JPS59117522A - Polyurethane elastomer - Google Patents

Abstract

PURPOSE:To obtain polyurethane elastomer having improved aging resistance, by using a liquid hydrogenated polyhydroxybutadiene polymer and a diisocyanate compound. CONSTITUTION:A liquid polyhydroxybutadiene polymer having >=70% 1,2-vinyl bond, >=80% hydrogenated double bond in the polymer, and preferably 500- 10,000 number-average molecular weight is blended with a diisocyanate compound (e.g., hexamethylene diisocyanate, etc.), and heated usually using a well- known catalyst at 70-110 deg.C for 24-120hr, to give the desired polyurethane elastomer. USE:A sealant, leather, sole of shoes, cloth, building material, etc.

Description

[Detailed description of the invention] This invention relates to polyurethane elastomers.

More specifically, the present invention relates to a polyurethane elastomer having excellent aging resistance and comprising a hydrogenated liquid polyhydroxybutadiene polymer and a diisocyanate compound.

Polyurethane elastomers generally have excellent physical properties,
It is widely applied in fields such as sealants, leather, shoe soles, textiles, building materials, and vehicle parts.

On the other hand, polyurethane elastomers have several drawbacks. One is discoloration and deterioration of physical properties due to sunlight, ultraviolet rays, etc., and the second is deterioration of physical properties due to heat.

Various attempts have been proposed to deal with discoloration and deterioration of physical properties due to sunlight, ultraviolet rays, etc., such as using various antioxidants and ultraviolet absorbers as weather resistance improvers, and using isocyanates as raw materials with excellent weather resistance. This method uses aliphatic or alicyclic isocyanates. On the other hand, no particularly effective method for reducing physical properties due to heat has been found so far. Some research has also been done on polyurethane elastomers using polybutadiene resins, but the same problems as described above remain.

In view of the above-mentioned current situation, the present inventors have conducted intensive research with the aim of developing a polyurethane elastomer with excellent aging resistance. The present invention was accomplished by discovering that a polyurethane elastomer with excellent aging resistance can be obtained by using a liquid polyhydroxybutadiene polymer in which 80 or more double bonds in the sitadiene polymer are hydrogenated.

That is, the present invention provides at least 7 1,2-vinyl bonds.
A liquid polyhydroxybutadiene polymer having 0% or more, and in which the double bonds in the polymer are hydrogenated by 8 or more, and the main components are a hydrogenated product of the liquid polyhydroxybutadiene polymer and a diisocyanate compound. It is a polyurethane disstomer characterized by:

The hydrogenated liquid polyhydroxybutadiene polymer used in the present invention has an average number of hydroxyl groups per molecule of 1.
This is a liquid polyhydroxybutadiene polymer having 8 to 2.1 double bonds, in which 80 or more double bonds are hydrogenated.

The liquid polyhydroxybutadiene polymer referred to herein is a polymer containing 70% or more of 1,2-vinyl bonds, and a polymer having a number average molecular weight of about 500 to 10,000 is used. Furthermore, the liquid polyhydroxybutadiene polymer does not necessarily have to be a homopolymer; for example, a copolymer with styrene, acrylonitrile, etc. can also be used.

In addition, when a polymer having less than 70 1,2-vinyl bonds is used, the hydrogenated product obtained becomes waxy at room temperature, and the obtained polyurethane elastomer has low elongation without becoming stiff and difficult to handle.

Such a hydrogenated product of a liquid polyhydroxycitadiene polymer can be obtained by a known method of hydrogenating a liquid polyhydroxyptadiene/polymer by adding a Raney nickel catalyst, a parent radium catalyst, or the like.

Specific examples of the hydrogenated liquid polyhydroxybutadiene polymer used in the present invention include, for example, N15so-PBGnyIQQQ and N15s manufactured by Nippon Soda.

-PBG knee 2000, N15so-PBG knee 300
As the hydrogenated product of the above-mentioned liquid polyhydroxyptazoene polymer, one in which 80 or more of the double bonds present in the polymer are hydrogenated is used.

If a hydrogenation rate of less than 80 drops is used, a sufficient effect on aging resistance cannot be obtained.

The diisocyanate compounds used in the present invention include conventional aromatic, aliphatic, and alicyclic diisocyanate compounds, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and lysine. diisocyanate, isophorone) isocyanate, etc., among which aliphatic ones such as hexamethylene diisocyanate and lysine diisocyanate or alicyclic ones such as isophorone diisocyanate are preferred. Diisocyanate compounds are used alone or in combination with other incyanate compounds.

In order to produce the polyurethane elastomer of the present invention, a diisocyanate compound is mixed with a hydrogenated liquid polyhydroxybutadiene polymer, defoamed under reduced pressure, and this mixture is cast into a mold, with a temperature of 70C to 1.10C. °C, 24-12
By heating for 0 hours, a cured polyurethane elastomer is obtained. The hydrogenated product of the liquid polyhydroxybutatsuene polymer and the OI''l/bar molar ratio are preferably in the range of 0.8 to 1.2.Also, a catalyst can be used for the purpose of shortening the curing time.Here, The catalyst mentioned above is a known catalyst that is generally used as a urethane catalyst, such as di-n-butyltin dilaurate, stannath octoate, etc., and the amount used is 0.01 to 5 parts by weight based on the total resin content. Various additives such as pigments and organic or inorganic fillers may be added as necessary.

The urethane elastomer obtained by the present invention has excellent aging resistance, so it can be used in sealants, leather, shoe soles, textiles, etc.
It can be widely used in fields such as building materials, vehicle parts, and binders for rocket propellants.

