JPS59210928A - Polyurethane elastomer - Google Patents

Abstract

PURPOSE:A urethane elastomer having properties indifferent to a temperature difference between a high temperature and a low temperature and excellent aging resistance, comprising a specified hydrogenated liquid polyhydroxybutadiene and a diisocyanate compound. CONSTITUTION:A mixture is prepared from 95-5wt% liquid polyhydroxybutadiene polymer having a 1,2-vinyl bond content >=70%, a number-average MW of 500-10,000, the number of hydroxyl groups per molecule of 1.5-2.1, and 5- 95wt% liquid polyhydroxybutadiene polymer having a content of trans-1,4-bond and/or cis-1,4-bond >=50%, a number-average MW of 500-10,000, and the number of hydroxyl groups per molecule of 1.2-2.5. At least 80% of the double bonds in this mixture are hydrogenated to obtain a hydrogenated liquid polyhydroxybutadiene polymer. The obtained polymer is mixed with a diisocyanate compound at an NCO/OH molar ratio of 0.8-1.2, and the mixture is cured by heating it to 70-110 deg.C for 24-120hr.

Description

[Detailed description of the invention] The present invention relates to polyurethane disstomers.

More specifically, the present invention relates to a polyurethane distomer comprising a hydrogenated product of a liquid polyhydroxybutadiene polymer and a twin cyanate compound.

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

Polyureno/elastomers, on the other hand, suffer from several drawbacks. One is discoloration and deterioration of physical properties due to sunlight and ultraviolet light, and the second is deterioration of physical properties due to heat.

To prevent discoloration and deterioration of physical properties due to sunlight, ultraviolet rays, etc., various attempts have been proposed, including those using various antioxidants and ultraviolet mosquito repellents as weather resistance improvers, etc.
j. This is a method in which an aliphatic or alicyclic incyanate having excellent weather resistance is used as the phase incyanate. On the other hand, no particularly effective method for reducing physical properties due to heat has been found so far. Also, polyptadiene/based 4Al
Although some research has been conducted on polyurethane elastomers using polyurethane, the above-mentioned problems still remain.

The present inventors have studied to solve these problems, and found that the double bond of a liquid polyhydroquine butadiene polymer having at least 70 1,2-vinyl bonds in the corpse is 80q6.
An application was filed for a method using the hydrogenated liquid polyhydroxybutadiene electrolyte (Japanese Patent Application No. 53-22013).
2) was achieved.

However, the polyurethane elastomer containing this hydrogenated 1,2-vinyl bond/fusorihydroxypucdiene polymer as a component has extremely excellent maximum elongation at the sieve, 1 impact resistance, and heat aging resistance. However, the drawback was that their properties at low temperatures deteriorated.

As a result of repeated efforts by the present inventors to overcome the above-mentioned points of interest, the inventors of the present invention have found that: By using Mizuhime Kamono in combination, it eliminates the difference in property values due to thermal redness at low and high temperatures, and has properties such as extremely stable elongation, impact resistance, and severe heat shock resistance. The present invention was completed by discovering that a polyurethane distomer can be obtained.

That is, the present invention comprises (A) a liquid polyhydroxybutatsuene polymer having 70% or more of L2-vinyl bonds (a) and a liquid polyhydroxybutanoene polymer having 50% or more of 1,4-bonds (b) 03) A polyurethane elastomer characterized by comprising as a main component a liquid polyhydroxybutanoene mixture in which 80 or more double bonds are hydrogenated, and 03) a diincyanate compound.

Next, the present invention will be explained in detail.

The liquid polyhydroxybutadiene polymer component (a) used in the present invention is a polymer containing 70% or more of 1,2-vinyl bonds, and has a number average molecular weight of 500 to 10,000 and a molecular weight of 1 molecule. The average number of xyl bases is 1.
It is a liquid polyhydroxygetadiene complex containing 5 to 2.1 molecules.

In addition, the liquid polyhydroxybutadiene polymer (b) component refers to trans-1,4-bonds and/or cis-1,4-bonds.
The number average molecular weight with 50% or more of bonds is 500 to 10.
(With JOO, the average number of dihydroxyl groups per molecule is 1.2~
It is a liquid polyhydroseptanoene composite having 2.511 d. In the liquid polyhydroxybutadiene polymer described in (a) above, the butadiene polymer need not be a homopolymer; for example, a copolymer with styrene, acrylonitrile, etc. can also be used.

