and (b) -(R_1O)_n- in the main chain (wherein R_1 is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 6 to 200), and It consists of a thiol group-containing polyether polymer that contains disulfide bonds and has a thiol group at the end, and the ratio of sulfur content / mercaptan content in the polymer is 1.06 or more, (a) / (b) = 95 A polymer composition characterized by being mixed at a weight ratio of /5 to 5/95. (2) The polymer composition according to claim 1, wherein the (
A polymer composition comprising: a) a polysulfide polymer; (b) the thiol group-containing polyether polymer; and further an oxidizing agent. (3) The polymer composition according to claim 1, wherein the (
A polymer composition comprising: a) a polysulfide polymer; (b) the thiol group-containing polyether polymer; further, an epoxy resin containing two or more epoxy groups in the molecule; and amines.