Next, the present invention will be specifically explained with reference to Reference Examples, Examples, Comparative Examples, and Test Examples, but the present invention is not limited thereto.

Reference Example 1 N15so, a liquid polyhydroxybutadiene polymer
-PBG-2QQQ (Product name manufactured by Nippon Bita, 1.2-
Vinyl bond = 90%, 1.4-) Lance bond: 10%
, number average molecular weight: 2,200, hydroxyl value: 42.5, iodine value: 396), 200 parts of Raney nickel catalyst, and 7,200 parts of dioxa were placed in a 1 ton autoclave and stirred at a hydrogen pressure of 30 KIF/c! , Hydrogenation was carried out at 130°C for about 7 hours, and after the reaction was completed, the reaction solution was heated to 50 to 60 °C.
After cooling to ℃, the catalyst was separated by heating and pressure filtration, and then the solvent was removed by vacuum distillation, resulting in a hydrogenation rate (=I calculated from the measured value of the prime value) of 95.
Liquid polyhydroxybutadiene polymer hydrogenated product [
8-4] was obtained.

In addition, by controlling the reaction time in the same manner, hydrogenated products [El-2), [8-31, and [S-5] with hydrogenation rates of 60%, 80%, and 98% as shown in Table 1 were obtained. Ta.

Furthermore, N15s instead of Nisθo-PBG-2000
o-PBG-1000 (trade name of Nippon Soda, 1,2-vinyl bond: 91.0%, 1.4-trans bond: 9
．． 0%, number average molecular weight: 1400, hydroxyl value: 68.
3, iodine value 398) and N15so-PBG-30
00 (trade name manufactured by Nippon Ichida, 1,2-vinyl bond: 8
9.8, 1.4-) lance bond: 10.2%, number average molecular cap: 3300, hydroxyl value 28.1, iodine value 396) were used in exactly the same manner as shown in Table 1. 98 hydrogenated product [:5-7), CEI-9] was obtained.

Reference Example 2 N15s having a 1,2-vinyl bond used in Reference Example 1
Liquid polyhydroxybutadiene polymer Po1y BD R-45HT having 1.4- ) lance bond instead of o-PBG Q-like polyhydroxybutanoef polymer
(Product name manufactured by Arco, 1.4-) Lance connection = 60
%, 1.4-cyx bond: 20%, 1,2-vinyl bond:
20%, number average molecular weight: 2800, hydroxyl value: 44,
Hydrogenation was performed in the same manner as in Reference Example 1 using iodine value: 397) to obtain the 95-hydrogenated product shown in Table 1 [S-11,
:l was obtained.

9 - Examples 1 to 5 Each sample (S-
3), [8-4), (8, -5), (s-7], (S-
9) was blended with isophorone diisocyanate and di-n-butyl tin laurate in the composition shown in Table 2, and the blended mixture was thoroughly mixed uniformly and degassed under reduced pressure. Cast using the mold α), 8
Comparative Examples 1 to 3 Each sample (S-
2), [S-11] and hydrogenated product (S-11,
(S-10': Each polyurethane elastomer was produced in the same manner as in Examples 1 to 5 by blending isophorone diisocyanate and cy-n-butyltin laurate in the composition shown in Table 2.

Test Example A heat aging test was conducted on each of the polyurethane elastomers obtained in Examples 1 to 5 and Comparative Examples 1 to 4 by the method shown below, and the results are shown in Table 3.

<Test method> Each of the polyurethane elastomers obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was punched out as a test piece using a No. 3 dumbbell.
Samples (A) and 13 in which the test pieces were stored at 20 °C for 15 days
Measure the tensile strength and elongation of each sample heated at 5°C for 15 days, calculate the measured value of (B)/measured value of (A) It was taken as the elongation residual rate. The measurement is JI8K 630
1 under standard conditions.

As is clear from the results in Table 3, it is recognized that the present invention has superior heat aging resistance compared to the comparative example, and this good heat aging resistance indicates that oxidative deterioration is difficult to undergo, that is, for a long period of time. It is a polyurethane elastomer with excellent aging resistance that can be used for.

Patent Applicant: Nippon Soda Co., Ltd. Agent Haruyuki Ito Yoshimi Yokoyama Procedural Amendment February 1980-Japanese Patent Office Commissioner Kazuo Wakasugi 1, Indication of Case Patent Application No. 220132 of 1980 2 , Name of Invention Polyurethane Distomer 3, Relationship with the Amended Person Case Patent Applicant Address: 2-2-1 Otemachi, Chiyoda-ku, Tokyo 100 (430
) Nippon Soda Co., Ltd. Representative Takeo Sannomiya 4, Agent Address: 2-2-1 Otemachi, Chiyoda-ku, Tokyo 100 Nippon Soda Co., Ltd. Tel: (245) 6234 Description: Correct the detailed description of the invention.

1) On page 4, line 12 of the specification, "to a polymer" is corrected to "a polymer."

2) On page 4, line 13, "by method" is corrected to "by hydrogenation method".

3) Correct "propellant" in line 5 from No. 6 to "propellant".

4) On page 7, line 7, change “200 copies” to “2o.”

Department,” is corrected.

5) In the second line from the bottom of page 8, ``In the same manner as in Reference Example 1 using '' is corrected to ``In the same manner as in Reference Example 1 except for using .''

6) On the 10th page, in the 6th line from the bottom, "End" is corrected to "Mi".

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Claims (1)

[Claims] 1. A liquid polyhydroxybutadiene polymer having at least 70% or more of 1,2-vinyl bonds, and in which 80% or more of the double bonds in the polymer are hydrogenated. A polyurethane elastomer whose main components are a hydrogenated compound and a diisocyanate compound.