(a) As a specific example of a liquid parihydroxyl compound containing 70 or more 1,2-vinyl bonds,
For example, the product name manufactured by Nippon Soda ■, N15so -PBG-
1,OOQ, G-2,UOO,G-3,000
(As a specific example of a liquid polyhydroxy polymer having 50% or more of 1,4-bonds in the rono component,
For example, PQLY B manufactured by AROO Chemica1 in the United States.
Examples include LIR-45a'r, FC-4,5M, and the like.

The liquid polyhydroxybutadiene polymer in which 8U% or more of the double bonds contained in the mixture of the above @) component and <'-) component of (A) used in the present invention are hydrogenated and the (A) component and ( B) It can be obtained by a known method of adding hydrogen to a polymer prepared by mixing the components in a predetermined ratio using a catalyst such as Raney nickel, palladium, or platinum.

In the present invention, the blending ratio of component (a) and component (b) is 95 to 5 layers of component (a) and 5 to 9 of component (b).
Preferably, the amount of component (a) is from (9) to 70% by weight, and the amount of component (b) is from 70 to 30% by weight. In addition, if a hydrogen atom with a hydrogen addition ratio of less than 80% is used, many double bonds remain in the resulting Nidistomer, resulting in a Nidistomer having sufficient elongation, impact resistance, and heat aging resistance. In addition, if the blending ratio of (in component and (b) component is outside the range of (in component 95 to 5% by weight) and (rono component 5 to 95% by weight), it is possible to obtain Stable elongation over time, 1
1ii'j It is not possible to obtain anti-shock properties, heat shock resistance, etc.

Note that it is generally recommended to mix and hydrogenate component (A), the hydrogenated liquid polyhydroxyptanoene aggregate, from the viewpoint of reaction and workability. Although preferred, it may be used in advance by combining component (A) with component (B).

The diincyanate compounds used in the present invention include conventional aromatic, aliphatic, and alicyclic diincyanate compounds, such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate. , lysine diisocyanate, inphorone diisocyanate, etc. Among these, aliphatic ones such as hexamethylene diisocyanate and lysine diisocyanate, or alicyclic ones such as inphorone diisocyanate are preferred. Diincyanate compounds are used alone or in combination with other isocyanate compounds.

In order to produce the polyurethane elastomer of the present invention, a twin cyanate compound is mixed with the hydrogenated liquid polyhydroxybutadiene polymer, degassed under reduced pressure, and the mixture is poured into a mold at 70°C or more. 110"0124~12
A cured polyurethane elastomer is obtained by heating for 0 hours. The mixing ratio of the hydrogenated product of the liquid polyhydroxybutylene polymer and the diincyanate compound is variously selected depending on the physical properties of the intended elastomer.

The 10H molar ratio is preferably in the range of 0.8 to 1.2. Catalysts are also used to shorten curing time. The catalyst mentioned here is a known catalyst that is generally used as a urethane catalyst, such as di-n-butyltin dilaurate and stannath octoate. It is used in an amount of 01 to 5% by weight.

Furthermore, various additives such as pigments, organic fillers, or inorganic fillers may be added, if necessary.

The urethane nidistomer obtained by the present invention has stable characteristics even under temperature differences between low and high temperatures, and has excellent aging resistance, so it can be used in sealants, leather, shoe soles, etc.
Widely used in the fields of textiles, building materials, vehicle parts, binders for rocket propulsion, potting materials for core parts, lining materials for chemical tanks, waterproofing agents, and modifiers for rubber, urethane resin, and epoxy resin. Widely available.

Next, reference examples, working examples, and comparisons? The present invention will be described in detail by citing examples, but the present invention is not limited to these examples.

In addition, parts and units in the examples indicate parts by weight and % by weight.

Reference 31 1.2-vinyl bond liquid polyhydroxybutane dipolymer N-PBG-1000 (trade name manufactured by Nippon Kunsai Co., Ltd., 1,2-vinyl bond: 9o, 1.4-
) Lance bond: 10%, number average molecular weight: 1550% 1 hydroxyl group 68.5, iodine value 396) 100 parts, 1
．． 4-) Liquid polyhydroxybutaje heptapolymer POLY BD R-45HT having lance bonds (trade name manufactured by Arco, 60% 1,4-trans bonds, 1,4
- Cis bond 111.2 - Vinyl bond: 20%, - Number average molecular weight: 210°, Hydroxyl value: 44, Iodine value: 39
7) 100 parts of Raney nickel catalyst and 7200 parts of dioxa were placed in a No. 17 autoclave and hydrogenated at a hydrogen pressure of 3Q K9/crl and 130°C for about 7 hours while stirring, and after the reaction was completed, the reaction solution was After cooling to ℃, the catalyst was separated by heating, pressurizing and filtration, and then the solvent was removed by distillation under reduced pressure. Hydroxybutadiene/Electrolyte Hydroxybutadiene (S-1)
Reference Example 2 to be Obtained By controlling the hydrogenation reaction time in Reference Example 1, a liquid polyhydroquine getadiene polymer hydrogenated product (S-2) with a hydrogenation rate of 81% was obtained.

Reference Example 3 IJISSO-PBG-1 which is a 1,2-vinyl-bonded polyhydroxybutatsuene'j4 combination in Reference Example 1
140 parts of QQQ, 1,4 to trans-linked polyhydroxybuta'): r-7 polymer terol POLY BD
Hydrogenated liquid polyhydroxybutadiene polymer with a hydrogenation rate of 98% (S-3
) was obtained.

Reference Example 4 Nl5SO-PBG-1000, which is a 1,2-vinyl-bonded polyhydroxybutadiene aggregate in Reference Example 1
'1601B, 1,4-trans-linked polyhydroxybutadiene polymer POLY ED R-45HT
The water addition reaction and treatment were carried out in exactly the same manner except that 140 parts of was used to obtain a liquid hydrogenated j5 hydroxybutadiene complex (S-4,) with a water addition rate of 98 g.

Reference Example 5 RIBSO-PJ3G, a 1,2-vinyl-bonded liquid polyhydroquine getadiene polymer used in Silkworm
-1,000,200 parts, 20 parts of Raney nickel catalyst, and 200 parts of dioxane were placed in a 1-liter autoclave and hydrogen pressure was 30 Ky/ct & 130 while stirring.
Hydrogenation was performed at ℃ for about 7 hours, and after the reaction was completed, the reaction solution was heated to 50℃.
After being allowed to cool to ~60°C, the catalyst was separated by heating, pressurizing and filtration, and then the solvent was removed by vacuum distillation to obtain a liquid polyhydroxybutadiene polymer hydrogenated product with a hydrogenation rate of 98%. (IE-5) was obtained.

Reference Examples G-type polyhydroxyptadiene y i combined POLY BD with M 1,4-h lance bond used in Reference Example 1
200 parts of R-45HT, an additional part of Raney nickel catalyst, and 200 parts of dioxane were placed in a 1 ton autoclave and hydrogenated at 130°C under a hydrogen pressure of 3Q Fqz/ctl with stirring for about 7 hours. After the reaction, the reaction solution was heated to 6
After cooling to 0'C, the catalyst was taken out and heated, pressurized and filtered to separate the catalyst, and then the solvent was removed by lying pressure distillation to form a liquid polyhydroxyptadiene/lid combination with a hydrogenation rate of 98%. Hydrogen radical CB-6) was obtained.

Table 1 shows the characteristic values of the liquid poly and droxybutanoene polymer hydrogenated (IJI) products obtained in Reference Examples 1 to 6 above.

Examples 1 to 4 Isophorone diisocyanate and di-n-butyltin dilaurate were added to each of the hydrogenated samples (S-1) to CS-4 shown in Table 1 that were neglected in Reference Examples 1 to 4 in Table 2. The mixture was mixed well and uniformly and degassed under reduced pressure. After step 7, 10X 100X O,3 (on
) and cured at 80° C. for 72 hours to produce each polyurethane disstomer.

Then each polyurethane elastomer 'i3 obtained
The tensile strength and elongation of sample CAI were punched out using a No. 1 dumbbell and kept at 135℃ for 15 days.
Sample [B] heated for 5 days also under standard condition (℃)
Measurements were taken at , and custom tests and aging resistance tests using temperature changes were conducted. The results are shown in Tables 3 and 4.

Examples A mixture (1:
1 heavy f-) to isophorone diisocyanate, di=
A polyurethane elastomer was produced in the same manner as in Examples 1 to 4 by blending n-pteletinnolaurate with the composition shown in Table 2. Then, in the same manner as in Examples 1 to 4, the polyurethane elastomer was subjected to temperature change. Characteristic tests and aging resistance tests were conducted and the results are shown in Table 35 and Table 4.

Comparative Example 1 and Comparative Example 2 Hydrogen 7J shown in Table 1 obtained in Reference Example 5 and Reference Example 6
゛≦Inholo 7 soisocyanate and non-n-glytin dilaurate were added to the additives Tani bar materials (S-5,) and (S-6) in the fJi body shown in Table 2, and Examples 1 to 5 were obtained. Each polyurethane distomer was produced in a similar manner. Next, a characteristic test by temperature change and an aging resistance test were conducted in the same manner as in Examples 1 to 5, and the results are shown in Tables 3 and 4.
It was shown to.

As is clear from Tables 3 and 4, the elastomer obtained according to the present invention exhibits better characteristics than the comparative example, even with respect to the temperature difference between low and high temperatures, and is also lagging behind in heat aging resistance. ing.

In particular, having these properties means that the polyurethane distomer is resistant to change due to differences in temperature, has excellent stability, and can be used for a long period of time.

Procedural amendment February d, 1983 Patent Katanaga Kazuo Wakasugi, Indication of the case, 1984 Patent Application No. 84694 2, Name of the invention Polyurethane elastomer 3. Person making the amendment Relationship to the case Patent Applicant address: 2-2-1 Otemachi, Chiyoda-ku, Tokyo 100 (430
) Nippon Soda Co., Ltd. Representative Takeo Sannomiya 4 Agent Address: 1-2 Otemachi 2-chome, Chiyoda-ku, Tokyo 100 Nihon Kyokudatsu Co., Ltd. Tel: (245) 6234 (6286) Haruyuki Ito, 1- Same address (7125) Yoshimi Yokoyama 5. Specification to be amended @ Column 5 of Detailed explanation of the Kusunoki invention in the claims, Contents of the amendment (1) The entire scope of the claims in the specification shall be amended and corrected as per the appendix.

1) For the first method on page 3, line 8 of the specification, insert "invented and separately patented" in its entirety after J.

2) “1,4 combination” in the third line from the bottom of the third page, all 1-1
．． 4-Correction to “Conjunction”.

3) “Using water additives in combination” on the second line from the bottom of page 3
is corrected to "by hydrogenating the mixture."

4) On the 4th page, line 8 from the bottom, "1 compound" is corrected to "compound."

5) In the third line of page 6, "to a single coalescence" is corrected to "polymer".

6) In the 5th line of page 6, "by a method" is corrected to "by a hydrogenation method".

7) Delete "'used something" on page 6, line 11.

8) Correct ``1-'' in the first line of page 7 to ``1-(b).''0 9) Correct ``1)'' in the third line of page 7 to ``Shukuguchi).'' .

10) Correct "propellant" in the first line of page 9 to "l".

11) 7th line from the bottom of the 11th negative l-1000,200
Corrected to ``200 copies,'' of course.

1z page 12, line 5, 1200 copies.'' 1200 copies.
Department,” is corrected.

1, (5) A mixture of a liquid polyhydroxybutadiene polymer (a) having 70 or more 1,2-vinyl bonds and a liquid polyhydroxybutadiene compatible material (b) having 50% or more 1,4-bonds. A polyurethane elastomer whose main components are a liquid polyhydroxybutadiene vehicle combination in which the double bonds contained therein are hydrogenated to 80φ or more, and a [F]) diincyanate compound=02 The above ① component and ( The polyurethane disstomer according to the scope of Patent No. 511, item 1, wherein the blending ratio with component (a) is 95 to 51% by weight and (b) is 5 to 95% by weight.

Claims (1)

[Scope of Claims] 1. (A) A liquid polyhydroxybutanoene polymer (A) having 704 or more 1.2-vinyl bonds, and 1.4
- Two sets of bonds contained in the mixture with liquid polyhydroxybutadiene melon aggregate (b) having 50q6 or more bonds are 8
A polyurethane elastomer 2 characterized in that the main component is a quasi-shaped polyhydroxybutadiene 7 subunit with 0% or more hydrogenated 7J [+] and (B) a diisocyanate compound, the above (a) component and (b) component The polyurethane entomer according to claim 1, wherein (a) is 95 to 5% and (2) is 5 to 95% in the blending ratio.